Electronic structure and effective masses of InN under pressure

I. Gorczyca, J. Plesiewicz, L. Dmowski, T. Suski, N. E. Christensen, A. Svane, C. S. Gallinat, G. Koblmueller,

and J. S. Speck
Citation: Journal of Applied Physics 104, 013704 (2008); doi: 10.1063/1.2953094
View online: http://dx.doi.org/10.1063/1.2953094
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/104/1?ver=pdfcov
Published by the AIP Publishing
Articles you may be interested in
Electronic and structural properties of InAs/InP core/shell nanowires: A first principles study
J. Appl. Phys. 111, 054315 (2012); 10.1063/1.3692440
Effect of edge threading dislocations on the electronic structure of InN
Appl. Phys. Lett. 98, 072103 (2011); 10.1063/1.3553772
Band gap and band parameters of InN and GaN from quasiparticle energy calculations based on exactexchange density-functional theory
Appl. Phys. Lett. 89, 161919 (2006); 10.1063/1.2364469
Density-functional theory band gap of wurtzite InN
J. Appl. Phys. 97, 123708 (2005); 10.1063/1.1939069
Effective electron mass and plasma filter characterization of n-type InGaAs and InAsP
J. Appl. Phys. 92, 3524 (2002); 10.1063/1.1504170

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00

JOURNAL OF APPLIED PHYSICS 104, 013704 2008

Electronic structure and effective masses of InN under pressure

I. Gorczyca,1,a J. Plesiewicz,1 L. Dmowski,1 T. Suski,1 N. E. Christensen,2 A. Svane,2
C. S. Gallinat,3 G. Koblmueller,3 and J. S. Speck3
1

Institute of High Pressure Physics, Polish Academy of Sciences, Warsaw, Poland

Department of Physics and Astronomy, University of Aarhus, DK-8000 Aarhus C, Denmark
3
Materials Department, University of California, Santa Barbara, California 93106-5050, USA
2

Received 22 February 2008; accepted 7 May 2008; published online 8 July 2008
The pressure dependence of the electronic band structure of InN is investigated with emphasis on
the conduction band effective mass and its dependence on free-electron concentration. Transport
measurements are performed under hydrostatic pressure on three n-type samples of InN with
different electron concentrations. The effective mass extracted from the electron mobility is found
to increase with pressure, however with a pressure coefficient, which is lower for the samples with
higher electron concentration. Calculations of the InN band structure are performed within the
density functional theory by means of the linear muffin-tin-orbital method, including an empirical
adjustment to reproduce known band edges at ambient pressure. The calculated variations of the
highest occupied conduction band energy and the electron effective mass with free-electron
concentration are compared to available experimental information. The results show a pronounced
deviation from parabolic behavior of the lowest conduction band, and for k 0 this induces large
differences between the values of the optical and curvature masses. Both the fundamental band gap
and the electron effective mass increase with pressure, but due to the nonparabolic character of the
conduction band, the pressure coefficient of the effective mass decreases with electron
concentration, in agreement with the experimental observation. 2008 American Institute of
Physics. DOI: 10.1063/1.2953094
I. INTRODUCTION

InN and its alloys with GaN and AlN have attracted
substantial attention during the last decade due to their technological applications in the fabrication of optoelectronic devices operating in a wide spectrum of wavelengths from the
red to the ultraviolet. Knowledge of the electronic band
structures of these materials is crucial for improving the laser
characteristics. Early experimental studies of InN suggested
a direct band gap Eg of 2 eV,13 but later experiments
performed on high-quality samples with low free-electron
concentration, mostly grown by molecular beam epitaxy
MBE, revealed that the fundamental gap is much smaller,
in the range 0.71.0 eV, depending on the electron
concentration.48 Recently, optical studies for samples with
very low free-carrier concentrations showed that the gap is in
the range 0.60.7 eV,914 while the analysis of lowtemperature absorption and emission spectroscopy data led
to gap values of Eg = 0.61 eV at 77 K11, 0.69 eV at 02
K,12,13 and 0.62 eV at 90 K.14 The discovery of the low
band gap of InN has extended the range of available direct
band gaps of III-nitrides and their alloys into the nearinfrared part of the spectrum.
Theoretical studies of the III-nitride band structures have
been the subject of many publications. Ab initio calculations
for InN, which used the local density approximation LDA
to the density functional theory, found very low values of the
fundamental energy gap, in the range 0.4 to 0.4 eV.1520
a

Author to whom correspondence should be addressed. Electronic mail:

iza@unipress.waw.pl.

0021-8979/2008/1041/013704/9/$23.00

Empirical or semiempirical calculations of the InN band

structure2124 produced the band features of InN by adjusting
the form factors to available experimental data. The early
band-gap value of Eg 2 eV was used in all empirical calculations up to the year 2000. With the revised experimental
value, it also has become necessary to revise the band structure calculations. Now, the methods which use band-gap adjustments lead to band-gap values around 0.85 eV,25 or 0.8
eV Ref. 26 for wurtzite InN. Many recent calculations employ various schemes that either go beyond the LDA or
modify the LDA potentials. Several authors reported the
band gap of wurtzite InN in the range 0.580.88 eV obtained
by that kind of calculation.2733 Simultaneously, the large
band-gap values found in earlier experiments have been explained as a consequence of high values of electron doping,
which increases the Fermi level appreciably above the conduction band minimum CBM.30,31 On the other hand, there
are some recent experiments34 which suggest that the low
value of the InN band gap could be caused by surface gap
states or resonances due to In precipitates. From these lowtemperature measurements a band-gap value around 1.4 eV
was deduced.
A second very important and still not well-determined
parameter in InN is the electron effective mass m. Early
measurements of the electron effective mass in heavily
doped InN films found a range of values from2 0.11m0 m0 is
the free-electron mass to 0.24m0.35 Infrared ellipsometry
measurements36 on MBE-grown InN layers led to a value of
m = 0.14m0. All other recent experiments agree in finding
that the effective mass of the CBM in InN is in fact significantly smaller,8,3740 but still the experimentally derived val-

