a
solidi
ORIGINAL PAPER Texto
Chemical Vapor Deposition
Self-Induced Nucleation Growth of GaN Columns by
Chemical Vapor Deposition ISSN: 1862-6300 (print). 1862-6319 (online)
Francisco S. Ramírez-González,* Godofredo García-Salgado, Cris!oforo Morales,
Tomás Díaz, Enrique Rosendo, Fabiola G. Nieto-Caballero, Jos!e A. Luna,
Antonio Coyopol, Román Romano, Reina Galeazzi, and Hugo Martínez
First published: 14 February 2018
GaN columns are grown by (1 1 1) GaAs nitridation at 1000 ! C. GaAs wafers
are used as a substrate and Ga source. The nitridation is performed using a
hydrogen and ammonia flow mix into a horizontal chemical vapor deposition
(CVD) system at atmospheric pressure. XRD in correlation with pole figure
shows that the structure is wurtzite with a (0 0 0 2) preferential plane. The
SEM images show the growth of GaN columns with an agglomerate
formation on top. EDS results show that the agglomerate is Ga rich,
suggesting a self-induced nucleation growth. The growth mechanism is
discussed briefly. The average diameter and length of the columns are around
1.2 and 10 mm, respectively. The method reported here do not use a template
or foreign metallic particles catalyst.
1. Introduction
The study of the heteroepitaxial process of GaN on different
substrates obey to the interest of minimize the lattice
mismatch.[1] The material strain produces several defects,
affecting the electrical and optical material properties. GaN
wires have been proposed as promised solution of the lattice
mismatch problem, since allows the lattice relaxation improving
the material properties, depending of the wire geometry.[2,3]
F. S. Ramírez-González, Dr. G. García-Salgado, Dr. C. Morales,
Dr. T. Díaz, Dr. E. Rosendo, Dr. J. A. Luna, Dr. A. Coyopol,
Dr. R. Romano, Dr. R. Galeazzi
Centro de Investigaci!on en Dispositivos Semiconductores
Benem!erita Universidad Aut! onoma de Puebla
14 Sur y Av. San Claudio
72570 Puebla, M!exico
E-mail: f25rmz@hotmail.com
Dr. F. Gabriela Nieto-Caballero
Facultad de Ciencias Químicas
Benem!erita Universidad Aut! onoma de Puebla
14 Sur y Av. San Claudio
72570 Puebla, M!exico
Dr. H. Martínez
Centro de Nanociencia y Micro y Nanotecnologías
Instituto Polit!ecnico Nacional
Calle Luis Enrique Erro s/n
Unidad Profesional Adolfo L! opez Mateos
Col. Zacatenco, C.P. 07738 DF, M!exico
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/pssa.201700791.
DOI: 10.1002/pssa.201700791
Phys. Status Solidi A 2018, 1700791 1700791 (1 of 5)
physica
status
www.pss-a.com
Berlin Germany SCIE
The metal-catalyzed vapor-liquid-solid
(VLS) growth method is used for GaN
wires growth by chemical and physical
vapor deposition utilizing Au, Ni, Fe, and
Co particles.[4,5] The metallic particles
introduce undesired contamination. This
drawback has motivated self-induced nu-
cleation growth studies of GaN wires. The
self-induced nucleation of GaN wires has
been reported with molecular beam epitaxy
(MBE)[6] and hydride vapor phase epitaxy
(HVPE).[3] Metal catalysts is currently used
in GaN wires growth by metal–organic
chemical vapor deposition (MOCVD).[7]
The growth of self-induced GaN wires by
MOCVD has been reported using selective
growth on patterned surfaces, which
require a substrate preparation before the wire growth[6,8,9] or
a deposited layer.[7,10,11]
The GaAs nitridation is used as a buffer layer to reduce the
lattice mismatch, to grow the zinc-blende or wurtzite GaN
structure, or to enhance the photoluminescence.[12–16] Our
interest in this method is based in the possible obtainment of
auto-sustainable GaN, because it allows to remove the grown
material from the substrate.
