Journal of Crystal Growth 246 (2002) 341346

Strong exciton energy blue shift in graded wurtzite and

zincblende GaN=Al0:2 Ga0:8N single quantum wells
E.W.S. Caetano, V.N. Freire*, G.A. Farias
! Caixa Postal 6030, Campus do Pici, 60455-900 Fortaleza, Ceara,
Departamento de F!sica, Universidade Federal do Ceara, ! Brazil

Abstract

The binding and total exciton energies in zincblende and wurtzite GaN=Al0:2 Ga0:8 N quantum wells are calculated
taking into account the existence of graded interfaces. It is shown that a strong exciton energy blue shift is due to the
nonabrupt interfaces. In the case of the wurtzite phase, a graded interface 1 nm thick blue shifts by approximately
200 meV the exciton total energy practically independent of the well width. In contrast, in the zincblende phase the blue
shift depends strongly on the well width due to the absence of built in electric elds related to the piezoelectric and
spontaneous polarizations.
r 2002 Elsevier Science B.V. All rights reserved.

PACS: 68.65.Fg; 71.35.
y; 77.84.Bw

Keywords: A1. Excitons; A1. Graded interfaces; A1. Spontaneous and piezoelectric polarizations; A3. Quantum wells; B1. Nitrides

GaN/AlGaN quantum wells have received
much attention due to the development of light
emitting diodes (LEDs) and laser diodes (LDs)
operating in the greenviolet range of the electro-
magnetic spectrum [1]. They are usually grown in
the stable wurtzite phase, but they are also grown
in the metastable cubic phase (zincblende). The
existence of strong built-in electric elds in
wurtzite GaN/AlGaN single quantum wells due
to spontaneous and piezoelectric polarizations has
stimulated many theoretical and experimental
works [26]. The piezoelectric eld induced by
the lattice mismatch between the materials changes
their optical properties. Bernardini and Fiorentini
*Corresponding author. Tel.: +55-85-2889937; fax: +55-85-
2874138.
E-mail address: valder@sica.ufc.br (V.N. Freire).
0022-0248/02/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 2 ) 0 1 7 5 9 - 1
[2,3] have predicted that the emission energy of
these structures depends on the quantum well
width. The separation of the wavefunctions
provoked by the existence of the built-in electric
eld reduces the oscillator strength, increases the
radiative recombination time, and leads to the
build-up of an electronhole plasma in the well
that screens the electric eld in excitation condi-
tions [7,8].
There is experimental evidence supporting the
existence of graded interfaces in GaN/AlGaN
quantum wells. Kisielowski et al. [9] have mapped
the In molar fraction distribution at the atomic
scale in a AlGaN/InGaN/GaN quantum well
through high-resolution transmission electron
microscopy (HRTEM). Their results revealed the
existence of an InGaN/AlGaN interface 2:5 nm
thick in their samples. Shirasawa et al. [10] have
342 E.W.S. Caetano et al. / Journal of Crystal Growth 246 (2002) 341346
estimated the interfacial roughness in GaN/
AlGaN heterostructures grown through metalor-
ganic vapor phase epitaxy (MOVPE), pointing to
an interfacial roughness ranging from 20:7 nm;
depending on the growth interruption time. To the
knowledge of the authors, only Wang et al. [11]
have addressed in their calculations the role of
graded interfaces in the conned exciton properties
in AlGaN/GaN single quantum wells (SQWs).
Their work, however, neglected the existence of the
above mentioned built-in electric elds, but has
indicated the existence of strong interface related
blue shifts in the conned exciton energy.
In this work, a theoretical calculation of the
conned exciton energy in wurtzite and zincblende
nonabrupt GaN=Al0:2 Ga0:8 N single quantum wells
is performed taking into account the existence of
internal electric elds due to spontaneous and
piezoelectric polarizations. In particular, the strain
attenuation at the interfaces due to the interfacial
smoothness is considered. We demonstrate that
the existence of graded interfaces strongly blue
shifts the conned exciton energy. In the case of
the wurtzite structure, this blue shift increases
dramatically due to the built-in electric eld, being
practically independent of the well width.
To investigate the effect of graded interfaces on
the ground state electronheavy hole (eh) exciton,
we have adopted the effective mass approximation
considering the following Hamiltonian:
 
