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Journal of Crystal Growth 351 (2012) 101–106

Contents lists available at SciVerse ScienceDirect

Journal of Crystal Growth


journal homepage: www.elsevier.com/locate/jcrysgro

Mushroom structure of GaN template for epitaxial growth of GaN


Sung Bo Lee n, Tae-Wan Kwon, Jungwon Park, Won Jin Choi, Hae Sung Park
Iljin Materials, R&D Center, LED Division, Ansan 425-090, South Korea

a r t i c l e i n f o abstract

Article history: In the present study, we show the formation of mushroom morphology produced by a ramp anneal of a
Received 14 February 2012 low-temperature GaN buffer layer. Structural analysis by transmission electron microscopy indicates
Received in revised form that the cap of the mushroom has the stable wurtzitic GaN structure, whereas the stem possesses the
24 April 2012
metastable zinc-blende structure. With the air gap introduced between the substrate and the cap of the
Accepted 26 April 2012
mushroom structure, threading dislocations propagate along its stem. The formation of the mushroom
Communicated by C. Caneau
Available online 5 May 2012 morphology is suggested to result from the nucleation of wurtzitic GaN on the surface of the low-
temperature buffer layer during the ramp anneal, followed by mass transport of GaN from the buffer
Keywords: layer, which remains zinc-blende during the anneal, to the surface, because wurtzitic GaN has the lower
A1. Mass transfer
structure energy than zinc-blende GaN. This study extends limits of the conventional use of the buffer
A2. Single crystal growth
layer, laying the foundation for the development of low-cost recipes for achieving GaN templates with a
A3. Metalorganic vapor phase epitaxy
B1. Gallium compounds low density of threading dislocations.
B2. Semiconducting III–V materials & 2012 Elsevier B.V. All rights reserved.
B3. Light emitting diodes

1. Introduction by dielectric materials, such as SiO2 or SiN, separated by window


areas, so that TDs in the layer cannot propagate upwards to the
Since sapphire and GaN are dissimilar in lattice parameter and overlayer during subsequent regrowth. However, the processes
thermal expansion coefficient, direct deposition of GaN on the are achieved at the expense of additional steps, which lead to an
sapphire substrate at a high temperature results in three-dimen- increase in production costs.
sional growth, revealing a noncontinuous film, and the resulting Here, we report the formation of mushroom morphology by a
film contains a high density of threading dislocations (TDs), which simple anneal of a LT GaN buffer layer, a remarkable effect that
are detrimental to light-emitting devices. Thus, it is well accepted seems to provide a more effective way to produce a low-dislocation-
that, for two-dimensional growth of high-temperature (HT) GaN density GaN than the previously suggested methods [3–6,8–11].
epitaxial layers, a buffer layer should be grown at lower tem- When our GaN buffer layer grown at a low temperature (550 1C) by
peratures beforehand to promote uniform coverage on the sap- metalorganic chemical vapor deposition (MOCVD) was ramped to a
phire. The growth of a low-temperature (LT) buffer layer between high temperature (1050 1C) and then cooled to room temperature
the two materials has been employed to accommodate the without being held at the high temperature, it was found that it had
mismatches [1,2]. And several approaches have been implemen- evolved into a mushroom-like structure. The ramp anneal was
ted to reduce the TD density by modifying the buffer layer. The performed in only NH3 and H2 ambient without any introduction
modifications were done by Si/N treatments [3,4], by lowering of Ga source. From the structural analysis by transmission electron
NH3 flow rate [5] or, by lowering V/III ratio [6]. During an anneal, microscopy (TEM), the structure of the mushroom’s cap was
the LT layer undergoes transformation into larger islands with identified as the stable wurtzitic (hereafter, wz) hexagonal GaN
better crystallinity. Threading dislocations (TDs) are accepted to (wz GaN), and the stem region as the metastable zinc-blende (zb)
form by coalescence of those islands [7] and thus, the reduction in cubic GaN (zb GaN). A better-developed (0001) surface was achieved
density of islands by those annealings leads to a decrease in TD by Mg doping. A mechanism for the formation of the mushroom
density. Other promising attempts include the epitaxial lateral structure is suggested.
overgrowth (ELOG) technology and its variants, such as maskless
ELOG [8,9] pendeoepitaxy [10] and air-bridged ELOG [11]. In the
ELOG processes, part of the defective initial GaN layer is masked 2. Experimental methods

