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Phys. Status Solidi A 207, No. 6, 14001403 (2010) / DOI 10.1002/pssa.200983561

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applications and materials science
Stress relaxed nanoepitaxy GaN for
growth of phosphor-free indium-rich
nanostructures incorporated in
apple-white LEDs
C. B. Soh*,1, W. Liu1, S. J. Chua**,1,2, N. S. S. Ang1, A. M. Yong1, S. C. Lai1, and J. H. Teng1
1
Institute of Materials Research and Engineering, A
STAR (Agency for Science, Technology and Research),
3 Research Link, Singapore 117602, Singapore
2
Singapore-MIT Alliance, 4 Engineering Drive 3, Singapore 117576, Singapore

Received 1 October 2009, revised 17 December 2009, accepted 19 December 2009

Published online 17 May 2010

Keywords electroluminescence, InGaN/GaN, LEDs, nanostructures, MOCVD, photoluminescence, quantum wells

* Corresponding author: e-mail cb-soh@imre.a-star.edu.sg, Phone: 65-8748257, Fax: 65-67740142

** Corresponding author: e-mail elecsj@nus.edu.sg; Phone: 65-65164784, Fax: 65-67740142

Phosphor-free apple-white light emitting diodes (LEDs) have
been fabricated using dual stacked InGaN/GaN multiple
quantum wells (MQWs) comprising a lower set of long wave-
length emitting indium rich nanostructures incorporated in
MQWs with an upper set of cyan-green emitting MQWs. The
LEDs were grown on nano-epitaxial lateral overgrown (ELO)
GaN template formed by regrowth of GaN over SiO2 film
patterned using an anodic alumina oxide mask with holes of
125 nm diameter and a period of 250 nm. The MQWs grown
on the nano-ELO GaN templates show stronger photolumines-
cence intensity and a higher activation energy for their peak
emission. A minimal shift in the electroluminescence (EL)
spectra with higher injection current applied for LEDs grown on
ELO-GaN compared to conventional GaN template, suggests a
reduction in strain of the quantum well layers on the nano-ELO
GaN template. An enhancement in the light extraction effi-
ciency is also achieved with multiple scattering via the
embedded SiO2 mask.

2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction In recent years, GaN light emitting
diodes (LEDs) have been applied for various applications
such as street, traffic, and facade lightings as well as in
automobiles and backlighting for displays. Solid-state
lighting would replace conventional light bulbs and will
change the way we light the world [1]. InGaN/GaN multiple
quantum wells (MQWs) are often employed as the active
layers due to their relatively high recombination efficiency,
and blue to green III-nitride LEDs are commercially
available. However, III-nitride faced several constraints
when we attempt to incorporate high indium content
materials due to the large lattice mismatch (11%) between
InN and GaN [2, 3]. This leads to strong piezoelectric field
effect and reduction in internal quantum efficiency with
higher indium incorporation. Conventional white LEDs are
thus generated with a phosphor coating of blue LEDs to give
white light. Recently, there have been reports on growth of
phosphor-free white LEDs with laterally distributed MQWs
[4], micro-structured multifaceted quantum wells [5], and
pre-strained InGaN well layer [6]. Our group has been
researching on quantum dots incorporated MQWs and we
have generated phosphor-free white LEDs with indium-rich
quantum dots incorporation. The MQWs with incorporated
quantum dots have a broad emission spectrum covering from
400 to 700 nm for white light generation [7]. However, there
is a need to improve the light extraction from the LEDs.
Various patterning techniques have been employed to
enhance light extraction from LEDs, which includes surface
roughening [8], geometric modification [9], and use of
photonic crystals [10]. In this work, four MQW samples with
conventional InGaN/GaN MQWs and indium-rich nanos-
tructures were grown for our study on both nano-ELO
template and conventional GaN template as summarized in
Table 1.
2 Experimental The u-GaN sample used for the
preparation of the nano-ELO GaN template was grown by
metalorganic chemical vapor deposition (MOCVD) at

