You are on page 1of 6

Home Search Collections Journals About Contact us My IOPscience

Fabrication of a nano-cone array on a p-GaN surface for enhanced light extraction efficiency

from GaN-based tunable wavelength LEDs

This article has been downloaded from IOPscience. Please scroll down to see the full text article.

2008 Nanotechnology 19 405303

(http://iopscience.iop.org/0957-4484/19/40/405303)

View the table of contents for this issue, or go to the journal homepage for more

Download details:
IP Address: 194.57.171.11
The article was downloaded on 14/10/2011 at 12:55

Please note that terms and conditions apply.


IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 19 (2008) 405303 (5pp) doi:10.1088/0957-4484/19/40/405303

Fabrication of a nano-cone array on a


p-GaN surface for enhanced light
extraction efficiency from GaN-based
tunable wavelength LEDs
C B Soh1 , B Wang1 , S J Chua1,2 , Vivian K X Lin1 , Rayson J N Tan1
and S Tripathy1
1
Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology
and Research), 3 Research Link, 117602, Singapore
2
Department of Electrical and Computer Engineering, National University of Singapore,
117576, Singapore

E-mail: cb-soh@imre.a-star.edu.sg and elecsj@nus.edu.sg

Received 8 May 2008, in final form 28 July 2008


Published 20 August 2008
Online at stacks.iop.org/Nano/19/405303

Abstract
We report on the fabrication of a nano-cone structured p-GaN surface for enhanced light
extraction from tunable wavelength light emitting diodes (LEDs). Prior to p-contact
metallization, self-assembled colloidal particles are deposited and used as a mask for plasma
etching to create nano-cone structures on the p-GaN layer of LEDs. A well-defined periodic
nano-cone array, with an average cone diameter of 300 nm and height of 150 nm, is generated
on the p-GaN surface. The photoluminescence emission intensity recorded from the regions
with the nano-cone array is increased by two times as compared to LEDs without surface
patterning. The light output power from the LEDs with surface nano-cones shows significantly
higher electroluminescence intensity at an injection current of 70 mA. This is due to the internal
multiple scattering of light from the nano-cone sidewalls. Furthermore, we have shown that
with an incorporation of InGaN nanostructures in the quantum well, the wavelength of these
surface-patterned LEDs can be tuned from 517 to 488 nm with an increase in the injection
current. This methodology may serve as a practical approach to increase the light extraction
efficiency from wavelength tunable LEDs.
(Some figures in this article are in colour only in the electronic version)

1. Introduction (ηout ) [3, 4]. First, the internal quantum efficiency of the
LEDs on c-plane sapphire is influenced by its crystal quality
The past decade has seen a tremendous advancement in the and the built-in electric field due to spontaneous and strain-
GaN-based light emitting diodes (LEDs) from the early blue induced piezoelectric polarization [4, 5]. Second, the critical
emission [1] to the present-day highly efficient phosphor- cone angle for light to escape from GaN to air is 23◦ . This
coated white LEDs [2]. This research area has attracted
gives a low light extraction efficiency of about 4% for large
considerable attention due to the possibility of replacing
area LED devices [5, 6]. The majority of photons reaching
fluorescent lamps by LEDs for the next generation lighting
applications. However, there is a general concern to improve the surface are internally reflected and subsequently absorbed
the achievable efficiency of the LEDs. There are two by the substrate. To increase the light extraction efficiency,
approaches to increase the overall external quantum efficiency surface roughening, [5, 7] nanorods LEDs with self-assembled
of InGaN-based LEDs: mainly through the increase of internal Ni metal islands [8], and sapphire substrate patterning [9, 10]
quantum efficiency (ηint ) and the light extraction efficiency have been implemented for InGaN-based LEDs.