104, 013704-1

2008 American Institute of Physics

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00

013704-2

J. Appl. Phys. 104, 013704 2008

Gorczyca et al.

ues of the electron effective mass scatter over a wide range

from39 0.044m0 to37 0.085m0. One reason for this spread
in measured masses could be that the electron effective
mass is also strongly influenced by the free-electron
concentration.8,41
In the present work, further investigations of the dependence of the absorption threshold and the electron effective
mass on free-carrier concentration are undertaken. Both experiment and theory are involved, and special emphasis is
put on the pressure variation of these quantities. The electron
mobility is measured as a function of pressure and electron
concentration in three samples of InN. This leads to determination of the electron effective mass behavior with pressure
and free-carrier concentration. The dispersion of the lowest
conduction band with k -vector is found to be strongly nonparabolic; this implies that the values of the optical effective
mass and the curvature effective mass differ substantially for
k 0. The calculated k dependencies of the conduction band
energy and the optical effective mass are compared with the
experimentally observed8,41 dependence of the optical absorption edge and the electron mass on free-electron concentration, assuming a degenerate Fermi gas behavior of the free
carriers. Data for transport properties such as the mobilities
obtained in the present Hall experiments should be related to
the curvature mass.
The organization of the paper is as follows: The experimental setup and the theoretical methodology are described
in Sec. II, and in Sec. III the electronic band structure and its
dependence on free-electron concentration and pressure are
analyzed. The electron effective mass and its k - and pressure
dependence are discussed in Sec. IV. Finally, Sec. V summarizes the results.
II. METHODOLOGY
A. Experiment

The Hall effect measurements have been performed in

the Van der Pauw configuration, using indium contacts. Pressures up to 1.35 GPa have been applied by a gas compressor
with helium as a pressure-transmitting medium. The electron
concentration, ne, and mobility, , have been measured at
room temperature for a set of three InN samples of 1 m
thickness and characterized by different ne. The samples
have been grown by plasma-assisted MBE by means of a
Varian/EPI 620 chamber with conventional Knudsen cells for
group III sources and an EPI Unibulb radio-frequency
plasma source for the active nitrogen species. Two of the
samples, S1 and S2, with In-face polarity, are grown on Gaface GaN buffer layers and GaN templates deposited on sapphire substrates Lumilog, with a growth temperature of
about 450 C. Details of the epitaxial procedure can be
found in Ref. 42. The third sample S3 with N-face polarity
has been grown at about 550 C on a GaN buffer deposited
on a C-face of 6H SiC substrate.43 The concentrations of
electrons and their mobilities at 300 K in the three samples
are as follows: ne = 0.42 1018 cm3 and = 2170 cm2 / V s
in sample S1, ne = 2.1 1018 cm3 and = 780 cm2 / V s in
sample S2, and ne = 2.4 1018 cm3 and = 680 cm2 / V s in
sample S3.

B. Theory

The electronic band structure of InN is calculated using

the linear muffin-tin-orbital LMTO method44 in a fullpotential version.45 The In 4d semicore states are included as
local orbitals.45 The calculations are performed for the wurtzite structure, in which InN crystallizes at ambient pressure.
The unit cell contains four real atoms and four so-called
empty spheres included for the accuracy of interpolation of
the charge density between the muffin-tin spheres at the sites
of real atoms. Equal atomic-sphere radii for real atoms and
different values for two types of empty spheres are chosen.
Further details of the LDA-LMTO calculations are given
elsewhere.17,4649 To correct for the LDA band-gap error, a
semiempirical correction scheme is applied, described in detail below, leading to values for gaps and effective masses as
well as their pressure coefficients in quantitatively better
agreement with experiment.

1. Band-gap correction LDA+C

It is well-known that the LDA Ref. 50 understimates

the band gaps of semiconductors. In several cases, including
that of InN, the gap errors are k -dependent, which leads to
errors in the derived effective masses; see Ref. 46. Therefore,
a correction procedure is needed which corrects not only the
fundamental gap, but also the dispersion of the lowest conduction band, whereby the effective mass at the -point is
modified. A correction using a scissors operator a rigid
shift of the unoccupied bands is useless, since it does not
change the dispersion of the conduction band and the mass
would still be in error. Therefore, a slightly more advanced
procedure for correcting the band gaps and dispersion has
been used in the present work, introducing at the sites of the
atoms and the empty spheres additional external potentials of
the form46

r0
r
Vr = V0 exp
r
r0

where V0 and r0 are adjustable parameters. At the real

atomic sites V0 is usually chosen to be very large, and the
range parameter, r0, small. In this way the potentials become
sharply peaked at the nuclear positions, and they produce
artificial Darwin shifts, i.e., they push s-states, which have
nonzero density at the nuclei r = 0, upwards in energy. In
compound semiconductors different parameters in Eq. 1 are
chosen at anion and cation sites. The fact that for the relatively open wurtzite structure we need to insert the interstital
empty spheres implies additional flexibility in the adjustment
of the lowest conduction band. By introducing extra potentials also on these sites we can make gap correction not only
at the point, but also at other points in the Brillouin zone
BZ. The potentials are transferable 46,51 in the sense that
they can be determined at ambient conditions by adjusting to
experimental gap values, and then used unchanged while the
volume is varied, i.e., in pressure studies as performed in this
work. Furthermore, they may be determined for different
compounds e.g., GaAs and AlAs and subsequently applied,
with the same parameters, to systems where the two com-

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00

013704-3

J. Appl. Phys. 104, 013704 2008

Gorczyca et al.

