Solid State Communications 125 (2003) 205–208

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Near band-edge optical properties of cubic GaN

J.R.L. Fernandeza, O.C. Noriegab, J.A.N.T. Soaresb, F. Cerdeiraa,*, E.A. Menesesa,
J.R. Leiteb, D.J. Asc, D. Schikorac, K. Lischkac
a
Instituto de Fı́sica GW, Universidade Estadual de Campinas, CP 6165, 17083-970 Campinas, SP, Brazil
b
Instituto de Fı́sica, Universidade de São Paulo, CP 66318, 05315-970 São Paulo, SP, Brazil
c
Universität Paderborn, FB-6 Physik, D-33095 Paderborn, Germany

Received 25 September 2002; accepted 18 October 2002 by C.E.T. Gonçalves da Silva

Abstract
We used photoluminescence, photoluminescence excitation spectroscopy (PLE) and photoreflectance (PR) to study the
optical properties of thin films of cubic GaN, deposited by plasma-assisted molecular beam epitaxy on a GaAs (001) substrate.
Our results show a clear step-like absorption edge, resulting from the merging of the free exciton with the continuum.
Quantitative values for the absorption-edge energy and lifetime broadening are obtained. The dependence of the latter on
temperature, as well as some features of the PR spectrum, reveal that the cubic material still presents residual strain and
distortions. A secondary absorption-edge due to hexagonal inclusions is also observed in the PLE spectra.
q 2003 Elsevier Science Ltd. All rights reserved.
PACS: 78.20. 2 e; 78.40.Fy; 78.55.Et
Keywords: A. Epitaxy; A. Thin films; B. Preparing and processing; D. Phenomena and properties

