Applied Physics Express 12, 015502 (2019) LETTER

https://doi.org/10.7567/1882-0786/aaef40

Crystal structure control of Au-free InAs and InAs/GaSb heterostucture nanowires

grown on Si (111) by metal-organic chemical vapor deposition
Ramesh Kumar Kakkerla1 , Deepak Anandan1 , Sankalp Kumar Singh1 , Hung Wei Yu1 , Ching-Ting Lee4,
Chang-Fu Dee5 , Burhanuddin Yeop Majlis5, and Edward Yi Chang1,2,3*
1
Department of Materials Science and Engineering, National Chiao Tung University, University Road, Hsinchu, 30010, Taiwan, Republic of China
2
Department of Electronics Engineering, National Chiao Tung University, University Road, Hsinchu, 30010, Taiwan, Republic of China
3
International College of Semiconductor Technology, National Chiao Tung University, University Road, Hsinchu, 30010, Taiwan, Republic of China
4
Department of Photonics Engineering, Yuan Ze University, Taoyuan 32003, Taiwan, Republic of China
5
Institute of Microengineering and Nanoelectronics, Universiti Kebangsaan Malaysia, Bangi, 43600, Malaysia
*
E-mail: edc@mail.nctu.edu.tw
Received October 10, 2018; accepted November 6, 2018; published online November 26, 2018

In this letter, the growth of gold-free GaSb on various InAs nanowire (NW) crystal structures using metal-organic chemical vapor deposition is
demonstrated. The GaSb was grown radially and axially on wurtzite (WZ), zinc-blend (ZB) and polytype (mixture of WZ and ZB) InAs NWs. The
effect of the various InAs crystal structures on GaSb was studied. This study demonstrates the control of the crystal growth of InAs and InAs/GaSb
heterostructure NWs through the optimization of growth parameters and crystal transfer from core to shell, such techniques are necessary for the
growth of NWs for future nanoelectronic device applications, such as TFET. © 2018 The Japan Society of Applied Physics