In the present study GaN films were grown on c-plane sapphire


n
Corresponding author. Tel.: þ82 31 599 6972; fax: þ 82 31 599 6910. substrates (4 in diameter) by low-pressure metalorganic chemical
E-mail addresses: bolee@iljin.co.kr, bolee@snu.ac.kr (S.B. Lee). vapor deposition (MOCVD) in a vertical reactor (AIXTRON) using

0022-0248/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jcrysgro.2012.04.036
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102 S.B. Lee et al. / Journal of Crystal Growth 351 (2012) 101–106

tri-methyl gallium (TMGa) and ammonia (NH3) as source materials (Gatan Inc., Pleasanton, USA) attached to a field-emission SEM
for Ga and N, respectively. Hydrogen (H2) was used as the carrier (SU70, Hitachi, Japan) and X-ray diffractometry (XRD) (X’Pert Pro,
gas. The deposition and heat-treatment process in the present study PANalytical B.V., Almelo, The Netherlands). The panchromatic CL
was composed of three steps: (i) LT GaN buffer deposition, (ii) ramp images were taken at room temperature at an acceleration voltage
anneal of the buffer layer, and (iii) HT deposition. The flow rates of of 5 keV, providing fast two-dimensional views of the luminescence
TMGa and NH3 were 201 mmol/min and 6200 sccm, respectively, intensity distribution reflecting the local variation of defect density.
during GaN deposition (i and iii), the V/III ratio being 1376. The flow Dislocations appear as dark spots in a CL image, where the
rate of H2 was 56 slm during all the steps. The ramp anneal (ii) was luminescence intensity is decreased due to non-radiative recombi-
performed in only NH3 and H2, whose flow rates were the same as nation, serving as contrast [12]. The full-width at half-maximum
in the buffer growth at the low temperature. The reactor pressure in (FWHM) values of the (0002) and (10–12) planes were measured by
steps (i), (ii), and (iii) was 150, 300, and 300 Torr, respectively. XRD. Defect structures were characterized by transmission electron
Before deposition, all substrates were cleaned with solvents and microscopy (TEM). Specimens for TEM were prepared in a focused
subjected to a heat-treatment in flowing H2 at 1100 1C. Ga-ion beam (FIB) workstation (FEI Nova 200 Nanolab dual-beam
First, an undoped (u-) GaN layer was deposited at a growth FIB, FEI, The Netherlands). The prepared specimens were examined
pressure of 150 Torr and temperature of 550 1C to a thickness of in a field-emission TEM (Tecnai G2 F30 S-Twin, FEI, The Nether-
100 nm under a gas mixture of TMGa, NH3, and H2. The lands) operated at 300 keV (0.2 nm point-to-point resolution).
deposition time at the low temperature was 827 s. The LT GaN
layer was ramped to a high temperature of 1050 1C at a rate of
60 1C/min and then cooled to room temperature without being 3. Results
held at the high temperature.
Next, we examined the effects of the incorporation of Mg on Fig. 1(a) shows a high-resolution TEM (HRTEM) image of an
the mushroom morphology. Biscyclopentadienyl-magnesium undoped GaN (u-GaN) buffer layer ( 100 nm thick) grown at
(Cp2Mg) was used as the source material for Mg. First, an Mg- 550 1C. It was composed of columnar grains (10–25 nm in diameter)
doped GaN layer was grown on the sapphire substrate at 550 1C to with a high density of stacking faults and twins, and fast Fourier
a thickness of  100 nm under the V/III ratio of 1376, as for the transform (FFT) analysis shows that its crystal structure was zinc-
u-GaN layers. During the growth, the flow rate of Cp2Mg during blende (inset in Fig. 1(a) taken along the [110] zone axis). After being
the deposition was 1.6 mmol/min. As for the aforementioned heated to 1050 1C in only NH3 and H2 ambient and then cooled down
u-GaN buffer layer, the ramp anneal was performed in only NH3 to room temperature without being held at the high temperature,
and H2 ambient. Then, to know whether the mushroom structure surprisingly, it was observed that the continuous film had developed
can be useful as a template for a u-GaN overgrowth layer, u-GaN into mushroom shapes, as demonstrated by scanning electron
was further deposited on the mushroom structure at 1050 1C for microscopy (SEM) in tilted view and cross-section bright-field TEM
4600 s under the same V/III ratio as in the LT growth (1376). The (Fig. 1(b) and (c), respectively). Fig. 1(c) shows that the cap of the
resultant GaN film thickness was 3 mm. mushroom structure was faceted with the top (0001) facet and the
Surface morphologies were examined using a scanning electron side facets of {10 11}, which are identified by the measured angle of
microscope (SEM) (FEI Nova 200 Nanolab dual-beam, FEI, The  601, which is close to the angle between the (0001) and (1011)
Netherlands) and a scanning probe microscope (Dimension 3100, planes of GaN (621). (Some facets in Fig. 1(c) exhibit angles much
Veeco Instruments Inc., USA). Crystalline quality was examined by smaller than 621, resulting from cross-sectioning some (10 11)
cathodoluminescence (CL) in panchromatic mode using MonoCL4 facets of the irregular-shaped cap, which were not parallel to the