0957-4484/08/405303+05$30.00 1 © 2008 IOP Publishing Ltd Printed in the UK


Nanotechnology 19 (2008) 405303 C B Soh et al

vapour deposition (MOCVD) reactor. Trimethylgallium


(TMG), trimethylindium (TMI) and ammonia are used as the
precursors for Ga, In, and N, respectively. N2 and H2 serve
as the carrier gas for growth of InGaN and GaN, respectively.
For the LEDs, multiple quantum well (MQW) structures with
three periods are grown with a 4 nm thick Inx Ga1−x N well
(where 0.2 < x < 0.28) and 8 nm thick GaN barrier on top
of the Si-doped GaN/sapphire template. The trimethylindium
(TMIn) and trimethylgallium (TMGa) flow during the growth
of the InGaN well layer is kept at 30 and 25 μm min−1 at
a chamber temperature which is linearly graded from 765
to 760 ◦ C. After the growth of the GaN barrier, a 2 nm
thick InGaN layer (labelled as α -InGaN) is first grown at
a chamber temperature of 765 ◦ C. The TMGa flow is then
stopped and the TMI flow is lowered to 10 μm min−1 for
TMIn treatment. In the absence of TMGa flow, the impinging
indium atoms act as an antisurfactant, enabling them to be
easily absorbed by N-dangling bonds at the underlying InGaN
layer to form indium rich InGaN interconnected quantum dots
(QDs) or nanostructures. The growth of indium rich InGaN
nanostructures has been reported in detail in our previous
work [14]. The InGaN nanostructures are then capped by a
2 nm thick InGaN layer (labelled as γ -InGaN) with TMIn
flow of 40 μm min−1 and a chamber temperature which was
reduced linearly to 760 ◦ C. Such a procedure completes
the growth of InGaN nanostructures embedded within InGaN
Figure 1. (a)–(d) Schematic drawings of the steps involved during wells. After the growth of the InGaN/GaN MQWs, an AlGaN
the fabrication of surface nanostructures in the p-contact region of layer is then deposited, which serves as an electron blocking
LEDs by nanosphere lithography. (e) An SEM image of the layer prior to the top p-GaN growth.
nanospheres generated after RIE etching with a diameter
a = 300 nm and a separation between spheres (centre to centre),
d = 380 nm. (f) A micrograph of the patterned nano-cone arrays on 2.2. Fabrication of a nano-cone array on the p-GaN surface
the p-GaN surface.
The fabrication steps used to generate a large area nano-cone
array on the p-contact region are outlined in figure 1. (a) The
In this work, in order to enhance the light extraction wafer was first spin-coated at 800 rpm with a mono-dispersed
from LEDs, we propose the use of self-assembled polystyrene polystyrene (PS) sphere solution. Depending on the speed of
nanospheres as etched mask materials to form an array of nano- rotation of the spin coater, a monolayer, bilayer or mixture
cones on the p-GaN surface. This technique is a known method of both arrays of polystyrene spheres can be deposited on the
to fabricate large area nanostructures with sufficient control of surface. The size and spacing between the spheres control the
the size and the shape, besides the advantages of having a low shape of the cone after etching. It is essential that a monolayer
cost and high throughput. Previously this method has been of polystyrene spheres be obtained as a bilayer array can affect
demonstrated for a GaN/Si(111) template [11] and organic the shape of the p-GaN nanostructures formed after etching
LEDs [12] as well as 2D slab InGaAs light emitting structures. with the nano-patterned polystyrene mask. (b) The 2D close
However, for the case of voltage tunable LEDs [13], surface packed array of PS spheres was then etched using oxygen as
patterning may play an important role, since the internal an ambient gas in a reactive ion etching (RIE) system. This
quantum efficiency of LEDs decreases for green emitters. The first etching step reduces the size of the spheres. Figure 1(e)
guiding of emitted light from the active junctions is strongly shows an SEM image of the uniform array of nanospheres
dependent on the surface nanostructuring and reflectivity at with a diameter of 280–300 nm and a spacing of 370–390 nm
GaN/air interfaces. The focus of this study is to demonstrate (measured from the centre to centre of two adjacent spheres)
improved light extraction through the formation of surface on the p-GaN surface after RIE etching. (c) The photoresist
nano-cones from a wavelength tunable blue-green LED on was then spin-coated on the nanosphere-patterned LEDs wafer
c-plane sapphire. to define the p-contact region for the LEDs. Using inductive
coupled plasma (ICP) etching in BCl3 (20 sccm) and Cl2
(8 sccm) gases at 6 ◦ C, the p-GaN surface not covered by the
2. Experimental details and methodology
photoresist was etched to form the array of cones. (d) The
2.1. Growth of the wavelength tunable LEDs sample was then immersed in toluene solution and placed in
the ultrasonic bath to remove the residual PS nanospheres.
The LED structure is grown on the c-plane sapphire substrate The photoresist was then removed using acetone and methanol
using an EMCORE D125 turbo disc metalorganic chemical solutions.

