Applied Surface Science 234 (2004) 5053

Optical properties of zincblende GaN/BN cylindrical nanowires

E.W.S. Caetanoa, V.N. Freirea,*, G.A. Fariasa, E.F. da Silva Jr.b
a
Departamento de Fsica, Universidade Federal do Ceara, Caixa Postal 6030, Campus do Pici, 60455-760 Fortaleza, Ceara, Brazil
b
Departamento de Fsica, Universidade Federal de Pernambuco, Cidade Universitaria, 50670-901 Recife, Pernambuco, Brazil

Available online 6 July 2004

Abstract

We calculate the confined exciton energy of zincblende GaN/BN cylindrical nanowires using a two-parameter variational
approach within the effective mass approximation. Feasibility of light emission in the 300
700 nm range is attained, depending
both on the nanowire radius and the graded interface thickness. It is shown that in actual zincblende GaN/BN nanowire samples,
the existence of non-abrupt interfaces can blue shift the exciton recombination energy up to 100 meV for non-abrupt interface
thickness of just a few monolayers.
# 2004 Published by Elsevier B.V.

PACS: 79.60.Jv; 81.07.Vb; 78.30.Fs; 78.55.Cr; 71.35.-y; 71.35.Cc

Keywords: Gallium nitride; Boron nitride; Quantum wires; Optical properties; Excitons

1. Introduction features and their physical properties are strongly

Gallium nitride (GaN) and its ternary alloys have
attracted considerable interest due to their promising
applications in optoelectronics such as light emitting
diodes (LEDs) and laser diodes (LDs) in the visible
and ultraviolet spectral regions [1,2], Cubic boron
nitride (c-BN), on the other hand, is a material that
presents very interesting properties, such as extreme
hardness, high thermal conductivity, high melting
temperature, large band gap, chemical inertness, ther-
mal stability, low dielectric constant, and the feasi-
bility of being doped both p- and n-type [3]. In recent
years, quantum wires based on the nitride system have
received much attention [46] mainly because one-
dimensional (ID) nanostructures present remarkable
*
Corresponding author. Tel.: 55 85 2889937;
fax: 55 85 2874138.
E-mail address: valder@fisica.ufc.br (V.N. Freire).
dependent on size and geometry [7].
From the experimental point of view, several reports
on the synthesis of GaN nanowires by various methods
have been published [810]. Han et al. [11] demon-
strated an efficient method to synthesize GaN nanor-
ods coated with insulating BN layers  5 nm thick,
where the GaN core is crystalline with either a cubic or
hexagonal structure, diameters ranging from 10 to
85 nm, and lengths up to 60 mm. However, impurities,
doping, and strain shifts and broads the exciton reso-
nance, which makes exciton-related properties an
indication of material quality.
To date, a clear picture of the interfaces of GaN
nanowires is still not clear, despite the progress on
building these structures. However, it was reported
the existence of 0.5
1.5 nm thick graded interfaces
in AlxGa1
xN/InxGa1
xN/GaN single quantum wells
[12,13]. Kimura et al. [14] have grown boron nitride
films on a roughened surface of GaN by plasma-assisted

0169-4332/$ see front matter # 2004 Published by Elsevier B.V.

doi:10.1016/j.apsusc.2004.05.050
 E.W.S. Caetano et al. / Applied Surface Science 234 (2004) 5053 51

chemical vapor deposition. They have estimated a is the corresponding position-dependent effective
5.3
10.6 nm surface roughness for their BN/GaN sam- mass (confinement potential), and e is the dielectric
ples. In InxGa1
xN/GaN multiple quantum wells, alloy constant of GaN, taken as 9.7 [16].
disorder and interface roughness has to be included in The dependence of the BxGa1
xN band gap energy
order to interpret the photoluminescence emission spec- and i-type carrier effective mass is obtained through
trum and the decay dynamics [15]. Therefore, it is the following linear relations:
reasonable to suppose the existence of graded interfaces
in nitride-based quantum wires. Eg x 1
xEgGaN xEgBN ; (2)
In this work, we present results of how the existence mi x 1
xmGaN xmBN
i i : (3)
of non-abrupt interfaces changes the electron-heavy
hole exciton confinement energy in an infinite cylind- The BN molar fraction is assumed to depend on r
rical zincblende GaN/BN quantum wire. For the cubic according to an error function-like profile:
zincblende phase, there are no spontaneous polariza- 