1. Introduction the cubic polytype is expected to increase the optical

Although significant advances in growth, doping, and
device applications of group-III nitrides have been achieved
with the stable hexagonal phase of these materials, less
progress has been made with the metastable cubic (c-)
modifications [1 – 4]. Recently, c-GaN grown by metal
organic chemical vapor deposition (MOCVD) and molecu-
lar beam epitaxy (MBE) was successfully used to make p – n
junction light-emitting diodes (LEDs) [5– 7]. The fabrica-
tion of the first c-InGaN/GaN double-heterostructure LED
grown by MOCVD has been also reported recently [8]. On
the contrary to their hexagonal counterparts, the cubic
structures can be grown free from modulation due to
spontaneous polarization and strain-induced piezoelectric
fields. The spatial separation of the carriers wave function,
induced by the quantum-confined Stark effect in the
hexagonal phase, is avoided in the cubic structure. Thus,
* Corresponding author.
E-mail address: fernando@ifi.unicamp.br (F. Cerdeira).
0038-1098/03/$ - see front matter q 2003 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 3 8 - 1 0 9 8 ( 0 2 ) 0 0 7 6 8 - 8
recombination efficiency in nitride-based quantum wells.
The growth of high-quality c-GaN epitaxial layers is
essential for the use of cubic nitrides in the electronic and
optoelectronic device technology. The comparative studies
of the physical properties of c-GaN layers grown on
different substrates are important for the improvement of
the quality of the material. Here we report the results of
studying the optical properties of c-GaN, grown on GaAs
(001) substrates, using photoluminescence (PL), photo-
luminescence excitation spectroscopy (PLE), and photo-
reflectance (PR). The PLE experiments, carried out for the
first time on this kind of samples, allow the identification of
the optical transitions taking place in the layers. The results
obtained by the different techniques are compared to one
another and show a high degree of consistency.
2. Samples and experiment
The c-GaN layers were grown by plasma-assisted MBE,
206 J.R.L. Fernandez et al. / Solid State Communications 125 (2003) 205–208
using a Riber-32 system, equipped with elemental sources
of Ga and As, and an Oxford Applied Research CARS 25
rf-activated plasma source. Before starting the c-GaN
nucleation, a GaAs buffer layer was grown. The nucleation
of c-GaN was initiated at a substrate temperature of 600 8C
using a N/Ga flux ratio of about 4. After deposition of 10 –
20 ml, the nucleation stage was stopped and the substrate
temperature raised to 680– 740 8C. The static GaN(001)
surface exhibits a clear 2 £ 2 reconstruction during this
period. The growth process was monitored continuously by
reflection high-energy electron diffraction (RHEED) and
RHEED image-recording systems. Details of the growth
procedure were reported in Ref. [9]. Our samples show Hall
background p-type concentrations of about 1016 cm23. The
width of the GaN layer is , 300 nm.
Both PL and PLE spectra were excited with an air-cooled
1000 W Xe lamp filtered with a 1.0 m SPEX monochro-
mator with a 1200 groove/mm grating. The monochromatic
light was focused onto the sample, contained in an Air
Products cold finger cryostat at T . 10 K. Emitted light was
focused into a double grating SPEX monochromator and
detected by a cooled RCA Ga– In– As photomultiplier tube.
Quartz lenses were used both for excitation and collection of
emitted radiation.
Room temperature PR experiments were performed with
an air cooled 1000 W Xe lamp as the excitation source. The
light was dispersed through a 0.50 m monochromator with a
1200 groove/mm grating and focused onto the sample by a
lens system with a spot of approximately 1.5 £ 1.5 mm2.
The reflectivity was modulated by the unfocused beam of a
He– Cd laser (50 mW), mechanically chopped at 200 Hz.
The intensity of the monochromatic light, as well as that of
the modulating one, was controlled by neutral density filters.
The reflected light was detected by an UV-enhanced Si
photodiode operating on photovoltaic mode. The ac signal
was analyzed by a lock-in amplifier.
3. Results and discussion
PL and PLE spectra are displayed in Fig. 1. The PL
spectrum obtained here by low power density excitation
with a filtered Xe-arc is entirely similar to the spectra
obtained by excitation with laser sources reported by other
authors [10]. Two clear narrow structures characterize this
spectrum, attributed to acceptor – donor transitions
Table 1
Observed critical point energies (Ei) and FWHM (Gi) (in parentheses) by different optical techniques. The last column lists assignments for the
critical points in the spectra
Technique E1 (G1) (eV)
PL (10 K) 3.26 (0.03)
PLE (10 K) 3.26 (0.05)
PR (300 K) 3.16 (0.06)
Fig. 1. Low temperature (10 K) PL and PLE spectra of GaN. Arrows
indicate the photon energy location of the structures listed in
Table 1.
(3.15 eV) and bound exciton (3.26 eV), respectively (see
Table 1). Structures located at lower energies than these two
provide ideal candidates for centering the analyzing
spectrometer in the PLE experiment. Best results are
obtained when this centering is done at the PL peak of
2.86 eV. The resulting PLE spectrum mimics the absorption
spectra and closely resembles two broadened step functions
located at different photon energies. This lineshape is
characteristic of a Mo singularity with an exciton which is
broad enough to merge with the continuum [11]. Fitting this
spectra with two broadened step functions, we obtain values
for the photon energy of the two absorption edges, as well as
for their broadening parameters (full width at half-