2
Nanotechnology 19 (2008) 405303 C B Soh et al

Figure 3. (a) An optical micrograph of an LED die; (b) the tilted


plane view SEM image at the Ni/Au p-contact regions; (c) AFM
line-section analysis of the nano-cone p-contact region giving the
clear dimensions of the cone structure (diameter = 315 nm and
height = 152 nm); (d) an SEM image of the Au p-bond pad on the
patterned region.
Figure 2. Fabrication steps for making a nano-cone p-GaN surface in
InGaN/GaN-based LEDs. (a) Deposition of the polystyrene (PS)
spheres by spin coating, (b) RIE etching in O2 ambient to control the 3. Results and discussion
size of the PS spheres, (c) spin coating of photoresist and lithography
to define the p-contact region for ICP etching, (d) removal of the Figure 3(a) shows an optical micrograph of the fabricated
photoresist and the PS after etching. (e) Optical micrograph of the GaN LED die. The dark patch contrast represents the nano-
patterned LEDs.
cone-patterned region on the Ni/Au contact area. Figure 3(b)
represents the tilted plane view scanning electron microscopy
(SEM) image of the ordered nano-cone array on p-GaN at the
2.3. Device fabrication
p-contact region after Ni/Au metallization. The dimension of
After patterning of the p-GaN surface, fabrication of LEDs each cone is approximately 300 nm in diameter with a height
was carried out with metallic contacts. Figure 2 shows the of 150 nm, which is further confirmed by the atomic force
flowchart for the fabrication of these LEDs. (a) The photoresist microscopy (AFM) line-section analysis over the patterned p-
was first spin-coated on the sample and lithography was done contact region as shown in figure 3(c). Based on mathematical
to cover the p-GaN region with a nano-cone array that serves calculation, the surface area of our fabricated cone is about
as the top surface for light extraction. (b) ICP etching was 1.4 times higher than its base. This implies a bigger exposed
then carried out to etch the mesa to a depth of 0.7 μm so as area for light extraction as compared to a non-patterned p-GaN
to reach the n+ -GaN region. (c) Electron-beam evaporation contact. Such a roughened surface of the GaN also assists in
was used to coat the transparent Ni/Au (5/6 nm) layers on the multiple light scattering at the p-GaN/air interfaces. As for
p-GaN surface and an additional Au layer was subsequently the p-bond pad, a thick 500 nm Au layer was deposited on
deposited to form the p-bond pad. Rapid thermal annealing the transparent Ni/Au coated nano-cone p-GaN surface. The
was then carried out at 550 ◦ C for 5 min in air ambient to rough and grainy dome-like structure of Au bond pad on the
form an intermediate Ni–O semiconductor layer embedded nano-cone p-contact is shown in figure 3(d).
in Ni–Ga–O islands which in turn is believed to serve as After the fabrication of the nano-cone array on the p-
a low barrier contact to p-GaN [15]. The specific contact GaN surface as shown in figure 1, the emission from the
resistance using a Ni/Au (5/6 nm) metallization scheme on sample with/without the patterned regions was tested using
our sample determined by a circular transmission line mask room temperature photoluminescence (PL) mapping. Figure 4
(CTLM) pattern is about 10−4  cm2 . (d) The lithography shows the photoluminescence map over the wafer with the peak
and deposition of the n-contact metal Ti/Al (25/200 nm) on emission at approximately 495.8 nm. The PL intensity of the
n+ -GaN layer was then carried out followed by annealing in sample with the surface nano-cone structures is three times
nitrogen ambient at 550 ◦ C for 2 min. The processed GaN LED as much, as compared to the region without the nano-cone
die with deposited Ni/Au p-layer, the Au bond pad on the nano- structures. The squarish (yellow) patch-like patterns indicate
cone surface, and the fabricated Ti/Al n-contact on the n+ GaN the die regions with the regular nano-cone arrays giving
region can be clearly seen in figure 2(e). stronger luminescence than the conventional p-GaN region