TABLE I. Optimized lattice parameters: a, c / a, and u, bulk modulus, B, and

its pressure derivative, B, of wurtzite InN compared with experimental
values.
a

c/a

BGPa

Present theory

3.519

1.6135

0.3795

133

3.9

Experiment

3.544a
3.55b

1.613a
1.61b

125.5c
139d

12.7c

Reference 1.
Reference 56.
c
Reference 57.
d
Reference 58.
b

pounds are combined, for example superlattices and

heterojunctions.52
This ad hoc method for correcting the LDA band-gap
errors was developed in the context of LMTO calculations,
and it was extensively used in LMTO Refs. 17, 46, 47, 49,
51, and 52 or linearized augmented plane wave
calculations.25,26,53 Recently, it has also been applied in a
pseudopotential framework.54 The described procedure is
simple, but it requires knowledge of experimental values of
gaps in the materials considered. For InN we adjusted to the
gaps at the , L, and M points of the BZ, as determined in
recent experiments performed on high-quality samples.
2. Structural parameters

The band structures of wurtzite InN are calculated at

theoretically optimized lattice parameters, found by minimization of the total energy with respect to volume, c / a ratio,
and internal bond-length parameter u. The results are summarized in Table I and Figs. 1 and 2. The optimized equilibrium values of the lattice parameter, a, c / a ratio, and
u-parameter, together with the bulk modulus and its pressure
derivative, are quoted in Table I and compared with available
experimental data. The agreement between theory and experiment is excellent and of the same accuracy as found in
other works.19,26,55 The experimental value of B is significantly larger than found by calculation, both present and
previous.55
The axial ratio, c / a, and the u-parameter for the wurtzite
phase of InN are plotted in Fig. 1 as functions of relative
volume, V / V0, where V0 denotes the experimental equilibrium volume. Figure 2 shows the equation of state a and
the bulk-modulus versus volume relation b.
The calculated c / a ratio is seen to decrease with compression Fig. 1a in agreement with the experimental
behavior.57 The u-parameter increases slightly as the crystal
is compressed. Unfortunately, no experimental determinations of this parameter have been published. It emerges from
Fig. 2 that the structural optimization has a minute effect on
the equation of state and bulk modulus.
InN transforms from the wurtzite to the rocksalt structure at 12.1 GPa according to the experiments in Ref. 57.
Deriving the enthalpies versus pressure for the two phases
from the present calculation, we find the transition pressure
to be 9 GPa, i.e., considerably smaller than the 21.6 GPa
given in Ref. 17. The difference between the two theoretical
values is mainly caused by the fact that the atomic spheres

FIG. 1. Structural parameters, c / a axial ratio and u as functions of the

volume given relative to the experimental equilibrium volume, V0
= 30.704 3 / f . u. Dots and full lines: Calculated by total-energy minimization. Open circle: Experimental value for c / a. The wurtzite InN phase is
only stable for V / V0 larger than 0.91.

approximation44 was used in Ref. 17. The present theoretical

value is close to the 1011.1 GPa calculated by Serrano et
al.59
III. FEATURES OF THE BAND STRUCTURE

In Table II the calculated LDA and LDA+ C band gaps

are compared to the experimental values and other theoretical results. The adjustment exploited the recent experimental
values for the zone center gap being in the range 0.60.7 eV,
914
as well as the results of spectroscopic ellipsometry on
MBE-grown InN films,60 following the assignments made in
Ref. 31. Experimental effective mass values were not specifically included in the adjustment procedure, only gaps.
Some of the gaps depend rather sensitively on the structural parameters, u and c / a; see Table III.
The calculated LDA+ C band structure is shown in Fig.
3. The calculation is scalar relativistic, i.e., all relativistic
effects except spin-orbit coupling are included. Labels of the
irreducible representations agree with Ref. 62. The state at
the valence-band maximum px , py is called 6. Other papers, for example Refs. 63 and 64, refer to this as 5. The
band structure presented here is very similar to that obtained
by ab initio pseudopotential calculations27 with selfinteraction corrections band gap= 0.58 eV and differs from
the earlier InN band structure obtained24 by the empirical
pseudopotential method. In the latter case, the main difference is due to the old, larger band-gap value, 2 eV, to
which the calculations in Ref. 24 were adjusted, but there are
also differences in the shape of the conduction band in other

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00

013704-4

J. Appl. Phys. 104, 013704 2008

Gorczyca et al.

TABLE III. InN derivatives in eV of band gaps, Evc, with respect to u and
c / a calculated at the equilibrium volume.