Fig. 1. (a) High-resolution TEM image of the buffer layer (taken along the [1-100] zone axis of the sapphire substrate (or, equivalently, the [110] zone axis of zinc-blende
(zb) GaN or the [2-1-10] axis of wurtzitic (wz) GaN, following the epitaxial relationship between the three phases)). Inset of (a): FFT pattern of a white-boxed region in (a),
indicating that the layer was severely-faulted zinc-blende. The streaking along the /111S direction resulted from a high density of stacking faults, which were parallel to
the (0001) plane of the sapphire substrate. (b) Tilted-view SEM image of the buffer layer after undergoing the ramp anneal. (c) Cross-section bright-field image taken along
the [1-100] zone axis of the sapphire substrate. (d) Cross-section g–3 g weak-beam dark-field image of the ramp-annealed layer (taken near the [2-1-10] zone axis of wz
GaN with g ¼0002). TDs have screw (s), edge (e) and mixed (m) characters, and in (d) a mixed (m) dislocation is seen. (e) High-magnification image of the white-boxed
region in (d) (along the [1-100] zone axis of the sapphire substrate). (f)–(h) are FFT patterns of white-boxed regions of the mushroom shown in (e)).
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S.B. Lee et al. / Journal of Crystal Growth 351 (2012) 101–106 103