tion. At the same time, piezoelectric effects can be 1 2r
R s
xr 1
erf ; (4)
eliminated by a suitable choice of growth axis. It is 2 s=2
shown the existence of non-abrupt interface related where R is the quantum wire radius, and s is the
blue shifts of the luminescence spectra up to graded interface thickness, which is due to effects such
100 meV for interfaces as thin as few monolayers. as inter-diffusion during actual GaN/BN wire growth
processes.
The confinement potential for the i-type carrier
2. Numerical method depends on the corresponding band offset Qi and it
is given by:
We consider an infinite cylindrical wire made of
zincblende GaN and BN, the former embedded in the Vi ri Qi Eg xxi
EgGaN : (5)
latter. The symmetry axis of the wire (z axis) is along
Kimura et al. [14] have obtained a band diagram of the
the (0 0 1) direction. We have performed our calcula-
BN/GaN structure. From their results, we estimate
tions using a two-parameter variational approach, and
Qe 0.83, Qh 1
Qe 0.17 for zincblende GaN/
assuming a graded interface picture within the effec-
BN heterojunctions. For these effective masses, we
tive mass approximation. The carriers effective
adopt the ab initio results obtained by Ramos et al.
masses are isotropic, obtained by averaging in the
[17].
parallel and perpendicular directions to z. Therefore,
In order to find the exciton energy, we define a two-
the Hamiltonian describing an electron-heavy hole
parameter variational wavefunction, C ce
h(re, rh;
ground state exciton confined in a zincblende GaN/
b, l)ce(re)ch(rh) where
BN cylindrical quantum wire with graded interface is
given by: ce
h re ; rh ; b; l
2
 p!
2 2
^ EgGaN
h re 1 re2 rh2
2bre rh z z
H re Ve re exp

exp
e h ;
2 me re l l
|{z}
^e
H (6)
2


h 1 e2 and ci(ri) (i e, h) is the ground state solution of

rh rh Vh rh
;
2 mh rh 4pee0 jre
rh j ^ i ci Ei ci . The wave-functions ci(ri) and the cor-
H
|{z}|{z}
^h
H ^ e
h
V responding energy levels are calculated using a mod-
(1) ification to the cylindrical geometry of the multistep
method proposed by Ando and Itoh [18]. The two
where EgGaN 3.4 eV is the GaN band gap, ri is the variational parameters, b and l, are related to the
cylindrical coordinate of the i-type carrier (i e, h, for radius and symmetry of the ground state exciton,
electrons and heavy holes, respectively), mi(ri) (Vi(ri)) 0
respectively. The ground state exciton energy EEXC is
52 E.W.S. Caetano et al. / Applied Surface Science 234 (2004) 5053

Table 1
Parameters of zincblende GaN and BN [17]

III-nitride Eg (eV) me/m0 mh/m0

GaN 3.4 0.15 1.48

BN 6.0 0.74 0.90
m0 is the free electron mass.

thereby given by:

 
^
CjHjC
0
EEXC min : (7)
l;b hCjCi
We calculate the exciton binding energy EB0 by sub-
0
tracting Eg, Ee and Eh from EEXC , EB0 EEXC
0