In this letter, we present GaN micrometric columns growth by
GaAs (1 1 1) substrate nitridation with a flow mix of hydrogen
and ammonia. In our experiments, the substrate is the only one
Ga atoms source, not photolithography or any kind of deposited
layer was used.
2. Experimental Section
The substrate cleaning process (wet cleaning) consisted in an
immersion for 5 min in ultrasonic bath in xylene, acetone, and
methanol (separately). After that, the wafer was immersed into a
solution of H2SO4 þ H2O2 þ DI-water (5:1:1) at 60 ! C for 2 min,
and then, HCL þ H2O2 (1:1) at room temperature for 2 min.
After the cleaning process, the sample was placed on a
graphite susceptor into a horizontal chemical vapor deposition
(CVD) reactor. The system was purged with hydrogen to
eliminate the residual oxygen into the reactor. With the system
sealed, the pressure was raised to atmospheric pressure using a
H2 flow of 2100 sccm. After that, an exhaust valve was opened to
allow the H2 flow out and equilibrate the pressure with the
atmospheric pressure. The exhaust line has a bubbler with
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
Figure 1. GaN columns obtained at 1000 ! C by GaAs (1 1 1) nitridation. a) SEM image shows hexagonal columns grown in aleatory directions, (b) the
average diameter was around 1.2 mm measured at the average column height, and (c) the average length of the columns was around of 10 mm.
glycerin to trap the As. The flow must exceed a pressure of
47.88 Pa (abs) to be able to exit the reactor through the bubbler.
The heat system was turned on and the temperature was raised
to 350 ! C with a H2 flow. After 3 min, the temperature was
increased to 550 ! C and a NH3 flow of 200 sccm was added, the
samples remained for 10 min (dry cleaning). Afterward, the
temperature was raised to 1000 ! C for 1 h. Immediately after
the nitridation time, the heat system was shut down and the
reactor was evacuated while the sample temperature was
around 1000 ! C. Finally, the samples were cooled without
cool-control using an electric fan.
The flows were controlled with a mas-flow controller UNIT
model UFC-7360. The heat system consisted six 1600 W
Figure 2. EDS characterization performed at 2.5, 5, 10, 15, 20, 25, and
30 KeV on the top of one column. The plots were placed from the
minimum (at the bottom) to the maximum (at the top) beam energy.
Excess gallium at the tip suggests a self-induced nucleation growth.
Phys. Status Solidi A 2018, 1700791 1700791 (2 of 5)
Texto
a
solidi
physica
status
www.pss-a.com
IR-lamps Philips 13568U/98, the heat rate was of 220 ! C min#1.
The average time to increase the temperature from 24 to 350 ! C
was 2 min, from 350 to 550 ! C 1 min, and from 550 ! C to 1000 ! C
3 min. The temperature control is a 2208e Eurotherm connect-
ed to a 7100A Eurotherm Single Phase Power Thyristor Unit.
The cooling average time was of 20 min (from 1000 to 24 ! C).
The sample surfaces showed a yellow–brown layer; the back of
the substrate in contact with the susceptor and the surface
exposed to the gas flow. The last one was studied, GaN hexagonal
columns were unintentionally formed. The material can be
easily separated from the substrate by exerting a slight force
parallel to the surface.
The morphology was studied by scanning electron micro-
scope (SEM), using a JEOL JSM 7800 F. The chemical
composition was studied by energy dispersive spectroscopy
(EDS), using a detector EDAX model Apollo XL. The X-ray
diffractometer Bruker D8 with a Cu anode X-ray tube and a
nickel filter to remove kβ, the resulting kα1 and kα2 beams with a
mean wavelength of 0.1542 nm focused onto the sample. Pole
diagrams were measured in a PANalytical X’Pert PROMRD
system with a Xe gas-based proportional detector with a parallel
plate collimator. The samples were static, and the diffraction
plane was perpendicular to the surface. Photoluminescence
characterization was made at room temperature using a 325 nm
He–Cd, 10 mW Kimmon laser beam focused on the sample, the
resulting photoluminescence was directed to a 0.85 m mono-
chromator and measured using a GaAs photomultiplier.