viewing direction (the [2 1 10] zone axis of GaN).) The characters
and morphology of TDs can be clearly discerned in weak-beam dark
field, as exemplified in Fig. 1(d). TDs propagated upwards typically
along the stem to the cap, but due to the air gap between the
substrate and the laterally grown part in the cap (designated as wing),
the wing region (especially its upper part) was relatively free of TDs
(Fig. 1(d)). Fig. 1(e) shows a high-resolution image of the white-boxed
region in Fig. 1(d). Through phase analysis by FFT shown in Fig. 1(f)–
(h), the cap of the mushroom, including its lower part, was identified
as wurtzitic, but its stem remained zinc-blende. The lower part of the
cap had wurtzite structure with a high density of stacking faults. The
phase difference between the cap and the stem hints at the driving
force for the formation of mushrooms, which will be discussed later.
The Mg-doped buffer layer, after undergoing the ramp anneal
step, also showed a mushroom structure, as for the u-GaN buffer
layer, but featured better-developed (0001) surface facets than
the u-GaN mushroom, revealing a higher ratio of the length in the
direction normal to the [0001] direction to that parallel to the [0001]
direction (Fig. 2(a)–(c)). TD propagation along the stem is also seen in
Fig. 2(c). As for the ramp-annealed u-GaN mushroom structure, FFT
analysis of the Mg-doped mushroom structure revealed that the cap
of the mushroom (also including its lower part) was wurtzitic with its
stem being zinc-blende (Fig. 2). Since the Mg-doped mushroom
structure showed a better surface coverage than the u-GaN mush-
room structure, the former was chosen as a template for a u-GaN
overgrowth layer. As shown in Fig. 3(a), the 3 mm thick film on the
Mg-doped GaN mushroom structure preserved the air gap. The
crystal structure of the whole film was wurtzitic, indicating that the
stem of the mushroom structure was transformed from zinc-blende
into wurtzitic during the HT GaN growth. Mg-induced pyramidal
defects [13] appeared near the sapphire/GaN interface with no
inversion domain boundary observed (Fig. 3(b)). Full-width at half-
maximum values of the XRD rocking curves for the (0002) and (10–
12) reflections were 387 and 496 arcsec, respectively. The atomic
force microscopy (AFM) image (Fig. 3(c)) over an area of 5  5 mm2
featured a root-mean-square roughness of 0.33 nm, and the high-
resolution panchromatic cathodoluminescence (CL) image shows a
density of dark spots of 2.2  108 cm  2 (Fig. 3(d)). A plan-view TEM
image taken near the sapphire/GaN interface (Fig. 3(e)) shows
coalescence boundaries, but no sign of such boundaries was observed
near the film surface, as shown in Fig. 3(f), which indicates a TD
density of  3.5  108 cm  2.
We illuminated the effect of HT anneal on the buffer GaN layer.
The anneal was not a growth, and therefore, did not include TMGa.
The u-GaN buffer layer was ramped to 1050 1C, as for the mushroom
structure (Figs. 1 and 2), and then further annealed at the high
temperature for 10 min and 30 min in only NH3 and H2 ambient. For
the specimen annealed for 10 min (Fig. 4(a)), not only the cap but
also the stem regions were identified as wurtzitic, as demonstrated
in Fig. 4(b). For the specimen annealed for 30 min, as shown in Fig. 2. After the ramp anneal, the Mg-doped buffer layer featured a mushroom
structure as demonstrated by SEM in tilted-view (a) and cross-section bright-field
Fig. 4(c), the buffer was severely etched. As in the case of the TEM (taken along the [1-100] zone axis of the sapphire substrate) (b). (c) Cross-
specimen annealed for 10 min, the remaining GaN had been section TEM (g–3 g weak-beam dark-field condition of a mushroom structure
transformed into faulted wurtzite, as shown in Fig. 4(d). (taken near the [2-1-10] zone axis of wz GaN with g ¼0002)). (d) High-magnifica-
tion image of the white-boxed region in Fig. 2(c) (along the [1-100] zone axis of
the sapphire substrate). (e)–(g) are FFT patterns of the white-boxed regions in (d).

4. Discussion
morphology. Therefore the overgrowth at the high temperature can
The streaking along the /111S direction in the FFT pattern in occur on the remaining crystallites and also directly on the sapphire
Fig. 1(a) resulted from a high density of stacking faults, which substrate. Such an overgrowth will deteriorate material quality,
create hexagonal regions (wurtzite) locally [14]. That is, the buffer because TDs would propagate upwards freely in the absence of the
layer had zinc-blende structure with wurzitic layers embedded. air gap. The air gap is likely to be well trapped for the overgrowth on
The observation is consistent with previous results showing that top of mushrooms with better coverage (i.e., with wider (0001)
the buffer layer is largely a mix of zinc-blende and wurtzite surface). Actually, while the HT overgrowth on the u-GaN mushroom
structures instead of equilibrium wurtzite structure [14–16]. layer did not show the air gap clearly (not shown here), that on the
As shown in Figs. 1(b) and 2(a), some crystallites were observed to Mg-doped mushroom with the better coverage exhibited the air gap
remain unchanged without being transformed into the mushroom (Fig. 3(a)). Of course, the overgrowth could occur on the remaining
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104 S.B. Lee et al. / Journal of Crystal Growth 351 (2012) 101–106

Fig. 4. (a) High-magnification bright-field TEM image of the buffer layer after
annealed at the high temperature for 10 min following the ramp anneal (taken
along the [1-100] zone axis of the sapphire substrate). (b) FFT patterns of white-
boxed regions of the mushroom shown in (a) (indicated by numbers, 1  4).
(c) Cross-section TEM image of the buffer layer annealed for 30 min. (d) FFT
pattern of white-boxed regions in (c).