_2 1 q q 1 q2
H#
r 2 2
2me2h r qr qr r qf
 
_2 q 1 q _2 q



2 qze m> ze qze 2 qzh
 e
1 q
 Ve ze Vh zh
m>h zh qzh
e2

;
4peE0 r2 ze
zh 2 1=2
where r; f; and za a e for electrons and a h
for heavy holes) are the relative electronheavy
hole cylindrical coordinates; m> >
e ze and mh zh
are the electron and heavy hole effective masses
along the growth direction 0 0 0 1 for the
wurtzite phase and 0 0 1 for the zincblende
phase); e is the dielectric constant for the material
inside the quantum well, and me2h is the in-plane
reduced effective mass of the electronheavy hole
pair. The connement potential Va za is the sum
of two terms, VaQW za VaFSPPZ za ; the former
due to the conning quantum well prole, and the
latter due to the existence of the built-in electric
eld. They are given, respectively, by
VaQW za Qa Eg wza
Eg w 0; 2
 
d dVaFSPPZ za
eza E0
dza dza
d
qa PSP za PPZ za ; 3
dza
where Qa is the band offset for the a-type carrier,
wza is the Al molar fraction at za ; and Eg w is the
band gap for the alloy Alw Ga1
w N; Eg w
EgAlN w EgGaN 1
w
bw1
w: wz is the Al
molar fraction prole for the quantum well. We
consider error function-like graded interfaces,
where the quantum well borders are situated at
the grading prole half-point. qa is the electric
charge for the corresponding carrier, and PSP z
and PPZ z are, respectively, the spontaneous and
piezoelectric polarizations at z: The piezoelectric
polarization for a wurtzite strained layer along the
0 0 0 1 direction is
 
a
a0 C13
PPZ 2 e31
e33 ; 4
a0 C33
where a0 is the lattice parameter for the relaxed
layer, e31 ; e33 and C13 ; C33 are, respectively, the
piezoelectric and elastic constants, and a is the
lattice parameter of the strained layer.
The parameters for the Alw Ga1
w N alloy are
obtained through linear interpolation (Vegard
law) from those of GaN and AlN, as given in
Table 1. According to Ref. [16], the polarization is
known to be nonlinear in the composition, but we
1 believe that this fact does not affect appreciably
the present results, because the change of total
polarization due to these nonlinear effects is of
only 7% for the Al molar fraction we used in our
calculations. Since Eq. (1) is not analytically
solvable, we have adopted the effective potential
method [17] to nd numerically the exciton ground
state energy. In the calculations we have consid-
ered an Al molar fraction x 20% at the quantum
 E.W.S. Caetano et al. / Journal of Crystal Growth 246 (2002) 341346 343

Table 1
Zincblende and wurtzite GaN, AlN parameters [2,1115]. m0 is the free space electron mass

GaN (ZB) AlN (ZB) GaN (WZ) AlN (WZ)

Eg (eV) 3:3 6:00 3:50 6:28

m> jj
e me =m0 0:190:19 0:330:33 0:190:19 0:350:35
m>hh m jj
hh =m0 0:862:00 1:434:55 2:002:04 3:5311:14
e 9:5 9:0 9:5 9:0
a0 (nm) 0:3189 0:3112
PSP C=m2
0:029
0:081
C13 C33 (GPa) 103405 108373
e31 e33 C=m2
0:490:73
0:601:46