3. Results and Discussion
Figure 1a shows a SEM image of the GaN columns growth by
GaAs nitridation at 1000 ! C. The average diameter and length of
the columns were around 1.2 mm (Figure 1b) and 10 mm
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
Figure 3. XRD pattern of the GaN sample obtained at 1000 ! C. The
wurtzite structure present a (0 0 0 2) preferential plane. The cubic
phase presence is attributed to a structure mix on the basis of the
columns.
(Figure 1c), respectively; it can be appreciated that the columns
tips are thinner at the end and present an agglomerate on the
top. The growth direction was arbitrary, it does not follow the
direction of the gas flow. The thin wires between columns are
under study, but preliminary morphology studies indicate that
are similar to wires obtained by He et al.[17] The nitridation
temperature and the substrate orientation have an important
impact in the morphology. The nitridation temperature was
Figure 4. Pole figure of the GaN sample obtained at 1000 ! C at 2θ ¼ 34.5! ,
the peak around ψ ¼ 0! corresponds to (0 0 0 2) w-GaN. The z-GaN
structure is not observable around ψ ¼ 60! .
Phys. Status Solidi A 2018, 1700791
a
solidi
physica
status
www.pss-a.com
varied in 800, 900, and 1000 ! C and it was observed the GaN
columns formation only at 1000 ! C. On the other hand, when the
orientation of the substrate was changed from GaAs (1 1 1) to
GaAs (1 0 0) and the nitridation was performed at 800, 900, and
1000 ! C GaN columns formation were not observed.
Figure 2 shows an EDS characterization made on the top of
one column, performed at 2.5, 5, 10, 15, 20, 25, and 30 to increase
the beam penetration. The plots were placed from the minimum
(at the bottom) to the maximum (at the top) beam energy. The
change in the Ga presence, as the beam energy increases,
indicates that the metal agglomerates at the tip of the columns.
These results lead us to propose a self-induced VLS growth as the
possible mechanism involved in the GaN columns growth. The
amount of Ga available depends on the GaAs dissociation rate,
where Ga droplets are formed to lead a self-induced nucleation.[2]
A detailed investigation of the growth mechanism and the
influential factors (cleaning process, substrate orientation) are in
progress.
At 1000 ! C the substrate of GaAs is dissociated into Ga(l) and
As(g) forming agglomerates or drops of Ga, these are the seeds
for the column formation.[6,18,19] The material morphology is
related with the drops size. In our experiments, the GaAs
substrate is used as a Ga source, and on the same substrate the
GaN columns are grown. The GaAs dissociation rate influences
in the morphology. It is possible that at 1000 ! C and at
atmospheric pressure, part of the formed GaN is also dissociated
forming Ga(l) and N(g) available for the nucleation of the GaN,
contributing to the columns formation, as reported by Koleske
et al.[20] to determine this possibility it would be necessary to
carry out an in situ study.
The structural characterization (XRD) of GaAs (1 1 1) nitridated at
1000 ! C is shown in Figure 3. The structure corresponds to wurtzite
(w-GaN) structure with a preferential (0 0 0 2) plane. Low intensity
diffraction peaks at 40 and 86.8! matches with the (2 0 0) and (4 0 0)
zinc-blende GaN (z-GaN). The z-GaN structure was preferential in
our studies of nitridation at 900 ! C without GaN column formation.
At 1000 ! C, it was observed traces of agglomerates around the
columns, at the base, the columns growth could take place around
these agglomerates, when the temperature is increased.[21] Pole
Figure 5. Photoluminescence pattern obtained at room temperature. The
maximal intensity is centered at 372 nm.
1700791 (3 of 5) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
Figure 6. AFM GaAs substrate images. a) After the wet and dry cleaning. b) After having separated the GaN grown columns.
figure is shown in Figure 4 with 2θ ¼ 34.5! , the peak around ψ ¼ 0!
corresponds to (0 0 0 2) w-GaN. The z-GaN structure is not
observable around ψ ¼ 60! ,[12] the peak at (0 0 0 2) corresponds to a
wurtzite structure with the (0 0 0 2) orientation.
