Selective mask formation and gallium

nitride template fabrication on patterned

sapphire substrates for light-emitting
diodes
Cite as: AIP Advances 10, 095001 (2020); https://doi.org/10.1063/5.0021336
Submitted: 09 July 2020 . Accepted: 11 August 2020 . Published Online: 01 September 2020

Seunghee Cho, Woo Seop Jeong, Min Joo Ahn, Kyu-Yeon Shim, Seong Ho Kang, and Dongjin Byun

COLLECTIONS

Paper published as part of the special topic on Chemical Physics, Energy, Fluids and Plasmas, Materials Science
and Mathematical Physics

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Selective mask formation and gallium nitride

template fabrication on patterned sapphire
substrates for light-emitting diodes
Cite as: AIP Advances 10, 095001 (2020); doi: 10.1063/5.0021336
Submitted: 9 July 2020 • Accepted: 11 August 2020 •
Published Online: 1 September 2020

Seunghee Cho, Woo Seop Jeong, Min Joo Ahn, Kyu-Yeon Shim, Seong Ho Kang, and Dongjin Byuna)

AFFILIATIONS
Department of Materials Science and Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, South Korea

a)
Author to whom correspondence should be addressed: dbyun@korea.ac.kr

ABSTRACT
Patterned sapphire substrates are composed of multiple planes, leading to the undesirable polycrystalline growth of gallium nitride (GaN)
during template deposition. However, patterned sapphire substrates and templates with good crystalline quality would be useful for increasing
the light extraction efficiency in light-emitting diodes. In this study, a silicon dioxide (SiO2 ) mask was selectively introduced onto the lenses of
a patterned sapphire substrate to suppress the growth of polycrystalline GaN. The SiO2 mask prevented the negative influence of the patterned
sapphire substrate on GaN growth under various conditions. High-resolution x-ray diffraction analysis revealed that the GaN template grew
as a single crystal in the presence of the SiO2 mask. Furthermore, the compressive stress generated in the GaN template was relieved due to
the suppression of polycrystalline growth.
© 2020 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/5.0021336., s

I. INTRODUCTION
Compound semiconductors based on III-nitride materials,
which can typically be easily grown on sapphire, silicon carbide
(SiC), and gallium nitride (GaN) substrates, have been extensively
studied.1–4 Although sapphire and SiC substrates with lattice con-
stants similar to III-nitrides are expensive, they are still currently
used for applications such as light-emitting diodes (LEDs)5 and laser
diodes.6,7 In recent years, the use of buffer layers based on relatively
inexpensive silicon has been actively investigated for the growth
of III-nitrides on large-scale substrates.8,9 The most common tech-
niques used to deposit III-nitrides are molecular beam epitaxy and
metalorganic chemical vapor deposition (MOCVD),10,11 where the
latter method is mainly employed in the fabrication of LED chips. In
particular, GaN, aluminum nitride (AlN), and indium nitride (InN)
can be used in the active layer of LED chips to modulate the LED
emission wavelength from the visible to the UV regions and thus
obtain light sources with the desired wavelengths.12
The wavelength generated by the active layer is extracted from
the inside of the chip or trapped inside to be converted into thermal
energy with a concomitant reduction in light efficiency. In an effort
to enhance the light extraction and efficiency, many researchers have
switched from flat sapphire substrates to patterned sapphire sub-
strates (PSSs). In these systems, the light generated in the active
layer is reflected from the PSS to improve light efficiency.13–15 As
various planes exist in the PSS pattern, the active layer must be
grown on the bottom. However, the growth of the pattern affects
templates grown epitaxially, which can reduce the overall crystalline
quality.16,17
In this study, a SiO2 passivation layer was deposited on a PSS
to suppress the undesirable polycrystalline GaN growth on the pat-
tern. The crystalline quality was compared and analyzed via high-
resolution x-ray diffraction (HR-XRD). The quality of the obtained
template was evaluated using cathodoluminescence (CL) spectra and
images.
II. EXPERIMENTAL
Figure 1 presents a schematic diagram of the fabrication
process. The PSSs used in our experiments were cone-shaped
lenses. Acetone and isopropyl alcohol were used to remove organic

AIP Advances 10, 095001 (2020); doi: 10.1063/5.0021336 10, 095001-1

© Author(s) 2020
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FIG. 1. Schematics diagram of the fabrication process: (a) deposition of the AlN buffer layer on the PSS, (b) coating with the photoresist, (c) O2 plasma etching of the
photoresist, (d) deposition of the SiO2 layer, (e) removal of the photoresist and SiO2 mask from the bottom layer, and (f) deposition of the GaN template.