FIG. 2. Calculated pressure a and bulk modulus b as functions of the

volume. Full lines: Calculated with optimized structural parameters, dashed:
u and c / a fixed to their zero-pressure values. Note that wurtzite InN is
unstable above 12 GPa according to Ref. 57.

parts of the BZ, especially around the M point.65 A characteristic feature of our band structure, also found in Ref. 27
and in the GW G and W are the Greens function and the
screened Coulomb potential, respectively66 calculations,32,61
is that in comparison to the empirical band structure,24 the
CBM at the -point is much lower than the conduction band
edge at other k-points. The second conduction band state at
the -point 3c lies higher about 2.8 eV above the CBM
than in the empirical band structure24 about 1.5 eV above
the CBM, which in fact implies that the position of this state

vc

E vc / u

Evc / c / a

6 1
M4 M1
L1 L1
M3 M3
3 3

5
13
6
0
30

4
4
2
5
4

relative to the valence band maximum is approximately the

same in all the calculations considered.
The energy band structures of InN were calculated for a
few compressed volumes corresponding to hydrostatic pressures up to 10 GPa. The resulting pressure dependence of the
band gap is shown in Fig. 4. The gap is seen to increase
almost linearly with pressure. For comparison, the pressure
dependence of the band gap calculated without optimization
of the structural parameters i.e., using the lattice parameters
determined for V = V0 is also presented. It leads to the same
pressure coefficient but shows a slightly sublinear character.
At zero pressure the pressure coefficient is dEg / dp
= 30 meV/ GPa. This value is a little larger than the value
obtained earlier67 by LDA calculations without band-gap correction 25 meV/GPa, but is in excellent agreement with the
experimental10 value of 30 1 meV/ GPa absorption edge
measurements, and with recent photoluminescence
measurements,68,69 27.5 1 meV/ GPa, in the regime of low
electron concentrations.
One of the consequences of the narrow gap of InN is the
peculiar shape of the lowest conduction band, which deviates
markedly from parabolic dispersion for relatively small
k-values. In n-type material, when donor levels are situated
at high energy compared to the CBM, the extra electrons
constitute a degenerate Fermi gas with the Fermi level somewhere above the CBM, and the absorption edge, Eabs, becomes larger than the fundamental gap BursteinMoss
shift.70,71 This is a particularly strong effect in InN due to its
small effective electron mass.72 Fig. 5 shows the energy, Ec,

TABLE II. InN at zero pressure: Band gaps in eV calculated in LDA and
in LDA with band-gap correction LDA+ C, in comparison with experimental data and other calculations.

vc

6 1
M4 M1
L1 L1
M3 M3
3 3

Theory
LDA LDA+ C
0
4.78
5.00
6.19
8.76

0.60
5.24
6.18
7.99
8.56

Experiment

Other calculations

0.61,a 0.62,b 0.69c

5.35,d 5.38d
6.05d
7.87,d 7.63d

0.58,e 0.75,f 0.72,g 1.04h

5.64,f 5.96,g 6.56h
6.09,f 6.00h
7.94,f7.34,g 7.84h
9.62h

Reference 11.
Reference 14.
c
Referencess. 13 and 12.
d
Reference 60.
e
Pseudopotential calculation with self-interaction correction, Ref. 27.
f
LCAO calculation with correction, Ref. 31.
g
GW OEPx calculations as read from a figure in Ref. 32.
h
Quasiparticle self-consistent GW calculation, Ref. 61.
b

FIG. 3. The calculated band structure LDA+ C of wurtzite InN.

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00

013704-5

J. Appl. Phys. 104, 013704 2008

Gorczyca et al.

TABLE IV. InN electron effective mass parallel, m, and perpendicular, m,

2
m1/3 in units of the
to the c axis, as well as the averaged value m = m
free-electron mass calculated with band-gap correction LDA+ C. Experimental values and results obtained in other calculations are included for
comparison.
Theory

Experiment

0.068

0.070

0.069

Other calculation
b

0.039, 0.05,
0.07c
0.047,a 0.05,b 0.07,c 0.085g
0.044,a 0.05,b
0.07c

0.082,d 0.072,e
0.067,f 0.067h
0.088,d 0.068e
0.071,f 0.079h
0.086,d 0.069,e
0.070,f 0.075h

Reference 39.
Reference 38.
c
Reference 8.
d
Reference 30.
e
Reference 76.
f
Reference 32.
g
Reference 37.
h
Reference 61.
b

FIG. 4. The calculated LDA+ C minimum band gap at vs the theoretical

pressure p with full line and without dashed line relaxation of u and
c / a.

of the lowest conduction band calculated as a function of

electron concentration, ne, assuming the degenerate picture
and determining the connection between Fermi level and
electron concentration from the conduction band density-ofstates by integration. The energy values are given relative to
the valence-band top. The calculated concentration variation
of the lowest conduction band state is compared with
experimental41,72 results for the absorption edge Eabs. Eabs
and the Ec should be similar in the present case due to the
large heavy hole mass of InN see Fig. 3, allowing the dispersion near the valence-band top to be neglected in the
analysis. Figure 5 also shows the conduction band energies
as calculated with a simple parabolic model, where a fixed
value of 0.07m0 was assumed for m, i.e., the value of the
calculated effective mass at the bottom of the conduction
band see Table IV. With increasing energy above the CBM,
the conduction band flattens out compared to the parabolic fit
to the CBM, i.e., the effective mass increases. Therefore, for
n-type InN, the Fermi level of the free carriers will increase