of our future study will be to obtain a mushroom structure with


better coverage than shown in the present study.
The high density of stacking faults shown in the lower part
of the cap of the mushroom (Figs. 1(e) and 2(d)) appears to
propagate from basal-plane stacking faults in the stem. In the
initial stage of the mushroom formation, the faults would gen-
erate steps on the surface of the islands for nucleation and growth
of wz GaN. Shockley partial dislocations along the (111) planes of
zb GaN (stem) possibly run along the (0001) planes of wz GaN
(the bottom of the cap), resulting in stacking faults at the bottom
of the cap, as revealed in Figs. 1(e) and 2(d). That is, the stepped
surface of the zinc-blende island can act as a template for
wurtzitic growth, as proposed by Narayan et al. [14].
The ‘mottled’ contrast in the stem area shown in Fig. 1(d) was
due to defects (dislocations, stacking faults, and boundaries between
columns). Such a mottled contrast was also observed in the lower
Fig. 3. (a) Cross-section two-beam bright-field TEM image of the 3 mm u-GaN film part of the cap. As noted in the previous paragraph, stacking faults
grown at 1050 1C on the mushroom structure (taken near the [2-1-10] zone axis propagated from the stem to the lower part of the cap (Fig. 1(e)). We
with g ¼0002). A high-magnification image in g–3 g weak-beam dark-field (taken suppose that the contrast originated in stacking-fault-related
near the [2-1-10] zone axis of wz GaN with g ¼ 0002) of the white-boxed region in
(a) corresponds to (b). (c) AFM image of the 3 mm GaN grown on the mushroom
defects, such as stacking mismatch boundaries [17] and dislocations
structure. (d) Representative panchromatic CL image. Two-beam bright-field TEM [18]. Through TEM investigations Narayanan et al. [18] suggested
images taken near the sapphire/GaN interface (e) and near the film surface that TDs are generated by climb and glide of basal plane disloca-
(f) (near the [0001] zone axis with g¼ 11  20 (indicated by white arrows)). tions, which form by the dissociation of Shockley partial dislocations
bounding stacking faults. However, TDs were rarely observed to
propagate from the lower part of the wing, but originated at the
crystallites and on the sapphire also for the Mg-doped mushroom stem, as exemplified in Fig. 1(d). This observation indicates that the
structure, because the coverage was not perfect either. The width of density of TDs originating at the GaN/sapphire interface is much
the stem in the overgrowth on the Mg-doped mushroom (sometimes higher than that of TDs which might originate at stacking faults in
larger than 1 mm, Fig. 3(a)) was observed to be larger than in the Mg- the lower part of the wing.
doped mushroom structure itself (normally, 400 nm at most, For both Mg-doped and u-GaN mushroom structures, the caps
Fig. 2(c)). And we attribute the observation to the overgrowth on were faceted, exhibiting (0001) and {10–11} surface facets
the areas not covered by the mushrooms. Thus, one of the objectives (Figs. 1(c) and 2(b)), as shown in the literature [19,20]. However,
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S.B. Lee et al. / Journal of Crystal Growth 351 (2012) 101–106 105