3
Nanotechnology 19 (2008) 405303 C B Soh et al

(b)

Figure 4. (a) The photoluminescence (PL) mapping across the


region with and without the nano-cone structures, and (b) the PL
spectra recorded from two different regions.

(indicated in blue). The regions with and without the surface


nanostructures were labelled in figure 4(a). The nano-cone
structures assist the photons with multiple opportunities to
escape from the wafer surface and redirect the photons which
are originally emitted out of the escape cone back into the
escape cone. This is similar to the effect of the surface Figure 5. (a) Electroluminescence spectra from the LEDs with
nano-cone p-GaN surface. The inset gives the energy band structure
roughening technique adopted for flip-chip LEDs [6] and also
of the GaN/α -InGaN/InGaN nanostructure/γ -InGaN quantum well.
for wet-etched u-GaN template LEDs [16]. (b) Photographic images of the patterned LEDs at injection current
After the device fabrication, the effect of injection current of 10, 30 and 50 mA with their corresponding CIE coordinates.
on the electroluminescence (EL) from LEDs with nano-cone (c) Plots of the light output power and wavelengths as a function of
arrays and non-patterned p-GaN was studied. Based on the EL injection currents for both patterned and non-patterned LEDs.
spectra shown in figure 5(a) for the LEDs with the patterned p-
GaN region, there is a prominent shift in the wavelength from
516 nm at an injection current of 5 mA to 488 nm at 70 mA. where they recombine with holes to give bright green emission
A similar phenomenon is also observed for the non-patterned at 512 nm with CIE coordinates of (0.075, 0.405) for a current
p-GaN LEDs. This is attributed to the incorporation of indium injection of 10 mA (shown in figure 5(b)). The growth of
rich nanostructures embedded in the InGaN well layer. At low these InGaN nanostructures serves as effective carrier trapping
injection current, the electrons and holes recombine mainly at sites in the InGaN well as electrons having to overcome an
the InGaN nanostructures (with higher indium composition). additional potential barrier (at the interface of the InGaN
The band structure of the InGaN/GaN quantum wells (in the nanostructures to the upper 2 nm thick capped γ -InGaN).
absence of applied field) is shown in the inset of figure 5(a). Hence there is a greater tendency for the carriers to thermalize
The graded indium composition of the α -InGaN well layer in the InGaN nanostructures. With a higher injection current
causes the electrons to diffuse to the InGaN nanostructures, at 30 mA, the InGaN nanostructures are now saturated with