with carrier density at a lower rate than in the parabolic

model. In this way the nonparabolicity of the conduction
band in fact reduces the size of the BursteinMoss shift compared to the parabolic case. The agreement between the
present calculated conduction band dispersion and the optical
measurements of the absorption edge is excellent, and Fig. 5
illustrates the importance of taking into account nonparabolicity effects in order to quantify the dependence of the optical energy gap on free-electron concentration. The present
dependence of Ecne also agrees well with the theoretical
results from Ref. 32, where a similar comparison with the
experimental data is made.
Figure 5 furthermore includes a curve showing the calculated dependence of the optical gap on free-carrier concentration at a higher pressure p = 10 GPa. The absorption
edge increases with pressure, but one notices from the figure
that the increase is largest at small electron concentration,
i.e., the pressure dependence of the optical gap becomes
weaker as the electron concentration increases. This is a consequence of the effective mass being larger at higher pressure. This agrees with experimental results in Refs. 68 and
69.
It should be mentioned that high carrier concentrations
can cause a renormalization of the band gap. The present
calculations do not include such effects, which previously
were examined73 for GaN. In that case no significant changes
in the band structure were found for ne up to 4.4
1020 cm3.
IV. CONDUCTION-BAND MASS VERSUS PRESSURE
AND WAVE VECTOR

FIG. 5. The calculated values of the conduction-band energy Ec vs freecarrier concentration ne. The experimental points represent the values of
the absorption edges, Eabs, as obtained in Refs. 41a and 72b. The dashed
curve was calculated for a compressed crystal p = 10 GPa, whereas the
dotted curve represents a parabolic model p = 0 GPa like the full line.

In the previous section the pronounced nonparabolicity

of the lowest conduction band of InN was discussed. An
effect of the nonparabolic conduction band is that the optical
effective mass differs from the curvature effective mass,74
and one must be careful which mass is relevant in a given
experimental context.
The optical or slope electron effective mass at k-vector
k is given by

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00

013704-6

J. Appl. Phys. 104, 013704 2008

Gorczyca et al.

FIG. 6. The calculated effective optical mass vs electron concentration, ne,

for values of the external pressure. The points are data obtained from experiments. a Reference 8; b Reference 36; c Reference 37; d Reference 38; and e Reference 39.

mk =

2k
,
dEck/dk

and this is the mass determined by experiments based on

plasma edge absorption.75
On the other hand, the effective curvature mass, relevant
for electron transport, is
mk =

2
.
d2Eck/dk2

The two masses have the same value at the CBM, but as the
k-vector is moved away from the zone center, they differ. For
wurtzite compounds with an anisotropic conduction band the
effective mass depends on direction in k-space. We denote
the in-plane mass by m directions M and K in the
Brillouin zone and the mass corresponding to the c axis by
m direction A. The average effective mass is then m
2
= m
m1/3.
In Table IV the electron effective masses at the point
as calculated within the LDA+ C formalism are quoted and
compared to experimental values as well as other theoretical
results. The reported experimental values for the InN electron effective masses show a wide spread, ranging from39
0.044m0 to37 0.085m0. The most reliable values seem to be38
0.05m0 and8 0.07m0, since these authors take into account
the nonparabolicity of the conduction band and the freeelectron concentration in their analysis. The average effective mass calculated in the present work 0.069m0 is in the
reported range, and is also close to the value calculated by
k p theory32 0.070m0. The same value for m 0.069m0
was obtained by empirical pseudopotential calculations,76
but the corresponding values of m and m are oppositely
related m m to what is observed experimentally and by
the present calculation, as well as that of Ref. 32 m m.
The calculated optical effective electron mass as a function of free-electron concentration in n-type InN is shown in
Fig. 6 for two pressure values, p = 0 and p = 10 GPa. The
zero-pressure results are compared to the published experimental results.8,3639 The effective mass increases with electron concentration in a similar way in calculations and in

FIG. 7. The calculated electron curvature masses and optical masses vs a

Electron concentration, ne, and b Wave vector. Heavy full and dashed
curves are calculated along the A and M or M directions, respectively. The thin, dotted curves represent the averaged curvature mass for
a compressed InN crystal, p = 10 GPa, i.e., slightly below the transformation
to the rocksalt phase Ref. 57.

experiments; however, the limiting value at very low electron

concentrations is somewhat higher in theory than found experimentally, as already noted in Table IV. Comparing the
present results with those calculated by Ref. 32, the general
trends are very similar, however with a somewhat stronger
increase of the mass at high carrier concentrations in the
present work. Figure 7a compares the calculated effective
curvature and optical masses as functions of the free-electron
concentration, and Fig. 7b illustrates the variation of the
same masses with wave vector, i.e., the Fermi radius in the
directions specified of the degenerate electron gas in the lowest conduction band. As already discussed, the curvature
mass indeed rises much faster than the optical mass, due to
the flattening of the conduction band.

A. Pressure effects

The effective mass has been studied experimentally by

measurements of electron concentration and mobility as
functions of pressure for the three n-type InN samples described in Sec. II A. We are aware of a possible contribution
of charge transport within accumulation layer as well as an
interface between InN layer and buffer layer. To avoid these

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00

013704-7

J. Appl. Phys. 104, 013704 2008

Gorczyca et al.

