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Phys. Status Solidi C 6, No. S2, S519– S522 (2009) / DOI 10.1002/pssc.200880782

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current topics in solid state physics
Novel tunable phosphor-free
white III-nitride light emitting diodes based
on indium rich InGaN nanostructures
C. B. Soh*, 1, W. Liu1, S. J. Chua**, 1,2, J. H. Teng1, Rayson J. N. Tan1, and S. S. Ang1
1
Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link,
Singapore 117602
2
Singapore-MIT Alliance, National University of Singapore, 4 Engineering Drive 3, Singapore 117576

Received 9 September 2008, revised 17 November 2008, accepted 19 November 2008

Published online 16 February 2009

PACS 68.65.Fg, 68.65.Hb, 73.40.Kp, 78.60.Fi, 78.67.De, 85.60.Jb

*
Corresponding author: e-mail cb-soh@imre.a-star.edu.sg, Phone: +65-68748257, Fax: +65-67740142
**
e-mail elecsj@nus.edu.sg

Phosphor free tunable white light emitting diodes (LEDs)
have been fabricated using stacked InGaN/GaN quantum
wells (QWs) comprised of a lower set of red emitting QWs
with an upper set of blue and green emitting QW layers. With
antisurfactant treatment, indium rich InGaN nanostructures
are incorporated in the InGaN/GaN quantum well during
growth. AFM study shows the formation of InGaN nanostruc-
tures with an average diameter of 40-80 nm in the quantum
well layer. This growth technique enables red emitting III-
Nitride based LEDs to be generated. With the growth of addi-
tional stacked blue/green QWs on these red emitting QWs
with InGaN nanostructure incorporation for white light gen-
eration, competition arises between the quantum well layers
for thermalization of injected carriers. The transport of holes
from the p-GaN layer determines the radiative recombination
event as holes have a lower mobility than electrons. At low
injection current, emission from the upper blue/green QWs
layer dominates where electron–hole (e–h) pair recombina-
tion takes place. With higher injection current, more holes
diffuse across the GaN barrier to recombine with electrons at
the InGaN nanostructures in the lower sets of QWs. Based on
the band structure for the stacked QWs, the existence of these
In-rich nanostructures leads to more effective carrier trapping
at the lower set of QWs as electrons have to overcome an ad-
ditional potential barrier (at the interface of InGaN nanostruc-
tures to the InGaN well layer). There is also a higher ten-
dency for thermalization of carriers at the lower energy states.
The effect of band filling under higher injection current also
enables the excess holes to recombine at the lower set of QW
layers with indium rich nanostructure, which accounts for the
continuous increase in higher emission wavelength from the
EL spectra.

© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction There is an intensive research into
phosphor-free white III-Nitride Light Emitting Diode
(LEDs) in recent years due to disadvantages of using phos-
phors for light conversion. This includes issues such as
poor color rendering index, a short lifetime due to phos-
phor degradation and lower power efficiency [1]. Pioneer
work to generate phosphor free white light was done by
Damilano et al. [2] and Yamada et al. [3] by having
InxGa1–xN/GaN quantum wells (QWs) of different indium
composition. Each of these QWs hence emits at different
wavelength and the combination of these emissions gives
white light. Several techniques have since been proposed
for generation of phosphor free white LEDs. Huang et al.
has generated white emission using pre-strained growth of
InGaN/GaN quantum wells (QWs) [4] while Guo et al. has
used a single cascade LEDs chip consisting of InGaN and
AlGaInP multiple quantum wells (MQWs) based LEDs in-
tegrated by wafer bonding [5]. This technique required ad-
ditional wafer bonding step and the degradation of the two
materials system may differ with usage leading to change
in color quality with time. Recently, Funato et al. has dem-
onstrated a polychromatic emission (inclusive of white)
from LEDs using micro-structured multifaceted quantum
wells [6]. However, this required complex patterning of n-
GaN template and subsequent regrowth to form the re-
quired structure.

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S520 C. B. Soh et al.: Novel tunable phosphor-free white III-nitride light emitting diodes

To be free from the disadvantages of using phosphor After the growth of the After the growth of
for light conversion, our group has worked on the indium underlying InGaN the InGaN cap layer
rich InGaN nanostructures incorporation in the QWs to layer
shift the emission from the InGaN/GaN QWs to higher Sample A Sample C
wavelength [7, 8]. Using stacked InGaN/GaN QWs with
indium rich nanostructures incorporation, we have gener-
ated phosphor-free red-emitting LEDs as well as white
LEDs.