Supplementary material for this article is available online

O
ne-dimensional semiconductor nanowires (NWs)
represent a unique class of semiconductor nanos-
tructures. Semiconductor NWs have provided a new
platform for the evolution of many electronic,1) photonic2)
and energy applications3) over the past two decades because
of their unique optical and electronic properties. In particular,
III-Sb NWs are emerging as a promising class due to the
properties such as narrow direct band gaps and high carrier
mobilities which are desired for low power and high speed
applications. However, synthesizing the III-Sb NWs have
many challenges due to the low equilibrium vapor pressure of
Sb, which are generally not present for other III–V NWs,
demanding the need for in depth investigation.4) Crystal
quality has always been of utmost important parameter for
performance and reliability of III–V NW devices. In contrast
to III–V NWs, the crystal structure of III-Sb NWs has been
limited to zinc-blend (ZB) structure till date, with few reports
on wurtzite (WZ) antimonides.5) The crystal structure of a
material has a large impact on material and electronic
properties such as surface energies, bandgap energy and
band alignment. So, it can be beneficial to have control on the
growth of crystal structures of antimonides.
Although a good control has been demonstrated over the
dimensions, size dispersions, positioning and crystal structure
of the NWs using external catalyst like gold (Au),6,7) challenges
remain in the growth of Au-free NWs with good crystal quality.
Polytypism, twin defects and stacking faults can easily occur in
Au-free NWs grown along the 〈111〉 direction, and are difficult
to eliminate due to the small growth window,8) these defects
can dramatically affect the electronic properties of the
materials.9) An additional motivation to grow heterostruture
NWs is that the shell crystal structure is determined by the core
crystal structure and thus opening the way for crystal structure
engineering (band structure engineering) which cannot be
achieved using bulk material growth.10) In this paper, the
growth of gold-free GaSb on various InAs NW crystal
structures on Si substrate by metal-organic chemical vapor
deposition (MOCVD) is reported. GaSb was grown radially
and axially on polytype, WZ and ZB InAs NWs and the InAs
core crystal structure effect on the structure of the grown GaSb
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shell material is investigated. This results show that the growth
of InAs and InAs/GaSb heterostructure NWs with the various
crystal structures can be achieved through the optimization of
the growth parameters and crystal structure transfer from core
to shell. The techniques developed in this study are important
for the growth of NWs for next generation nano electronic
devices.
All NWs used in this study were grown on Si (111)
substrate in a shower head MOCVD system. The chamber
pressure was 100 mbar during the growth. All the NWs were
grown by previously established growth method.11) InAs
NWs were grown at conditions suitable to yield the various
crystal structures. Polytype InAs NWs were grown at 580 °C
for 180 s using TMIn and AsH3 with molar fractions of
1 × 10−5 moles min−1 and 4.5 × 10−3 moles min−1, respec-
tively. WZ InAs NWs were grown at 610 °C for 180 s using
TMIn and AsH3 with molar fractions of 3.2 × 10−5
moles min−1 and 4.5 × 10−3 moles min−1, respectively. ZB
InAs NWs were grown by adding antimony (Sb) during the
InAs NWs growth and ternary InAs(Sb) alloy NWs were
formed. For the InAs(Sb) NWs growth, the growth time was
increased to 10 min and the growth temperature, TMIn and
AsH3 flow rates were remained the same as used for polytype
InAs NWs growth. Following the growth of InAs NWs with
different crystal structures, GaSb was grown both in axial and
radial directions to study the core crystal structure effect on
the shell crystal structure. GaSb was grown with fixed growth
temperature (530 °C) and TMGa (7.64 × 10−5 moles min−1)
and TMSb (4.8 × 10−5 moles min−1) flow rates.
The morphology of these grown NWs was characterized
by high resolution field-emission scanning electron micro-
scope (SU8010, Hitachi, Japan) at 45° tilt angle. The NW
crystal structure was investigated by recording in the 〈110〉
zone axis (cubic notation) using 300 kV JEOL 2100 F high
resolution field emission gun transmission electron micro-
scope (HRTEM) with 0.17 nm point resolution in conven-
tional mode. TEM samples were prepared by gently touching
the substrate to the lacey carbon film covered Cu grid. The
NW chemical compositions were obtained by X-ray Energy
Dispersive Spectroscopy.
© 2018 The Japan Society of Applied Physics
Appl. Phys. Express 12, 015502 (2019) R. K. Kakkerla et al.

Fig. 1. (Color online) SEM and TEM analyses of (a)–(d) InAs NWs (polytype) grown at 580 °C, (e)–(h) InAs NWs (WZ) grown at 610 °C and (i)–(l) InAs
(Sb) NWs (ZB) grown at 580 °C. (a), (e), (i) are 45° tilted view SEM images of corresponding NWs (Inserts are high magnification images with scale bar
200 nm). (b), (f) and (j) are low magnification TEM images of Polytype InAs NW, WZ InAs NW and ZB InAs(Sb) NW respectively (inserts show the EDX
profiles). (c), (g) and (k) are HR-TEM images of corresponding NWs. (d), (h) and (l) are corresponding FFT profiles.