FIG. 8. The electron concentration ne as functions of the applied pressure

for three different samples.

effects we have chosen InN samples with a thickness exceeding 1 m where the above-mentioned effects are of minor
importance.77
It is found see Fig. 8 that the electron concentration
remains essentially independent of pressure during these
measurements. This indicates that in none of our samples
have the number of scattering centers and their screening
been significantly modified, when pressure in the range up to
1 GPa is applied. Consequently, provided that electrons are
predominantly scattered by ionized impurities/defects Coulomb potential, their effective mass variation with pressure
may be estimated from the mobility, , assuming 1 / m .
The experimentally estimated electron effective masses relative to zero-pressure values for the three considered samples
are shown in Fig. 9 as functions of pressure. The effective
mass is found to increase fairly linearly with pressure.
The pressure derivative of the electron effective mass,
defined as

= d lnm/dp,

varies in the range from = 0.056 to = 0.034 GPa1 for the

three samples, decreasing with electron concentration.
The calculated high-pressure behavior of the electron effective mass can be seen in Figs. 6 and 7, which include
results calculated at p = 10 GPa. The increase of m with

FIG. 10. Pressure coefficients of the calculated optical and curvature effective masses vs electron concentration. The estimates from experimental
data asterisks should be compared to the calculated curvature mass transport experiments.

electron concentration is found to be weaker at p = 10 GPa

than at ambient pressure. For concentrations higher than
1020 cm3 the optical effective mass is almost independent
of pressure see the curve for p = 10 GPa in Fig. 6. The
calculated pressure derivative of the electron effective mass
is equal to = 0.04 GPa1 at k = 0, but, as is clear from Figs.
6 and 7, decreases with k or ne. The effect is even more
pronounced for the curvature mass, where the pressure coefficient changes sign and becomes negative for concentrations
higher than 1019 cm3 where the p = 10 GPa curve crosses
the p = 0 curve in Fig. 7.
In Fig. 10 the experimentally estimated pressure coefficients of the effective mass are shown in comparison with
the pressure coefficients of the calculated optical and curvature effective masses. Both optical and curvature mass pressure coefficients, opt and curv, decrease with carrier concentration, but curv more significantly and more similar to the
experimental results. This observation is in agreement with
the fact that the experimentally estimated effective mass as
deduced from transport measurements should be evaluated as
the curvature mass.74

V. SUMMARY

FIG. 9. The effective electron masses relative to their zero-pressure values

vs applied pressure as derived from the mobility experiments.

The electronic structure of InN under pressure has been

examined by experiment and theory. The electron mobility
was measured on three n-type InN samples under pressure,
while theory used the full-potential LMTO method with gaps
empirically adjusted to experimental gaps LDA+ C. The
calculated band structures agree well with recent GW results
at zero pressure and reproduce the characteristic features
observed in experiments, i.e., nonparabolicity of the conduction band and pronounced influence of the free-electron concentration on the optical absorption edge. The experiments
and calculations agree in the main effects: i an increase of
the effective mass with pressure; ii an increase of the effective mass with electron concentration; and iii a decrease
of the pressure coefficient of the electron effective mass with
electron concentration k -vector. The effects ii and iii are