contaminants from the PSSs. Next, an AlN buffer layer was cross-sectional and top-view (inset) SEM images after vertical GaN
deposited on the PSS to reduce the stress in the final template growth at low temperature and high pressure, revealing that the SiO2
by avoiding the lattice mismatch that occurs when growing GaN mask formed on the PSS pattern prevented the GaN from forming a
directly on sapphire [Fig. 1(a)]. The AlN buffer layer was grown to seed layer. Finally, Fig. 2(f) shows the cross-sectional and top-view
a thickness of ∼25 nm via radio frequency sputtering at 1 mTorr, (inset) SEM images of a merged GaN template that grew to ∼4.5 μm
100 ○ C, and 400 W. on the PSS.
The PSS was then coated three times with the photoresist
(AZ-HKT-501) at 3500 rpm, followed by hard baking at 150 ○ C to
evaporate the solvent and slightly reduce the photoresist thickness
[Fig. 1(b)]. The photoresist coated on the specimen was then etched
using an O2 plasma etching system [Fig. 1(c)]. The etching condi-
tions were set such that the top of the PSS/AlN became exposed
through the photoresist, and the residual thickness of the photoresist
in the troughs varied depending on the conditions. Subsequently, a
100-nm-thick silicon dioxide (SiO2 ) mask was deposited onto the
surface, including the PSS lenses exposed by the plasma etching, via
plasma-enhanced chemical vapor deposition at 100 ○ C [Fig. 1(d)].
The photoresist remaining on the substrate was then dissolved
via sonication in acetone, thereby removing the SiO2 from the
troughs but not the cone-shaped lenses [Fig. 1(e)]. Finally, the GaN
template was deposited via MOCVD [Fig. 1(f)]. Vertical growth was
first performed at 1020 ○ C and 300 Torr, followed by horizontal
growth at 1100 ○ C and 85 Torr to merge the GaN.
Samples from each step of GaN template formation were ana-
lyzed by scanning electron microscopy (SEM), crystalline analysis of
the GaN template was conducted via HR-XRD and XRD, and the
stress on the template was evaluated using Raman spectroscopy.

III. RESULTS AND DISCUSSION

Figures 2(a) and 2(b) present the SEM images of the photoresist
coated on the PSS/AlN before and after O2 plasma etching, respec-
tively, where the degree of exposure of the PSS pattern is dependent
on the height of the remaining photoresist. Figure 2(c) shows an
SEM image of a SiO2 mask grown to ∼100 nm on an etched photore- FIG. 2. Characterization of various specimens from the fabrication process: SEM
sist mask. This image clearly demonstrates that the SiO2 remained images (a) after coating with the photoresist, (b) O2 plasma etching of the pho-
on the lenses after removal of the photoresist mask and the SiO2 toresist, and (c) after the growth of the SiO2 mask. (d) EDX mapping image of
deposited thereon. Figure 2(d) presents an energy-dispersive x-ray the obtained surface prior to GaN deposition, where the blue dots represent Si,
and SEM images showing (e) the vertical growth of GaN and (f) the merged GaN
(EDX) mapping image of the obtained surface prior to GaN deposi-
template.
tion in which the blue dots represent silicon. Figure 2(e) shows the