Eg
Ee
Eh . The effective masses and band gaps
adopted in this work are listed in Table 1. To inves-
tigate the effect of the interface thickness s, calcula-
tions are performed considering s 0.5, 1.0, and
1.5 nm. The wire radius ranges from 2 to 7 nm, which
is within the 2 nm limit average radius for the effective
mass approximation to be valid in the case of bound
Fig. 1. Binding (top) and total (bottom) ground state electron-
states [16].
heavy hole confined exciton energy in a zincblende GaN/BN
cylindrical quantum wire with interface thickness s 0, 0.5, 1.0,
and 1.5 nm.
3. Results
region of the electromagnetic spectrum (wavelengths
Fig. 1 shows the results for the ground state exciton between 357.30 and 387.45 nm). When the existence
binding energy EB0 (top graph) and total ground state of graded interfaces is taken into account, this picture
0
exciton energy EEXC (bottom graph) for abrupt and is dramatically changed. For s 0.5 nm and
0
non-abrupt zincblende GaN/BN quantum wires of R 2 nm, EEXC 3:55 eV (corresponding to an
several diameters. One can clearly see that interface wavelength of 349.25 nm), a value that is 80 meV
effects on EB0 are much smaller than the interface higher than the obtained for s 0. However, when the
0
related shift on EEXC when the wire radius is small. wire radius is larger than 6 nm, interface related
For a wire of radius 2 nm, the shift of EB0 due to an effects on the ground state exciton energy become
interface thickness increase from 0 to 1 nm is 13 meV very small. A similar behavior was found by Wang
0
(from 67 to 80 meV), while the shift of EEXC is et al. [19] for zincblende and wurtzite GaN/Alx-
220 meV (from 3.470 to 3.690 eV). However, the Ga1
xN single quantum wells, i.e. they observed that
shifts decrease strongly when the wire radius is the magnitude of the exciton energy blue shift is
7 nm, being of the order of few meV for both EB0 strongly dependent on the non-abrupt interface thick-
0
and EEXC . The ground state exciton binding energy ness.
decreases with the growth of the zincblende GaN/BN We define the exciton energy blue shift due to the
wire radius R because of the spreading of electron existence of a graded interface for a given wire radius
and hole wavefunctions, which reduces the Coulomb as the difference between the exciton energy for a non-
interaction. abrupt wire and the exciton energy for an abrupt one,
0 0
In the abrupt interface case (s 0), the exciton DEEXC(R, s) EEXC (R, s)
EEXC (R, s 0). In Fig. 2
0
energy decreases from 3.47 to 3.20 eV as the wire we present the behavior of EEXC for s 0.5, 1.0, and
radius increases from 2 to 7 nm (see the bottom part of 1.5 nm. For s 1 nm, DEEXC changes from 220 meV
Fig. 1). This range of energies spans the ultraviolet (R 2 nm) to 3 meV (R 7 nm). For R 3 nm and
 E.W.S. Caetano et al. / Applied Surface Science 234 (2004) 5053
Fig. 2. Dependence of DEEXC(s) with the zincblende GaN/BN
wire radius for graded interfaces of 0.5, 1.0, and 1.5 nm.
s 1 nm, DEEXC 64 meV. Therefore, in this case
there is a very strong exciton energy blue shift related to
the existence of a 1 nm thick graded interface, that
corresponds to an increase of almost 6% in comparison
to the abrupt quantum wire. If we consider an interface
thickness of 1.5 nm, and R 2 nm, DEEXC is 437 meV,
an increase of  12.7% in comparison to the abrupt
case. For the same interface thickness and a wire radius
of 3 nm, DEEXC 123 meV. These blue shifts are far
more pronounced than the ones found by Wang et al.
[19] for 5 nm wide GaN/Al0.3Ga0.7N single quantum
wells, where the ground state exciton energy blueshift is
33.5 meV in the zincblende phase, for an interface
thickness of 1 nm. The results here presented allow
us to estimate a broadening of about 100 meV in the
photoluminescence spectrum for GaN/BN wires with
R 3 nm, due to the existence of interfacial roughness
varying locally from 0.5 to 1.5 nm.
4. Summary and conclusions
In summary, we have shown the existence of
remarkable interface related blue shifts on the exciton
energy in cylindrical zincblende GaN/BN quantum
wires. For wires with radius smaller than 6 nm, there is
a considerable enhancement of the confined exciton
energy that pushes the recombination energy towards
the extreme ultraviolet region of the spectrum. Inter-
face effects can affect noticeably the photolumines-
cence spectrum, being responsible for a significant
part of their homogeneous broadening. An improve-
ment of the description of optical properties of zinc-
blende GaN/BN quantum wires demands a better
53
characterization of their interfaces from the experi-
mental point of view, and to take into account the
existence of graded interfaces in the theoretical cal-
culations.
Acknowledgements
The authors would like to acknowledge partial
financial support received from the Brazilian agencies
CAPES, FUNCAP, and CNPq/NanoSemiMat and
FINEP/CTPETRO grants no. 550.015/01-9 and no.
65.00.0280.00, respectively.
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