maximum, FWHM). These parameters are listed in Table
1. Arrows in Fig 1 indicate the location of these two critical
points in the absorption, designated as E1 and E2,
respectively, in order of increasing energy. We attribute
the first critical point (E1) to the absorption edge of cubic
GaN. This photon energy is only < 6 meV above the one
obtained in PL for the bound exciton (Table 1), as opposed
to the 14 meV difference between the free and bound
excitons [10], which would result from absorption and PL,
respectively. This can be considered a good agreement,
since the width of the singularity (50 meV) exceeds this
value by a factor of three (Table 1). This very large width is,
in turn, attributable to sample imperfections. This view is
reinforced when comparing the above results with those of
E2 (G2) (eV) Assignment
c-GaN bound exciton
3.5 (0.2) E1 (E2): absorption edge of c- (h-) GaN
Absorption edge of c- GaN
 J.R.L. Fernandez et al. / Solid State Communications 125 (2003) 205–208
Fig. 2. Room-temperature PR spectrum of GaN. Circles represent
experimental data while the solid line is a fit of the main absorption
edge with a third derivative lineshape (see text). The arrow indicates
the position of this edge (see Table 1).
the PR experiments, to be discussed next. The second
absorption edge is attributed to inclusions of hexagonal GaN
in the sample. The critical energy of this second absorption
edge is listed in Table 1 and is in good agreement with that
reported for hexagonal GaN by other authors [12,13].
The room-temperature PR spectrum of the sample is
shown in Fig. 2. This spectrum shows a sharp line which
exhibits the typical third derivative lineshape described by
Aspnes [14]. The result of fitting this transition for the type
of singularity described above (band edge with broad
exciton) [15] is shown as a continuous line in this figure. The
values for the transition energy and FWHM resulting from
this fit are listed in Table 1. The energy of the critical point
(E1) obtained in this way is downshifted by < 100 meV
from that obtained by PLE, which can be explained by the
temperature difference between these two experiments [10].
Two additional features are observed in the PR spectrum of
Fig. 2. A broad band below the absorption edge and a few
oscillations above it. The former can be attributed to
structural defects, such as appear in similar spectra of thin
layers of InxGa12xAs deposited on GaAs [16]. The second
feature could be attributed to Franz– Keldysh oscillations
produced by built-in electric fields [15,16]. Finally, the
FWHM of the main exciton at room temperature is only
about 20% larger that at 5 K. This is symptomatic of the fact
that line broadening is dominated by sample imperfections.
One feature of the PLE spectrum deserves further
comment. Namely, that the intensities features originating
in the cubic and hexagonal phases of GaN are similar to one
another. This could lead to the naive interpretation that,
since the absorption of the two phases appears to be equal
then they appear in the sample in equal amounts. This is, in
fact, not true, as evidenced by the absence of a line
attributable to h-GaN in the PL spectrum (around 3.5 eV).
Previous PL studies in similarly prepared samples [10] also
fail to find such a line. In fact, based on the reduced PL
207
intensities above the c-GaN gap, the authors of Ref. [10]
estimate that the fraction of the sample occupied by
hexagonal inclusions is less than 0.1%, and we expect the
same to be valid for our samples. In this case, how do we
explain the strong contributions which this minority phase
gives to the PLE spectrum? First we must bear in mind that,
although the shape of the PLE spectrum mimics the shape of
absorption spectrum, the intensities of the different features
do not represent actual absorption strengths. Rather, they
reflect the effect that such an absorption has on the
recombination efficiency of the PL feature on which the
analyzing spectrometer is centered. In our case, this means
that absorption by trace inclusions of the hexagonal phase
greatly enhance the recombination process leading to the
2.86 eV feature in the PL spectrum. We could speculate that
both this feature in the PL spectrum and the broad feature in
the PR spectrum at about the same photon energy are
produced by strain-related defects. In this case, the extreme
susceptibility of the PLE spectrum to h-GaN inclusions
would mean that these occur precisely at the locations of
these defects, such as the GaAs/GaN interface and stacking
faults throughout the volume of the c-GaN film. Regardless
of the reason responsible for this effect, PLE turns out to be a
powerful technique for detecting even minute amounts of
these inclusions and is, therefore, an excellent tool for
monitoring sample quality.
4. Conclusions
The picture emerging from the above discussion is one in
which the GaN layers are shown to be composed mainly of
the cubic phase, with some inclusions of hexagonal material
and residual strain and distortions which dominate the
broadening parameter associated with the main excitonic
transition at the direct gap. PLE is shown to be a good
technique to investigate h-GaN inclusions and strain-related
defects, thus being ideally suited to monitor sample quality.
Acknowledgements
The authors are grateful to Prof. Maria. J. S. P. Brasil for
her unstinting help in setting up the Xe-arc PLE facility.
Financial support from the Fundação de Amparo à Pesquisa
do Estado de São Paulo (FAPESP) and Deutsche For-
schungsgesellschaft (DFG) are gratefully acknowledged.
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