Figure 1(a) shows the InAs NWs with average diameter of
60 nm and average length of 1.4 μm. To study the structural
properties of InAs NWs, HR-TEM measurements were
performed. Figure 1(b) shows a bright field (BF) low
magnification TEM image along with EDX profile.
Figure 1(c) is an InAs NW HR-TEM image, which shows
a high density of twins and SFs. Figure 1(d) is the
corresponding Fast Fourier Transform (FFT) profile. The
steaky lines in FFT profile are indicative of structural defects
in the NW. Such twins and SFs were formed by random
stacking of the closest packed planes during the NW crystal
growth.12) The resulting mixture of WZ and ZB phases i.e.
polytype crystal structure is similar to previously reported
III–V NWs grown by MOCVD.13) Figure 1(e) shows InAs
NWs with 60 nm average diameter and 1.6 μm average
length. Changing growth temperature from 580 °C to
610 °C and TMIn flow rate from 1 × 10−5 moles min−1 to
3.2 × 10−5 moles min−1 did not change the NW diameter but
with only a small change in NW length. Figure 1(f) shows a
BF low magnification TEM image along with EDX profile.
Figure 1(g) is a HR-TEM image of the InAs NW grown. The
NW shows a homogeneous contrast within the NW, no twins
and SFs can be observed. Figure 1(h) shows the corre-
sponding FFT profile. The satellite spots are clearly seen and
no steaky lines are observed. This indicates that, InAs NWs
grown are pure WZ crystal structure without any defect. It
has been previously reported that, III–V NWs grown at
higher temperature with high group III (or low group V) gas
flow rate resulted in good crystal quality due to the change in
surface energies at the vapor–liquid and liquid–solid
interface.14,15) InAs NW crystal quality dependence on the
growth temperature and the NW diameter has been reported
elsewhere.16,17) Simulation shows InAs NW based Tunnel
FET has excellent device performance provided the crystal
quality is good.18) In order to grow InAs NW with pure ZB
crystal structure, antimony (Sb) was added during the InAs
NW growth. Figure 1(i) shows the InAs(Sb) NWs grown
with TMSb flow rate of 3.0 × 10−4 moles min−1 and other
parameters kept same as that of the polytype InAs NW
015502-2
growth. NW length decreased from 1.4 μm to 1 μm and
diameter increased from 60 nm to 130 nm [Fig. 1(i)]. This is
in contrast to the growth of pure InAs NWs, where an
increase in the V flux results in the NW diameter decrease
and the NW length increase.19,20) Although Sb is also a group
V element, the NW morphology becomes quite different,
suggesting a more complicated role of Sb on NW growth.
Decrease in length and increase in diameter of III-Sb NWs
due to addition of Sb during growth has been previously
observed.21,22) Figure 1(j) shows a BF low magnification
TEM image along with EDX profile indicating the presence
of Sb (8.1%). Figure 1(k) is an InAsSb NW HR-TEM image.
The NW shows a homogeneous contrast, no twins and SFs
are observed. Figure 1(l) is the corresponding FFT profile
showing pure crystalline ZB structure. Adding Sb into the
InAs NW during the growth reduced the SFs and twins in the
NWs. The results are in good agreement with the previous
reports, that Sb incorporation can suppress the defects
formation in the InAs NWs.23) In the view of these reports
and of the present work, it is clear that change in morphology
and crystal structure should be linked to the presence of
antimony. This could be due to its well-known surfactant
effect. Due to the Sb surfactant effect, as the TMSb flow rate
increases the diffusion length of the In adatoms is decreased
and manifested in an enhancement of the InAs(Sb) NWs
radial growth rate.24) In future, pure InAs NWs with ZB
crystal structure will be obtained either by further increasing
arsine flow or by decreasing indium flow from flow rates
used for polytype InAs NWs growth.15)
In order to investigate the GaSb shell crystal structure
dependence on the core InAs crystal structures, GaSb was
grown at 530 °C for 20 min on InAs NWs with various crystal
structures. Figure 2(a) shows the polytype InAs/GaSb hetero-
structure NWs with 150 nm average diameter and 1.52 μm
average length. Figure 2(b) shows a BF low magnification
TEM image along with images of other locations on the NW. It
should be noted that alternative dark and bright contrast bands
are observed, which is attributed to the twins and SFs in the
NW. Figure 2(c) is an InAs/GaSb NW HR-TEM image along
© 2018 The Japan Society of Applied Physics
Appl. Phys. Express 12, 015502 (2019)
Fig. 2. (Color online) Polytype InAs/GaSb heterostructure NWs (a) 45° tilted view SEM image (Insert is high magnification image with scale bar 200 nm).
(b) Low magnification TEM image showing the locations of other images. (c) HR-TEM image showing interface along radial direction. (d) Corresponding FFT
profile. (e) HR-TEM image showing GaSb growth along axial direction. (f) Corresponding FFT profiles of two locations.