well barriers. We note that our treatment of

Eq. (1) does not include exchange-correlation
corrections to single particle energies, and it is
not self-consistent. The total exciton energy, EEXC ;
is obtained by adding to the energy band gap of
the well, EgGaN ; the electron and hole connement
energies, Ee and Eh ; and subtracting the exciton
binding energy, Eb ; EEXC EgGaN Ee Eh
Eb :
Fig. 1 depicts the electron potential energy of
abrupt and graded quantum wells. It can be seen
that the existence of graded interfaces locally
reduces the electric eld strength and raise the
value of the potential energy minimum. Fig. 2
shows the binding Eb and total EEXC exciton
energies when the interface width is 0 nm (sharp Fig. 1. Electron potential energy in the case of abrupt and
wellsolid lines), 0:5 nm (nonabrupt well graded quantum wells.
dashed line), 1 nm (nonabrupt welldotted line)
and 1:5 nm (nonabrupt welldash-dotted line) for
a zincblende GaN=Al0:2 Ga0:8 N single quantum
well. In this case, there is no built-in electric eld. of approximately 2 MV=cm; inside this quantum
Nonabrupt interface effects become less important well, which is mainly due to the difference between
when the well width is larger. Consequently, the the GaN and AlN spontaneous polarizations. The
increase in the exciton binding energy due to the exciton binding energy is smaller than that
existence of graded interfaces is smaller for wider obtained for the zincblende single quantum well
wells. The asymptotic limit for the exciton binding as a consequence of the built-in electric eld that
energy is approximately 22 meV; in reasonable separates the electron and hole wavefunctions.
agreement with experimental data for the GaN There is a small increase of Eb when the existence
bulk exciton [18,19]. The total exciton energy of graded interfaces is take into account only when
varies from approximately 3:3 eV (well width the well width is not larger than 6 nm: The exciton
15 nm) to 3:5 eV (well width 3 nm), corresponding total energy, however, is much more inuenced by
to the extreme violet-ultraviolet range of the the existence of graded interfaces, as we will see
electromagnetic spectrum. later.
Fig. 3 presents the binding Eb and total EEXC The principal feature of the exciton total energy
exciton energies in a wurtzite GaN=Al0:2 Ga0:8 N is its strong red shift for larger well widths, ranging
single quantum well. There is a huge electric eld, from approximately 3:3 eV (well width of 3 nm) to
344 E.W.S. Caetano et al. / Journal of Crystal Growth 246 (2002) 341346
Fig. 2. The well width dependence of the ground state exciton
binding (top) and total (bottom) energies in a zincblende
GaN=Al0:2 Ga0:8 N SQW with abrupt and graded interfaces.
0:9 eV (well width of 15 nm), spanning completely
the visible spectrum (which corresponds approxi-
mately to the range 1:63:2 eV) and reaching the
ultraviolet and infrared regions. When the ex-
istence of graded interfaces is considered, this red
shift is attenuated by as much as 315 meV (see
Fig. 5).
Although the shift in Eb caused by the existence
of graded interfaces is small, the interface related
corrections on the electron and heavy hole energies
are much bigger, leading to the remarkable blue
shift in the exciton total energy we have found in
our calculations. This blue shift is especially
important for the wurtzite GaN=Al0:2 Ga0:8 N
single quantum well, as it can be seen comparing
Figs. 4 and 5. Fig. 4 shows the exciton energy blue
shift for the nonabrupt zincblende quantum well in
Fig. 3. The well width dependence of the ground state exciton
binding (top) and total (bottom) energies in a wurtzite
GaN=Al0:2 Ga0:8 N SQW with abrupt and graded interfaces.
comparison with the abrupt case. The blue shift is
of 130 meV for a well width of 3 nm and a
interface thickness of 1:5 nm (dotted line), decreas-
ing to 70 and 27 meV when the interface thick-
nesses are 1 and 0:5 nm; respectively. However,
when the well width is larger than 9 nm; the
interface related blue shift practically disappears.
This result is in sharp contrast with that
obtained for the wurtzite quantum well, which is
affected by the built-in electric eld. Fig. 5 depicts
the interface related blue shift of the total exciton
energy for three interface thicknesses: 0:5 nm
(solid line), 1 nm (dashed line) and 1:5 nm (dotted
line). This blue shift is independent of the quantum
well width and reaches 315 meV when the interface
thickness is 1:5 nm: Even for an almost abrupt
quantum well, with an interface thickness of
 E.W.S. Caetano et al. / Journal of Crystal Growth 246 (2002) 341346
Fig. 4. Exciton total energy blue shift as a function of the well
width in a zincblende GaN=Al0:2 Ga0:8 N SQW with graded
interfaces.
Fig. 5. Exciton total energy blue shift as a function of the well
width in a wurtzite GaN=Al0:2 Ga0:8 N SQW with graded
interfaces.
0:5 nm (approximately 1:5 AlGaN monolayer),
the exciton energy blue shift is 90 meV: Such
intense blue shift is caused by the small strain
attenuation and the smooth spontaneous polariza-
tion transition at the graded interfaces. The strain
attenuation, as well as the smooth transition of
spontaneous polarization, reduces locally the
electric eld strength. The sum of these effects
leads to an attenuation of the huge electric eld at
345
the interfaces, being such attenuation more im-
portant when the interface thickness is larger. The
well width does not contribute at all to this effect,
which explains the well width independence of the
exciton energy blue shift.
In conclusion, we have evaluated the effects of
nonabrupt interfaces on the ground state exciton
energy in zincblende and wurtzite GaN=
Al0:2 Ga0:8 N single quantum wells, in the latter
taking into account the existence of built-in electric
elds. It was demonstrated that the inclusion of
graded interfaces blue shifts the binding and total
exciton energies for a given well width. For the
zincblende phase, the calculations revealed that the
interface related conned exciton blue shifts are
stronger only in the case of thin quantum wells.
For wurtzite single quantum wells, the existence of
a huge built-in electric eld caused by spontaneous
and piezoelectric polarizations weakens the ex-
citon binding energy and strongly red shifts the
exciton total energy. Taking into account non-
abrupt interfaces, it was shown that there is a very
intense exciton energy blue shift which is practi-
cally independent on the well width. The results
allow us to suggest that to achieve a better
understanding of the conned exciton based
emission properties in actual GaN/AlGaN quan-
tum wells, it is necessary to use models in which
the existence of smooth interfaces is considered,
particularly for heterostructures grown in the
wurtzite phase, because of the polarization effects.
We acknowledge nancial support provided by
the National Research Council (CNPq) through
the grant NanoSemiMat Project (N. 550.015/01-
9). EWSC received a fellwoship from CAPES for
the development of the research. VNF and GAF
are CNPq Research Fellows.
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