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00

013704-8

caused by the nonparabolicity of the conduction band and its

pressure dependence, which are particularly pronounced in
InN.
ACKNOWLEDGMENTS

The work was partially supported by the projects of Polish Ministry of Higher Education and Science Nos. 1P03B
037 29 and 1P03B 021 29. The Danish Centre for Scientific
Computing is thanked for financial support for computing
facilities.
K. Osamura, S. Naka, and Y. Murakami, J. Appl. Phys. 46, 3432 1975.
V. A. Tyagai, A. M. Evstigneev, A. N. Krasiko, A. F. Adreeva, and V. Ya
Malakhov, Sov. Phys. Semicond. 11, 1257 1977.
3
T. L. Tansley and C. P. Foley, J. Appl. Phys. 59, 3241 1986.
4
S. Yamaguchi, M. Kariya, S. Nitta, T. Takeuchi, C. Wetzel, H. Amano, and
I. Akasaki, Appl. Phys. Lett. 76, 876 2000.
5
J. Wu, W. Walukiewicz, K. M. Yu, J. W. Ager, E. E. Haller, H. Lu, W. J.
Schaff, Y. Saito, and Y. Nanishi, Appl. Phys. Lett. 80, 3967 2002.
6
J. Wu, W. Walukiewicz, K. M. Yu, J. W. Ager, E. E. Haller, H. Lu, and W.
J. Schaff, Appl. Phys. Lett. 80, 4741 2002.
7
T. Matsuoka, H. Okamoto, M. Nakao, H. Harima, and E. Kurimoto, Appl.
Phys. Lett. 81, 1246 2002.
8
J. Wu, W. Walukiewicz, W. Shan, K. M. Yu, J. W. Ager, E. E. Haller, H.
Lu, and W. J. Schaff, Phys. Rev. B 66, 201403 2002.
9
V. Yu Davydov, A. A. Klochikhin, V. V. Emtsev, S. V. Ivanov, V. V.
Vekshin, F. Bechstedt, J. Furthmller, H. Harima, A. V. Mudryi, A. Hashimoto, A. Yamamoto, J. Aderhold, J. Graul, and E. E. Haller, Phys. Status
Solidi B 229, r1 2002.
10
S. X. Li, J. Wu, E. E. Haller, W. Walukiewicz, W. Shan, H. Lu, and W. J.
Schaff, Appl. Phys. Lett. 83, 4963 2003.
11
O. K. Semchinova, J. Aderhold, and J. Graul, Appl. Phys. Lett. 83, 5440
2003.
12
J. Wu, W. Walukiewicz, W. Shan, K. M. Yu, J. W. Ager, S. X. Li, E. E.
Haller, H. Lu, and W. J. Schaff, J. Appl. Phys. 94, 4457 2003.
13
B. Arnaudov, T. Paskova, P. P. Paskov, B. Magnusson, E. Valcheva, B.
Monemar, H. Lu, W. J. Schaff, H. Amano, and I. Akasaki, Phys. Rev. B
69, 115216 2004.
14
J.-W. Yoon, S. S. Kim, H. Cheong, H.-C. Seo, S.-Y. Kwon, H.-J. Kim, Y.
Shin, E. Yoon, and Y.-S. Park, Semicond. Sci. Technol. 20, 1068 2005.
15
M. H. Tsai, D. W. Jenkins, and J. D. Dow, Phys. Rev. B 38, 1541 1988.
16
Y. N. Xu and W. Y. Ching, Phys. Rev. B 48, 4335 1993.
17
N. E. Christensen and I. Gorczyca, Phys. Rev. B 50, 4397 1994.
18
W. R. L. Lambrecht and B. Segall, in Properties of Group III Nitrides,
edited by J. E. Edgar INSPEC, IEE, London, 1994, p. 154.
19
S.-H. Wei and A. Zunger, Appl. Phys. Lett. 69, 2719 1996.
20
J. A. Majewski, M. Stadele, and P. Vogl, MRS Internet J. Nitride Semicond. Res. 1, 30 1996.
21
S. N. Grinyaev, V. Ya. Malakhov, and V. A. Chaldyshev, Sov. Phys. J. 29,
311 1986.
22
C. P. Foley and T. L. Tansley, Phys. Rev. B 33, 1430 1986.
23
D. W. Jenkins, J.-D. Hong, and J. D. Dow, Superlattices Microstruct. 3,
365 1987.
24
Y. C. Yeo, T. C. Chong, and M. F. Li, J. Appl. Phys. 83, 1429 1998.
25
S.-H. Wei, X. Nie, I. G. Batyrev, and S. B. Zhang, Phys. Rev. B 67,
165209 2003.
26
P. Carrier and S.-H. Wei, J. Appl. Phys. 97, 033707 2005.
27
I. Mahboob, T. D. Veal, L. F. Piper, C. F. McConville, H. Lu, W. J. Schaff,
J. Furthmller, and F. Bechstedt, Phys. Rev. B 69, 201307 2004.
28
L. F. J. Piper, T. D. Veal, P. H. Jefferson, and C. F. McConville, Phys. Rev.
B 72, 245319 2005.
29
F. Bechstedt and J. Furthmller, J. Cryst. Growth 246, 315 2002.
30
D. Bagayoko and L. Franklin, J. Appl. Phys. 97, 123708 2005.
31
H. Jin, G. L. Zhao, and D. Bagayoko, J. Appl. Phys. 101, 033123 2007.
32
P. Rinke, M. Scheffler, A. Qteish, M. Winkelnkemper, D. Bimberg, and J.
Neugebauer, Appl. Phys. Lett. 89, 161919 2006.
33
L. F. J. Piper, L. Colakerol, T. Learmonth, P.-A. Glans, K. E. Smith, F.
Fuchs, J. Furthmller, F. Bechstedt, T.-C. Chen, T. D. Moustakas, and
J.-H. Guo, Phys. Rev. B 76, 245204 2007.
34
T. V. Shubina, S. V. Ivanov, V. N. Jmerik, D. D. Solnyshkov, V. A. Vekshin, and P. S. Kopev, Phys. Rev. Lett. 92, 117407 2004.
1
2