AIP Advances 10, 095001 (2020); doi: 10.1063/5.0021336 10, 095001-2

© Author(s) 2020
 AIP Advances
FIG. 3. XRD 2θ spectrum for the GaN template with the SiO2 mask: (a) GaN(002),
(b) Al2 O3 (006), and (c) GaN(004).
Figure 3 shows the XRD spectrum of a GaN template grown on
a sapphire substrate that induces epitaxial growth. The intense XRD
peaks at 34.6○ and 72.9○ , corresponding to GaN(002) and GaN(004),
respectively, indicate the epitaxial growth of GaN on the PSS. The
GaN template was thick, and the substrate peak [Al2 O3 (006)] was
weak. Comparison with the XRD data for GaN bulk films, revealed
that GaN template formed on the SiO2 mask also possessed a single
crystal shape.18
The crystallinity of GaN was confirmed by analyzing the XRD
rocking curves and pole figures for the GaN template with a SiO2
mask on the PSS lenses, as masks can affect the crystalline quality of
GaN templates.19,20 Figures 4(a) and 4(b) present the rocking curves
for the symmetric (002) and asymmetric (102) reflections, respec-
tively, for the GaN film with the SiO2 mask on the PSS and a GaN
film without a SiO2 mask. The full width at half-maximum (FWHM)
values for the symmetric (002) reflections of GaN with and with-
out the SiO2 mask were 141.3 arcsec and 124.85 arcsec, respectively,
AIP Advances 10, 095001 (2020); doi: 10.1063/5.0021336
© Author(s) 2020
ARTICLE scitation.org/journal/adv
while those for the asymmetric (002) reflections were 191.67 arcsec
and 228.28 arcsec, respectively. According to the results shown in
Fig. 4(a), the GaN template grown with the SiO2 mask possessed
improved crystallinity compared with that grown without the SiO2
mask. The PSS lenses were composed of various planes of Al2 O3
that could interfere with the epitaxial growth of GaN, and the crys-
tallinity was improved because the SiO2 mask suppressed the seed
layer growth of polycrystalline GaN on the PSS lenses. As shown by
the top-view SEM image presented in Fig. 2(e), the growth of GaN
seed crystals on the lenses was not observed. The sharper rocking
curve for GaN(002) with the SiO2 mask demonstrates the influence
of the latter on the crystallinity during the formation of the GaN
template. However, the crystallinity as indicated by the GaN(102)
rocking curve was somewhat reduced. Although the increased crys-
tallinity of GaN(102) improved the crystallinity of the GaN template,
it did not affect the overall crystallinity of the GaN template as much
as GaN(002). The high FWHM for the asymmetric (102) reflections
was attributable to edge dislocations in the GaN template. However,
the screw dislocations of GaN(002) displayed a lower dislocation
density in the presence of the SiO2 mask than in its absence. There-
fore, the GaN template with the SiO2 mask possessed a lower total
dislocation density.
The growth direction of the GaN grown epitaxially on the sub-
strate was confirmed by careful analysis of the pole figures using the
peaks shown in Fig. 3, where the tilt of the template was used to
determine the crystalline quality.21 Figure 5(a) presents the analysis
results based on GaN(002) in which one strong peak was observed at
psi = 0○ and phi = 301.3○ . The PSS was fabricated by dry etching of
the c-plane of the Al2 O3 substrate. GaN did not grow on the PSS pat-
tern composed of various planes, although it could be easily grown
on the bottom surface of the PSS composed of the c-plane. The GaN
possessed a wurtzite structure and had grown in the vertical (002)
direction. As shown in Fig. 5(a), the pole figure for GaN(002) was
concentrated at the center. In contrast, as shown in Fig. 5(b), the pole
figure for GaN(101) contained six symmetrical peaks, indicating that
GaN and Al2 O3 were composed of hexagonal structures.
The threading dislocation density of the GaN template with the
SiO2 mask was measured via CL spectroscopy, where the observed
wavelengths were used to identify threading dislocations, sample
impurities, and defects. Figure 6(a) presents the CL spectra of the
samples acquired at room temperature, where the red and black lines
FIG. 4. HR-XRD rocking curves for the
GaN templates with and without the SiO2
mask: (a) GaN(002) and (b) GaN(102).
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 AIP Advances
FIG. 5. HR-XRD pole figures for the GaN templates with the SiO2 mask: (a) GaN(002) and (b) GaN(101).
correspond to the samples with and without the SiO2 mask, respec-
tively. The bandgap of the GaN template was 3.4 eV, as indicated by
the emission wavelength of ∼364 nm. However, the GaN template
without the SiO2 mask also displayed emission at a wavelength of
422 nm (2.9 eV) owing to defects in the GaN template leading to a
trap state in the energy band diagram. Thus, the deep-level traps at
422 nm did not appear due to reduced defects in the GaN template
when using the SiO2 mask formed on the PSS pattern. Figures 6(b)
and 6(c) show the corresponding CL images of GaN templates with-
out and with the SiO2 mask, respectively. It is evident that the dif-
ference in threading dislocation in the former is more than that in
the latter. These results demonstrate that the GaN template with the
SiO2 mask contained fewer defects than the GaN template without
the SiO2 mask.
FIG. 6. CL spectroscopy of the GaN templates with and without the SiO2 mask: (a)
CL spectra, (b) CL image of the GaN templates without the SiO2 mask, and (c) CL
image of the GaN template with the SiO2 mask.
AIP Advances 10, 095001 (2020); doi: 10.1063/5.0021336
© Author(s) 2020
ARTICLE scitation.org/journal/adv
Raman spectroscopy was used to compare the internal stress in
the GaN templates. The GaN template without the SiO2 mask expe-
rienced less residual stress during merging than that with the SiO2
mask. As shown in Fig. 7, the E2 (high) Raman shift for the con-
ventional GaN template measured at room temperature occurred at
567 cm−1 , and the value for the GaN template with the SiO2 mask
was very close to that. Thus, the template formed using the SiO2
mask contained less residual stress.22
For growing GaN templates via MOCVD, the growth mod-
ules vary depending on the substrate and specific growth conditions.
However, controlling the growth conditions for GaN templates is
time consuming. Figure 8 presents the SEM images that demonstrate
the advantages of using a SiO2 mask. Figures 8(a) and 8(b) show the
GaN templates laterally grown on an AlN buffer layer without a SiO2
mask at 1100 ○ C and 85 Torr (high temperature and low pressure).
FIG. 7. GaN E2 (high) Raman shifts of the GaN templates with and without the SiO2
mask.
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curve analysis confirmed that the GaN templates with the SiO2 mask
possessed higher crystalline quality than that without the mask.
Moreover, the SiO2 mask reduced the internal stress introduced
during the growth of the GaN template. When GaN was grown
directly on the PSS, polycrystalline GaN grew on the PSS lenses. The
SiO2 mask inhibited this polycrystalline growth and thus improved
the crystalline quality of the template. According to SEM analysis,
the deposition of GaN under the same processing conditions had a
positive effect on template growth.

DATA AVAILABILITY
The data that support the findings of this study are available
from the corresponding author upon reasonable request.

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AIP Advances 10, 095001 (2020); doi: 10.1063/5.0021336 10, 095001-5

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