2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


Phys. Status Solidi A 207, No. 6 (2010)
Table 1 InGaN/GaN QWs structures grown on different tem-
plates.
template structure of the MQWs conventional nano-ELO
GaN template
conventional InGaN/GaN QWs A B
InGaN/GaN QWs with indium-rich C D
nanostructures incorporated
1020 8C with trimethylgallium (TMGa) and NH3 gas serving
as the precursors for Ga and N, respectively, at a chamber
pressure of 500 Torr. For the fabrication of nano-epitaxial
lateral overgrown (ELO) GaN template using the u-GaN
sample, an alumina mask was formed by a two step
anodization process carried out in 0.3 M oxalic acid at 2 8C
with an injection voltage of 60 V. After the first anodization
step, the sample was immersed in H2CrO4 acid at 60 8C for
25 min to remove the oxide, leaving behind the self-ordered
pattern of pits for a subsequent anodization. A regular array
of nanopores is generated on the alumina template after
the pores are enlarged in 5 wt% of H3PO4, which serve as
chemical etchant for alumina. Inductive coupled plasma
(ICP) etching in CHF3 ambient is done to etch the underlying
SiO2 to create nanopores before the alumina mask is
removed with chemical acid. The sample is then loaded
back into the MOCVD for growth of a 2 mm layer of GaN.
Subsequently, the InGaN/GaN quantum well layers (of
thickness 3/12 nm) were grown at 755 8C for four periods.
For the incorporation of indium-rich InGaN nanostructures,
the growth chamber was flowed with trimethylindium
(TMIn) for a period of 30 s before capping with an InGaN
well of thickness 3.0 nm at a temperature of 745 8C. The
detailed growth is reported elsewhere [11].
3 Results and discussion Figure 1a shows the tilted
view of the SiO2 mask after the top regrown GaN layers
were removed by focused ion beam (FIB). The nanopores
generated on the 200 nm thick SiO2 film have a diameter of
120130 nm and a lattice period, a of 240250 nm as shown
in the inset of Fig. 1a.
Figure 1 (a) SEM image after FIB to expose the transfer of the self-
ordered patterned site on SiO2 film with subsequent growth of GaN
pillars from these nano-pores on SiO2 as shown in inset. (b) Structure
of the nano-ELO GaN template with embedded GaN nano-pillars
and SiO2 mask.
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1401
Sample B
495 nm
Sample A
488 nm 513 nm
PL Intensity (a.u.)
Sample C
Sample D
Sample A
Sample B
10K
Sample D LO phonon
replica
579 nm
2D InGaN
wetting layer
Sample C 573 nm
400 450 500 550 600 650
Wavelength (nm)
Figure 2 (online colour at: www.pss-a.com) Low temperature PL
spectra of the InGaN/GaN MQWs at 10 K. Samples A and B with
structures on GaN and nano-ELO GaN template; samples C and D
with indium-rich nanostructures incorporated in InGaN/GaN struc-
tures on GaN and nano-ELO GaN template.
The subsequent growth of 2.0 mm GaN at higher TMGa
flow enables the pores to be covered up to form the nano-
ELO template. The RMS roughness of this nano-ELO GaN
template is 0.35 nm as compared to 0.29 nm for conven-
tional GaN template. The overall structure of the nano-ELO
template for growth of MQWs B and D is as shown in Fig. 1b.
Figure 2 shows the low temperature PL spectra of the
four MQWs samples grown on the different templates.
The MQWs on nano-ELO GaN template (sample B) lead to
a redshift in the peak emission as compared to MQWs on
conventional GaN (sample A) from 488 to 513 nm. The
incorporation of indium-rich nanostructures (sample D)
leads to a significant enhancement in indium incorporation
resulting in a PL peak emission at about 570 nm. The growth
of MQWs on the strain relaxed nano-ELO template enhanc-
ed the incorporation of indium in the InGaN nanostructures
which leads to a redshift in the emission peak by 7 nm
through comparison of the PL spectrum for samples C and D.
The shoulder emission at the higher wavelength side for
samples A and B corresponds to the LO phonon replica [12].
On the other hand, the broad emission at 530 nm is due to the
incorporation of InGaN wetting layer to enhance the
formation of the indium rich nanostructures. The enhance-
ment in the integrated PL intensity is 1.3, without taking into
account the emission from the InGaN wetting layer.
The varying temperature PL spectra for sample D is as
shown in Fig. 3 with an inset of their Arrhenius plot. The
emission at 650 nm is attributed to the use of HeCd laser for
excitation with its emission at 325 nm. A higher activation
energy (EA1  45.7 meV for sample D as compared to
EA1  26.3 meV for sample C) is obtained for the sample
grown on nano-ELO GaN template with the reduction in
defect density leading to a higher energy for carrier capture.
An additional activation energy at EA2  6.9 meV is obtained
for samples C and D due to atomic well width fluctuation
2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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1402 C. B. Soh et al.: Nanoepitaxy GaN for growth of P-free In-rich nanostructures in white LEDs

6
Embedded Indium
rich nanostructures 4K
5 20K
Integrated PL Intensity (a.u.)

10
4
MQW D 40K
70K
PL Intensity (a.u.)