the radial direction, which shows a high density of twins and
SFs. Figure 2(d) is the corresponding FFT profile with steaky
lines. It is observed that the defects inside the InAs core are
extended into the GaSb shell, which degraded the shell crystal
quality. So, it is essential to eliminate defects in the InAs core
NWs to achieve high-quality GaSb shell, which will be
discussed later in the paper. In addition to the radial growth,
the GaSb axial growth also observed. Figure 2(e) is a HR-TEM
image of InAs/GaSb NW showing GaSb grown along axial
direction. Two GaSb regions, one of lower InAs/GaSb core–
shell and one of upper GaSb are clearly visible [Fig. S1(c)–(d)
supplementary material is available online at stacks.iop.org/
APEX/12/015502/mmedia]. Interface between radial and axial
GaSb is abrupt [Fig. S1(a) in the supplementary material]. The
FFT images shown in Fig. 2(f) reveals that the axially grown
GaSb has a crystal structure of ZB with very few SFs. This
behavior emphasizes the novelty of NW growth. Even though
the substrate or lower part is of different material with huge
number of defects, a good quality crystalline material can also
be grown on the template. This ZB crystal structure usually
arises in the growth of InSb or GaSb NWs along 〈111〉
direction.25,26)
Figure 3(a) shows WZ InAs/GaSb heterostructure NWs with
140 nm average diameter and 1.72 μm average length.
Figures 3(b) and 3(c) show the TEM images of grown WZ
InAs/GaSb NW and exhibiting a clear contrast between the
core and the shell [Fig. S2(c) in the supplemetary material].
Figure 3(d) shows the corresponding FFT profile. Spots in the
profile are clearly seen and no steaky lines can be observed,
showing good crystalline WZ structure. However, the splitting
in spots due to the InAs and GaSb can barely be visible because
of the low lattice mismatch. InAs WZ crystal structure was
transferred successfully to GaSb shell through layer by layer
radial growth. This conforms that III-Sb WZ crystal structured
NW shells indeed can be grown on the side walls of WZ
structured NW cores. This crystal structure transfer from core
to shell through layer by layer has been observed and reported
for other III–V NWs.27) Figure 3(e) is a HR-TEM image of
InAs/GaSb NW showing GaSb shell grown along axial
direction [Fig. S2(d) in Supporting material]. The FFT image
shown in Fig. 3(f) reveals that the axially grown GaSb also has
015502-3
R. K. Kakkerla et al.
a WZ crystal structure which is in contrast to the polytype
where ZB axial growth was found. Axially grown GaSb
possessing WZ crystal structure has never been observed
before even by using an external catalyst.28) This situation is
additionally illustrated in the supplementary information.
Figure S2(a) (supplementary information) shows HRTEM
image of interface between InAs core and GaSb, showing
layer by layer growth without any defects.
Figure 4 shows the ZB InAs(Sb)/GaSb heterestructure
NWs. Figure 4(a) shows InAs(Sb)/GaSb heterostructure NWs
with 200 nm average diameter and 1.1 μm average length.
Figure 4(b) shows a BF low magnification TEM image.
Figure 4(c) is an InAs(Sb)/GaSb NW HR-TEM image along
the radial direction [Fig. S3(a) in the supplementary mate-
rial]. As the NW diameter is very large (∼200 nm), the
interface between core and shell was not clearly observed.
Figure 4(d) shows the corresponding FFT profile. Spots in
profile are clearly seen and no steaky lines were observed,
showing good crystalline ZB structure. The InAs(Sb) core
ZB crystal structure was transferred successfully to GaSb
shell through layer by layer radial growth as explained earlier
in the case of WZ structure. Shell with good crystalline ZB
structure and highly regular morphology has been grown on
the defect-free core for III–V NWs.29,30) Figure 4(e) is an
InAs(Sb)/GaSb NW HR-TEM image showing GaSb grown
along axial direction [Fig. S3(b) in the supplementary
material]. Interface between core and axial GaSb was not
clearly observed due to very large (∼200 nm) diameter. The
FFT image shown in Fig. 4(f) reveals that the axially grown
GaSb also has a ZB crystal structure. Here, as the shell follow
the core crystal structure, axially grown GaSb also has the
same crystal structure (ZB) as that of core by growing layer
by layer, the same as in the WZ case. Crystal structure
transfer among NW heterostrures along axial and radial
directions for III–V materials has been reported earlier.31)
Table I summarizes the the crystal structure, size and the
crystal quality of InAs/GaSb heterostructure NWs with
different InAs NW crystal structures.
In conclusion, we have demonstrated the growth of gold-
free GaSb on InAs NW with different crystal structures on Si
substrate by MOCVD. GaSb was grown radially and axially
© 2018 The Japan Society of Applied Physics
Appl. Phys. Express 12, 015502 (2019) R. K. Kakkerla et al.