2 Experimental procedure
A 2 μm n-GaN epilayer was grown on sapphire sub-
strate by Metalorganic Chemical Vapor Deposition
(MOCVD) system with TrimethylGallium (TMGa),
TrimethylIndium (TMIn) and ammonia which serve as the
source gas. The InGaN/GaN multiple quantum wells
(MQWs) were then grown on the n-GaN layer with 10 nm
thick GaN barrier and a 4 nm thick InGaN well which con-
sists of an (i) underlying InGaN wetting layer, denoted as
α-InGaN, (ii) TMIn treatment for indium-rich nanostruc-
tures growth followed by (iii) a cap InGaN layer, denoted Sample B Sample D
as the β-InGaN layer. The use of multiple InGaN layers for
grown of embedded indium rich InGaN nanostructures Figure 1 AFM images on the left shows the morphology of the
were partly to reduce the residual strain due the nanostruc- InGaN underlying layer (a) without TMIn (antisurfactant) treat-
tures formation [9]. Based on the above steps, the follow- ment of TMIn = 0 µmol/min and (b) with TMIn (antisurfactant)
ing InGaN/GaN QWs samples were grown for our study. treatment of 12 µmol/min. The AFM images on the right shows
the morphology of the sample after the growth of a InGaN layer.
Quantum well Sample A with only the α-InGaN layer,
Sample B with an additional TMIn treatment for indium
complete the well. The underlying InGaN acts as a strain
rich nanostructures growth, Sample C with α-InGaN fol-
adjustment template and enhanced the formation of in-
lowed by β-InGaN layer and lastly Sample D with α-
dium-rich InGaN nanostructures in the quantum well layer.
InGaN, indium rich nanostructures followed by β-InGaN
Figure 1 shows the SEM images of the quantum wells
layer.
sample A, B, C and D. In Fig. 1(a), the surface morphol-
For generation of the red-emitting LEDs, growth of the
ogy of sample A with the InGaN wetting layer (α-InGaN)
quantum well sample D was carried out and followed by a
was relatively smooth with terrace-like contours due to the
25 nm thick GaN cap layer before a 250 nm thick p-GaN
high NH3 flow. Whereas for sample B with TMIn treat-
epilayer was grown. As for generation of white light, a
ment after the InGaN wetting layer growth, two-
combination of quantum wells consisting of sample D fol-
dimensional islands of nanodots with size of 50-150 nm
lowed by two quantum wells with structure of sample C
were formed on top of the terrace-like structures of the In-
were grown at 765 °C and 780 °C. The latter quantum
GaN wetting layer as shown in Fig. 1(b). With growth of
wells were used to generate green and blue emission re-
the InGaN cap layer (β-InGaN), nanostructures of size 40-
spectively. These combined with the underlying red emit-
80 nm are formed on the underlying 2D elongated islands
ting quantum well gave white emission with growth of the
of InGaN as shown for sample D [8]. For case of growth
p-GaN epilayer to form the white LEDs. To determine the
on the α-InGaN (sample A) without the TMIn treatment,
composition of indium, x, in the InxGa1–xN well, 3 periods
the surface morphology after the growth of the InGaN cap
of each individual quantum wells, QWs of sample C at 780
o layer are undulated (as shown in Sample C) which would
C and 765 oC, sample D at 745 oC were grown. Micro-
be due to inhomogeneity in the incorporation of InGaN
Photoluminescence (micro-PL) measurement was con-
well at different region of the wafer. Hao et al. has reported
ducted for these MQWs sample. From the peak position of
similar observation of interface roughness for InGaN/GaN
the PL spectra, the composition of indium, x, in InxGa1–xN
quantum well due to phase separation and composition
well was determined to be approximately x ~ 0.18, 0.32
variation in the well [11].
and 0.45, respectively for the samples using Vegard’s Law
Figure 2 shows a monolithic red III-Nitride LEDs by
calculation.
using embedded indium rich nanostructures in the active
3 Results and discussions InGaN/GaN quantum well (QWs) layers. Indium dots were
To initiate the growth of indium-rich InGaN nanostruc- soldered on the p-GaN epilayer and the n-GaN region to
tures, TrimethylIndium (TMIn) treatment using indium as serve as the contact to the LEDs. Bright red emission at a
antisurfactant [8] was introduced on underlying InGaN peak wavelength of 650 nm was obtained with an injection
wetting layer before capping it with another InGaN layer to current of 40 mA. With addition of stacked layers of green