the presence of Mg (Fig. 2(a) and (b)) was observed to widen the remained zinc-blende, its cap was wurzitic. The wz GaN nuclei
(0001) facet relative to the {10–11} facets, as compared with the formed on the island surface will be driven to grow at the expense
u-GaN mushrooms (Fig. 1(b) and (c)). Beaumont et al. [19] of the zb GaN layer below (Fig. 5(b) and (c)), because of the lower
observed that the growth rates in the [0001] and /10–11S structure energy of wz GaN than that of zb phase [28].
directions were strongly affected by introducing Mg. The Mg If the mushroom structure was isothermally annealed at
incorporation was shown to favor the adsorption of Ga on the 1050 1C, the stem was observed to become wurtzite and the
{10–11} facets rather than on the (0001) facet, increasing the mushroom morphology collapsed (Fig. 4). Taking into account
growth rate in the /10–11S directions. As a result, the Mg that the mushroom is driven to form by the phase difference
incorporation promotes faster coalescence in the ELOG process between the cap and stem regions (Fig. 5), the transformation of
[21]. Thus we expect that the Mg incorporation would produce a the stem into wurtzite means the disappearance of the driving
mushroom structure with better surface coverage than without force, and as a result, the mushroom is expected to start to be
any introduction of Mg, and such a tendency is confirmed by a smoothed (indicated by an arrow in Fig. 4(a)) by mass transport
comparison between Fig. 1(b)–(d) (u-GaN mushrooms) and which would be totally driven by surface-energy minimization
Fig. 2(a)–(c) (Mg-doped mushrooms). [29,30]. Such mass transport would thus lead to a mound-like
As shown in Fig. 3(a), for the 3 mm thick GaN film on the Mg- structure, as shown in Fig. 4(a).
doped mushroom structure, several vertical TDs were observed to The HT anneal effect shown in Fig. 4 seems connected to the
propagate from positions away from the stem region. This question of why such a mushroom structure was not observed in
phenomenon is attributed to irregular shapes and random posi- the literature. In the commercial MOCVD growth process, before
tions of stems. Stems developed spontaneously during the ramp growth of HT GaN epitaxial layers, the buffer layer is ramped to a
anneal, featuring irregular shapes and being randomly located on high temperature (ramp anneal) and held at the high temperature
the substrate. Furthermore, TDs generally propagate upwards in for some period of time (HT anneal) with the Ga source off
curve, which is attributed to TD motion due to their interaction. [27,31–33]. These two anneals are included in the so-called recrys-
Thus, although part of a stem or other stems near the TEM- tallization step [27,31–33]. The previous studies [27,31–33] reported
imaged stem are not seen in a TEM image, TDs originating in them the morphological evolution of the buffer layer after the recrystalli-
can appear in the image. zation step. We believe that, since the recrystallization step included
Based on the aforementioned observations (Figs. 1 and 2), a the HT anneal, those studies might have missed the mushroom
plausible scenario is suggested for the mechanism of the mush- formation.
room development, as sketched in Fig. 5. At elevated tempera-
tures during the ramp anneal, the continuous buffer layer is
expected to break up into many three-dimensional islands due to 5. Concluding remarks
the high interfacial energy between GaN and sapphire (Fig. 5(a)),
as is normally observed after the HT buffer anneal process during To conclude, by a simple ramp anneal, we have successfully
MOCVD of GaN [22–24]. Simultaneously, the surface of the implemented a GaN template with the mushroom morphology. The
islands also undergoes decomposition of GaN during the ramp formation of the mushroom structure by the ramp anneal is inter-
anneal, producing metallic Ga atoms located on the film surface preted as proceeding through the following stages: (i) decomposition
[25–27]. The Ga atoms will be spontaneously reacted with of GaN on the surface of the LT GaN buffer during the ramp anneal,
nitrogen (from decomposed ammonia) to newly form GaN crystal (ii) formation of wz GaN on the surface by the reaction between Ga
nuclei on the surface (Fig. 5(a)) [25–27], which is most likely to (from decomposed GaN) and nitrogen, and (iii) mass transport of GaN
have wurtzite structure, stable at such elevated temperatures. The from zb GaN to the stable wz GaN, forming the cap. We have
formation of wurtzite GaN on the surface is clearly corroborated suggested that the mushroom morphology is formed during the ramp
by our present observations shown in Figs. 1(e)–(h) and 2(d)–(g), anneal. If an isothermal anneal at high temperatures is done after the
which shows that, while the stem of the mushroom structure ramp anneal, the mushroom structure is smoothed to become
mound-like, which is driven by surface energy minimization. Such
an isothermal HT anneal has been used after the ramp anneal as the
recystallization step in the literature. This may be the reason why the
mushroom morphology has not been reported so far. The Mg
incorporation induced a mushroom structure with a better surface
coverage than the u-GaN case. The present results provide a wider
perspective on the use of the LT GaN buffer layer, suggesting that
further improvements in fabricating the mushroom structure produce
a GaN substrate with a low dislocation density.

Acknowledgment

This research was supported by the Basic Science Research


Program through the National Research Foundation (NRF) of
Korea, funded by the Ministry of Education, Science and Technol-
ogy (2011–0027382) (Iljin).

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