4
Nanotechnology 19 (2008) 405303 C B Soh et al

carriers and excess high kinetic energy carriers can overcome nanostructures embedded in the graded InGaN well layer.
the potential barrier to diffuse to the γ -InGaN layer, and give This gives a wavelength tunable InGaN LEDs with embedded
rise to green emission with CIE coordinates of (0.125, 0.355). InGaN nanostructures. A comparative study on the light output
Further increase in injection current to 50 mA enables carriers power shows significant enhancement in light extraction from
to recombine radiatively at the α -InGaN as well as at γ -InGaN the LEDs with the nano-cone patterned p-GaN. The utilization
and InGaN nanostructures, which eventually led to cyan colour of such a low cost and controllable nanosphere lithography
emission at 492 nm with CIE coordinates of (0.156, 0.291). process would allow researchers to significantly improve the
Figure 5(c) shows the plots of light output power and light extraction efficiency from InGaN/GaN-based LEDs.
wavelength as a function of the injection current for both
types of LED. The nano-cone patterned and the non-patterned Acknowledgments
LEDs show nearly equal amounts of EL peak blue shift from
516 to 488 nm as the injection current is increased from 5 This work was supported by Exploit Technologies (ETPL),
to 70 mA. The light output power from both LEDs increases A-Star, Singapore. The authors are grateful for the financial
linearly with an initial injection current up to 50 mA but for support provided under the White LEDs Flagship project
the non-patterned GaN LEDs, it started to saturate at higher (IMRE/07-7P0601)
injection current. However, for the case of LEDs with nano-
cone p-GaN surface, the output power continues to increase
steadily even after 70 mA. The light output power of such References
patterned GaN LEDs was about 1.8 times higher than the
[1] Nakamura S and Fasol G 1997 The Blue Laser Diode
conventional non-patterned LEDs at the injection current of (New York: Springer)
70 mA. The use of nano-cone patterns on the p-GaN surface [2] Kanno H, Sun Y and Forrest Stephen R 2006 Appl. Phys. Lett.
improves the escape probability of photons due to the angular 89 143516
randomization of photons through internal scattering from [3] 2006 LED lighting technology: lessons from the USA DTI
the nano-cone sidewalls. As expected, this effect led to an Global Watch Mission
increase in the light extraction efficiency of these LEDs. Based [4] Sun Y, Cho Y-H, Kim H-M and Kang T W 2005 Appl. Phys.
Lett. 87 093115
on cathodoluminescence measurements, Pérez-Solórzano et al
[5] Lin C-F, Zheng J-H, Yang Z-J, Dai J-J, Lin D-Y, Chang C-Y,
[17] have identified confinement of emission mainly at the Lai Z-X and Hong C S 2006 Appl. Phys. Lett. 88 083121
sidewalls of pyramidal structures for InGaN/GaN MQWs [6] Fujii T, Gao Y, Sharma P, Hu E L, DenBaars S P and
emitting between 490 and 510 nm, and this is quite similar to Nakamura S 2004 Appl. Phys. Lett. 84 855
our observations in LEDs with nano-cone-patterned p-GaN. [7] Billeb A, Grieshaber W, Stocker D, Schubert E F and
Karlicek R F 1997 Appl. Phys. Lett. 70 2790
[8] Chiu C H et al 2007 Nanotechnology 18 445201
4. Conclusions [9] Wuu D S, Wang W K, Wen K S, Huang S C, Lin S H,
Huang S Y, Lin C F and Horng R H 2006 Appl. Phys. Lett.
In summary, the nanosphere lithography technique with 89 161105
polystyrene spheres as the etching mask is used to generate [10] Cuong T V, Cheong H S, Kin H G, Kim H Y, Hong C-H,
nano-cone structured p-GaN in InGaN/GaN LEDs. An Suh E K, Cho H K and Kong B H 2007 Appl. Phys. Lett.
enhancement in the integrated PL emission intensity is 90 131107
[11] Wang L S, Tripathy S, Wang B Z and Chua S J 2006 Appl. Surf.
observed from the patterned nano-cone regions of the p-GaN Sci. 253 214
surface. This is due to an increase roughening of nano- [12] Wang B, Ke L and Chua S J 2006 J. Cryst. Growth 288 119
cone sidewalls with an apex angle of ∼45◦ and multiple [13] Soh C B, Chua S J and Hartono H 2008 Phys. Status Solidi c
scattering of the emitted photons at the GaN/air interfaces. 5 2183
This detailed fabrication study ensures that nano-cone arrays [14] Soh C B, Liu W, Teng J H, Chow S Y, Ang S S and Chua S J
are patterned uniformly in the light emitting region and the 2008 Appl. Phys. Lett. 92 261909
[15] Cao X A, Stokes E B, Sandvik P, Taskar N, Kretchmer J and
electrical property of the p-GaN contacts does not degrade
Walker D 2002 Solid-State Electron. 46 1235
with additional processing steps. EL spectra show a change [16] Peng W C and Wu Y S 2006 Appl. Phys. Lett. 88 181117
of emission wavelength with injection current, and this is [17] Pérez-Solórzano V, Gröning A, Jetter M, Riemann T and
attributed to the carrier filling mechanism in the InGaN Christen J 2005 Appl. Phys. Lett. 87 163121

You might also like