J. Appl. Phys. 104, 013704 2008

Gorczyca et al.
35

T. Inushima, T. Shiraishi, and V. Yu. Davydov, Solid State Commun. 110,

491 1999.
36
A. Kasic, M. Schubert, Y. Nanishi, and G. Wagner, Phys. Rev. B 65,
115206 2002.
37
T. Inushima, M. Higashiwaki, and T. Matsui, Phys. Rev. B 68, 235204
2003.
38
S. P. Fu and Y. F. Chen, Appl. Phys. Lett. 85, 1523 2004.
39
T. Hofmann, T. Chavdarov, V. Darakchieva, H. Lu, W. J. Schaff, and M.
Schubert, Phys. Status Solidi C 3, 1854 2006.
40
B. R. Nag, Phys. Status Solidi B 237, R1 2003.
41
J. Wu and W. Walukiewicz, Superlattices Microstruct. 34, 63 2003.
42
C. S. Gallinat, G. Koblmueller, J. S. Brown, S. Bernardis, J. S. Speck, G.
D. Chern, E. D. Readinger, H. Shen, and M. Wraback, Appl. Phys. Lett.
89, 032109 2006.
43
G. Koblmueller, C. S. Gallinat, S. Bernardis, J. S. Speck, G. D. Chern, E.
D. Readinger, H. Shen, and M. Wraback, Appl. Phys. Lett. 89, 071902
2006; G. Koblmller, C. S. Gallinat, S. Bernardis, J. S. Speck, G. D.
Chern, E. D. Readinger, H. Shen, and M. Wraback, ibid. 34, 63 2003.
44
O. K. Andersen, Phys. Rev. B 12, 3060 1975.
45
M. Methfessel, Phys. Rev. B 38, 1537 1988; M. Methfessel, C. O. Rodriguez, and O. K. Andersen, ibid. 40, 2009 1989; the method was modified by M. van Schilfgaarde private communication andD. L. Novikov
private communication, andN. E. Christensen and D. L. Novikov, Solid
State Commun. 119, 477 2001, and references therein.
46
N. E. Christensen, Phys. Rev. B 30, 5753 1984.
47
M. Cardona, N. E. Christensen, and G. Fasol, Phys. Rev. B 38, 1806
1988.
48
N. E. Christensen and O. B. Christensen, Phys. Rev. B 33, 4739 1986.
49
I. Gorczyca and N. E. Christensen, Solid State Commun. 80, 335 1991.
50
R. O. Jones and O. Gunnarsson, Rev. Mod. Phys. 61, 689 1989, and
references therein.
51
I. Gorczyca, N. E. Christensen, and M. Alouani, Phys. Rev. B 39, 7705
1989.
52
M. Cardona, T. Suemoto, N. E. Christensen, T. Isu, and K. Ploog, Phys.
Rev. B 36, 5906 1987.
53
S.-H. Wei and A. Zunger, Phys. Rev. B 57, 8983 1998.
54
D. Segev, A. Janotti, and C. G. Van de Walle, Phys. Rev. B 75, 035201
2007.
55
C. Stampfl and C. G. Van de Walle, Phys. Rev. B 59, 5521 1999.
56
H. Schulz and K. H. Thiemann, Solid State Commun. 23, 815 1977.
57
M. Ueno, M. Yoshida, A. Onodera, O. Shimomura, and K. Takemura,
Phys. Rev. B 49, 14 1994.
58
A. U. Sheleg and V. A. Savastenko, Inorg. Mater. 15, 1257 1979.
59
J. Serrano, A. Rubio, E. Hernndez, A. Muoz, and A. Mujica, Phys. Rev.
B 62, 16612 2000.
60
R. Goldhahn, A. T. Winzer, V. Cimalla, O. Ambacher, C. Cobet, W. Richter, N. Esser, J. Furthmller, F. Bechstedt, H. Lu, and W. J. Schaff, Superlattices Microstruct. 36, 591 2004.
61
M. van Schilfgaarde, A. Svane, A. N. Chantis, N. E. Christensen, and T.
Kotani unpublished. The quasiparticle self-consistent GW method is described in S. V. Faleev, M. van Schilfgaarde, and T. Kotani, Phys. Rev.
Lett. 93, 126406 2004. For a recent application to spin-splitting in semiconductors, see A. N. Chantis, M. van Schilfgaarde, and T. Kotani, ibid.
96, 086405 2006.
62
K. J. Chang, S. Froyen, and M. L. Cohen, J. Phys. C 16, 3475 1983.
63
L. C. Lew Yan Voon, M. Willatzen, M. Cardona, and N. E. Christensen,
Phys. Rev. B 53, 10703 1996.
64
R. Laskowski and N. E. Christensen, Phys. Rev. B 74, 075203 2006.
65
The transition assignment at the M point to the experimental reflectivity
made in Ref. 22 and repeated in Ref. 24 is incorrect: The 4.95 eV transition assigned to M2M1 in the reflectivity spectrum must in fact be the
transition M4M1, as follows from a comparison of Table II and Fig. 2
band structure in Ref. 22.
66
L. Hedin, Phys. Rev. 139, A796 1965.
67
P. Perlin, I. Gorczyca, T. Suski, P. Wisniewski, S. Lepkowski, N. E. Christensen, A. Svane, M. Hansen, S. P. DenBaars, B. Damilano, N. Grandjean,
and J. Massies, Phys. Rev. B 64, 115319 2001.
68
A. Kamiska, G. Franssen, T. Suski, I. Gorczyca, N. E. Christensen, A.
Svane, A. Suchocki, H. Lu, W. J. Schaff, E. Dimakis, and A. Georgakilas,
Phys. Rev. B 76, 075203 2007.
69
G. Franssen, I. Gorczyca, T. Suski, A. Kamiska, J. Pereiro, E. Muoz, E.
Iliopoulos, A. Georgakilas, S. B. Che, Y. Ishitani, A. Yoshikawa, N. E.
Christensen, and A. Svane, J. Appl. Phys. 103, 033514 2008.
70
E. Burstein, Phys. Rev. 93, 632 1954.

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00

013704-9

T. S. Moss, Proc. Phys. Soc. London B67, 775 1964.

A. G. Bhuiyan, K. Sugita, K. Kasashima, A. Hashimoto, A. Yamamoto,
and V. Yu. Davydov, Appl. Phys. Lett. 83, 4788 2003.
73
M. Corti, A. Gabetta, M. Fanciulli, A. Svane, and N. E. Christensen, Phys.
Rev. B 67, 064416 2003.
74
J. S. Blakemore, J. Appl. Phys. 53, R123 1982.
71
72

J. Appl. Phys. 104, 013704 2008

Gorczyca et al.
75

I. Gorczyca, N. E. Christensen, and A. Svane, Solid State Commun. 136,

439 2005.
76
D. Fritsch, H. Schmidt, and M. Grundmann, Phys. Rev. B 69, 165204
2004.
77
H. Lu, W. J. Schaff, L. F. Eastman, and C. E. Stutz, Appl. Phys. Lett. 82,
1736 2003.

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
14.139.211.74 On: Sat, 07 Feb 2015 08:08:00