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 Contributed
Article

Phys. Status Solidi C 6, No. S2 (2009) S521

In terms of the Commission International de

(a) (b)
Figure 2 (a) Red emitting III-Nitride LEDs with embedded in-
dium rich nanostructures in the active InGaN/GaN quantum well
layers. (b) Tunable White LEDs with stacked InGaN/GaN QWs
structures comprising of a lower set of red emitting indium rich
nanostructures incorporated QWs with an upper set of blue and
green emitting QWs layer.
and blue emitting quantum wells, tunable white LEDs is
obtained as shown in Fig. 2b with a turn-on voltage at
4.5 V.
Figure 3 shows the room temperature broad electrolu-
minescence (EL) spectra taken from the tunable white
LEDs with increasing injection current. There is competi-
tion between the upper blue/green emitting quantum wells
and the lower red emitting quantum well layer for ther-
malization of injected carriers during radiative recombina-
tion. The transport of holes from the p-GaN layer deter-
mines the radiative recombination event as holes have a
lower mobility than electrons. At low injection current, in-
jected carriers recombine radiatively mainly at the upper
blue and the green emitting quantum wells layer which is
closer to the p-GaN epilayer due to the lower mobility of
the holes as compared to electrons. This accounts for the
apple white emission from the LEDs at injection current of
40 mA (as shown in Fig. 2a).
900
S3
800 Tunable White
700 LEDs
S2
Intensity (a.u.)
I’Éclairage (CIE) chromaticity diagram, the emission at
IInj = 40 mA is at (0.335, 0.420). With higher injection cur-
rent, more holes diffuse across the GaN barrier to recom-
bine with electrons at the InGaN nanostructures in the
lower sets of QWs. This would be due to the saturation of
the carriers in the green/blue QWs and hence there is a
higher tendency for the carriers to recombine at the lower
indium rich nanostructures incorporated QWs. A redshift is
observed from the dominant peak position of the red emit-
ting quantum well from λ = 580 nm at Iinj = 30 mA to
λ = 621 nm at Iinj = 100 mA. This leads to a change in the
chromaticity to position x,y = (0.395, 0.405), giving a rela-
tively warm white emission. Dussaigne et al. has observed
similar phenomenon from the monolithic white LEDs us-
ing quantum wells of different emission wavelength [12].
The band structure for the stacked QWs with different
indium composition in the InGaN well for the tunable
white LEDs is as shown in Fig. 4. The effect of spontane-
ous and piezoelectric fields on the schematic band struc-
ture of GaN/InGaN/GaN corresponding to a compressively
strained InGaN well system has been illustrated by Stevens
et al. [13]. With the incorporation of these In-rich InGaN
nanostructures, it leads to more effective carrier trapping at
the lower set of QWs as electrons have to overcome an ad-
ditional potential barrier (at the interface of InGaN nano-
structures to the InGaN well). Hence, there is a higher ten-
dency for thermalization of carriers at the lower energy
Lower set Upper set
+
n -GaN QWs QWs pGaN
underlying In0.3Ga0.7N
InGaN well
20mA
30mA GaN
40mA barrier

600 50mA
60mA GaN layer
500 GaN GaN
70mA barrier barrier barrier
400 80mA
S1 90mA
In0.4Ga0.6N Psp+Ppz
300 well
100mA Psp
200 Psp Psp
300K
100
0
40 mA
-100 (a)
In-rich E field (b) 40 mA
350 400 450 500 550 600 650 700 750 800 850 900
nanostructure

Wavelength (nm)
Figure 3 Electroluminescence (EL) spectra of the tunable White
LEDs taken at 300 K. The gray circular dots show the shift in the
dominant peak position with current. S1, S2 and S3 with the dot-
ted points show the shift in the emission wavelength with injec-
tion current.
Figure 4 Energy band structure of the LEDs at the in-
terface of the stacked quantum well structures.
states. Secondly, the effect of band filling of the upper set
of QWs under higher injection current (≥ 70 mA) also en-
ables the excess holes to recombine at the lower set of
QWs layer with indium rich InGaN nanostructures. This

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 pss c
solidi
physica
status
S522 C. B. Soh et al.: Novel tunable phosphor-free white III-nitride light emitting diodes
accounts for the continuous increase in intensity for the
higher emission wavelength peak, S3 from the EL spectra
whereas the emission spectra of the peaks S1 and S2 are
saturated with an current injection of Iinj = 80 mA.
In summary, we have demonstrated a red emitting III-
Nitride LEDs with indium rich InGaN nanostructures in-
corporation to shift the conventional quantum well emis-
sion to higher wavelength. With the insertion of additional
layers of green and blue quantum well, tunable white
LEDs can be generated. The color chromaticity of the
LEDs can be tuned due to the difference in the ease of car-
rier trapping and subsequent recombination at different
layers of the InGaN/GaN quantum wells with injection
current.
Acknowledgements The author would like to acknowl-
edge the grant provided by ETPL, A-Star to attend the IWN 2008
workshop and also the financial support for the project.
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