Fig. 3. (Color online) WZ InAs/GaSb heterostructure NWs (a) 45° tilted view SEM image (Insert is high magnification image with scale bar 200 nm). (b)
Low magnification TEM image showing the locations of other images. (c) HR-TEM image showing clear interface along radial direction. (d) Corresponding
FFT profile. (e) HR-TEM image showing GaSb growth along axial direction. (f) Corresponding FFT profile.

Fig. 4. (Color online) ZB InAs(Sb)/GaSb heterostructure NWs (a) 45° tilted view SEM image (insert is high magnification image with scale bar 200 nm). (b)
Low magnification TEM image showing the locations of other images, (c) HR-TEM image showing GaSb growth along radial direction. (d) Corresponding
FFT profile, (e) HR-TEM image showing along axial direction. (f) Corresponding FFT profile.

on polytype, WZ and ZB crystal structure InAs NWs and the Table I. Summary of the crystal structure, size and the crystal quality of
InAs NW crystal structure effect on the structure of the GaSb InAs/GaSb heterostructure NWs with different InAs NW crystal structures.
shell grown is studied. Polytype and pure crystalline WZ InAs (Core) InAs/GaSb (Core/Shell) GaSb (Axial)
InAs NWs were grown using the properly controlled growth
Polytype (60) Polytype (150) ZB (120)
parameters. Pure ZB InAs NWs has been grown by adding WZ (60) WZ (140) WZ (120)
Sb during the growth. For polytype crystal structure, GaSb ZB (130) ZB (200) ZB (80)
shell was grown around InAs core resulted in the same
*Inside brackets are the sizes of the NWs in nm.
polytype and axially grown GaSb possesses ZB structure. In
the case of WZ structure, a very good crystalline WZ GaSb InAs/GaSb heterostructure NWs crystal structures provides
shell was obtained. Surprisingly, axially grown GaSb also an effective approach for the growth of NWs for next
follows the InAs core crystal structure (WZ). Axially grown generation nano electronic device applications, such as
GaSb with WZ crystal structure has never been observed TFET.
before even by using external catalyst. For NW core with ZB Acknowledgment This work was supported by the “Center for
crystal structure, both axially and radially grown GaSb Semiconductor Technology Research” from The Featured Areas Research Center
Program within the framework of the Higher Education Sprout Project by the
possesses ZB structure. SEM and TEM measurements Ministry of Education (MOE) in Taiwan, R.O.C. Also financially supported in
revealed that InAs NWs with various crystal structures can part by the Ministry of Science and Technology (MOST), Taiwan, under Grant
be obtained by properly adjusting the growth parameters. MOST-107-3017-F-009-002.
This also reveals that InAs/GaSb core–shell NWs with the ORCID iDs Ramesh Kumar Kakkerla https://orcid.org/0000-0002-3938-
good crystal quality can be successfully grown and their 3649 Deepak Anandan https://orcid.org/0000-0002-7668-8169 Sankalp
Kumar Singh https://orcid.org/0000-0003-4282-8706 Hung Wei Yu
crystal can be tuned between WZ and ZB structures by tuning https://orcid.org/0000-0002-0063-4359 Chang-Fu Dee https://orcid.org/
the structure of the NW cores along both radial direction and 0000-0003-1015-9181 Edward Yi Chang https://orcid.org/0000-0003-1616-
axial direction. This demonstration of the control of InAs and 5240

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Appl. Phys. Express 12, 015502 (2019) R. K. Kakkerla et al.

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