MQW B
4 100K
MQW C
10
3
MQW A
140K
3 MQW A, E = 25.3meV 180K
MQW B, E = 40.3meV
MQW C, E = 26.3meV, E = 6.9meV
230K
10
2 MQW D, E = 45.7meV, E = 6.9meV 300K
2 0.00 0.05 0.10 0.15 0.20 0.25
-1
1/T (K )
Cap InGaN
1 well emission
MQWs D
0

400 450 500 550 600 650 700

Wavelength (nm)
Figure 3 (online colour at: www.pss-a.com) Temperature varying
PL spectra for MQWs D with inset giving the Arrhenius plot for the
MQWs sample.

with indium-rich nanostructures incorporated. On the other

hand, a better fitting using a single activation energy of
EA1  25.3 meV and EA1  40.3 meV is achieved for
samples A and B, respectively.
For the generation of phosphor-free white LEDs, a dual
stacked MQW structure consisting of embedded indium-rich Figure 4 (online colour at: www.pss-a.com) (a) Electrolumines-
InGaN nanostructures incorporated in the MQWs (sample C cence (EL) spectra of the LEDs with the stacked MQWs structures
or D) with conventional InGaN/GaN MQWs (sample A or B) grown on conventional GaN template (LEDs E) and on nano-ELO
as mentioned above were grown on GaN (LEDs E) and nano- GaN template (LEDs F) with injection current at 20 and 80 mA, (b)
ELO GaN template (LEDs F). Figure 4a shows the shows the emission from the LED die (LEDs F) on the IV probe
electroluminescence (EL) spectra for LEDs E and F at 20 stage.
and 80 mA. Both LEDs were grown in the same growth run
but on different templates. At 20 mA, integrated EL intensity layers with the reduction in strain by growing on nano-ELO
was improved by 50% for LEDs F over LEDs E. For an GaN template. The higher stability in the emission wave-
injection current of 80 mA, the improvement was only by length with increase in injection current for the sample
33% and the reduction is attributed to thermal heating in the grown on nano-ELO template enables an apple-white
packaged chip. The enhancement in the EL emission LED to be fabricated. Based on the measurement using
intensity of LEDs F as compared to LEDs E as shown in the spectroradiometer, CS-2000 system, with correlated
Fig. 4 is due to scattering of light from the GaN nanopillars color temperature of 4791 K and CIE(x, y) coordinate at
embedded in the SiO2 mask. The light which is internally 0.3712:0.5049. This phosphor-free apple-white LED has
reflected from the MQWs will be scattered when they are great potential to be applied as a commercial LED.
incident on the SiO2 pillars. The refractive index of SiO2 is
n1  1.46 and of GaN is n2  2.5. The critical angle is 40.468 4 Conclusions In summary, the use of nano-ELO
for light emission from GaN to SiO2 film which alters the GaN template for growth of LEDs is effective in enhancing
subsequent path of light reflected from SiO2 back to GaN. the light output performance of the LEDs through improve-
This causes multiple scattering from the sidewalls of the ment of internal quantum efficiency as demonstrated by
SiO2 mask and results in subsequent enhancement in light stronger PL emission and higher activation energy for its
extraction from the LEDs. dominant peak emission. The use of nano-ELO template also
There is minimal shift in its MQW emission wavelength enhances the indium incorporation in the InGaN well layer
at higher injection current of 80 mA as compared to 20 mA and it lowers the piezoelectric field effect in the MQW layer,
for the LEDs grown on the nano-ELO GaN template, LEDs F leading to a minimal shift in its MQW emission wavelength
(a shift of 0.6 nm for EL peak P1 and of 2 nm for peak P2). On with higher injection current. This enables an apple-white
the other hand, LEDs E show a shift of 1.4 nm for EL peak P1 LED to be generated with a dual stack of cyan emitting
and 12 nm for peak P2. This would be attributed to the InGaN/GaN MQWs and indium-rich InGaN nanostructures
smaller piezoelectric field between the well and the barrier embedded in the MQW layer.

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Phys. Status Solidi A 207, No. 6 (2010)
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