The photoluminescence pattern obtained at room temper-
ature is showed in Figure 5. The emission peak centered at
372 nm (3.34 eV) related with the band–band transition is
observed. The crystalline quality is like the reported by
Escobosa et al.[16] using a similar GaAs nitridation process.
The material grown by the described nitriding process can be
separated from the substrate. Figure 6a shows the substrate
morphology after having removed the grown material. AFM was
made of substrate subjected to both wet cleaning (chemical
immersion) and dry cleaning (inside the reactor), as described in
the experimental part, to observe the substrate morphology
before the growth process, the result is presented in Figure 6b.
The GaN material was detached from the substrate mechanically
exerting a slight pressure with tweezers tip at one end of the
substrate blade. The possibility of reusing the material is under
study.
4. Conclusion
In summary, it is reported the GaN columns growth by GaAs
(1 1 1) substrates nitridation at 1000 ! C and atmospheric
pressure. The substrate is the only Ga source. A better
understanding of the nucleation and the mechanism
involved in the growth are necessary, but the presence of
Ga at the column top indicate a self-induced nucleation
growth. We are working in the growth mechanism,
considering the substrate cleaning process, the nitridation
temperature, the substrate orientation, and the reactor
environment during the cooling.
Conflict of Interest
The authors declare no conflict of interest.
Phys. Status Solidi A 2018, 1700791 1700791 (4 of 5)
a
solidi
physica
status
www.pss-a.com
Keywords
CVD, GaN structures, nitridation, self-induced nucleation
Received: October 18, 2017
Revised: December 19, 2017
Published online:
[1] L. Liu, J. H. Edgar, Mater. Sci. Eng. R Rep. 2002, 37, 61.
[2] V. G. Dubrovskii, V. Consonni, A. Trampert, L. Geelhaar, H. Riechert,
Phys. Rev. B # Condens. Matter Mater. Phys. 2012, 85, 1.
[3] G. Avit, K. Lekhal, Y. Andr!e, C. Bougerol, F. R!everet, J. Leymarie,
E. Gil, G. Monier, D. Castelluci, A. Trassoudaine, Nano Lett. 2014, 14,
559.
[4] S. K. Lee, H. J. Choi, P. Pauzauskie, P. Yang, N. K. Cho, H. D. Park,
E. K. Suh, K. Y. Lim, H. J. Lee, Phys. Status Solidi Basic Res. 2004, 241, 2775.
[5] C. C. Chen, C. C. Yeh, C. H. Chen, M. Y. Yu, H. L. Liu, J. J. Wu,
K. H. Chen, L. C. Chen, J. Y. Peng, Y. F. Chen, J. Am. Chem. Soc. 2001,
123, 2791.
[6] T. Aschenbrenner, G. Kunert, W. Freund, C. Kruse, S. Figge,
M. Schowalter, C. Vogt, J. Kalden, K. Sebald, A. Rosenauer,
J. Gutowski, D. Hommel, Phys. Status Solidi B 2011, 248, 1787.
[7] M. M. Rozhavskaya, W. V. Lundin, E. Y. Lundina, V. Y. Davydov,
S. I. Troshkov, A. A. Vasilyev, P. N. Brunkov, A. V. Baklanov,
A. F. Tsatsulnikov, V. G. Dubrovskii, J. Appl. Phys. 2015, 117, 0.
[8] V. Purushothaman, V. Ramakrishnan, K. Jeganathan, CrystEngComm
2012, 14, 8390.
[9] W. Chen, J. Lin, G. Hu, X. Han, M. Liu, Y. Yang, Z. Wu, Y. Liu,
B. Zhang, J. Cryst. Growth 2015, 426, 168.
[10] K. A. Bertness, A. Roshko, L. M. Mansfield, T. E. Harvey,
N. A. Sanford, J. Cryst. Growth 2007, 300, 94.
[11] R. Koester, J. S. Hwang, C. Durand, D. L. S. Dang, J. Eymery,
Nanotechnology 2010, 21, 15602.
[12] H. Vilchis, V. M. Sanchez-R, A. Escobosa, Thin Solid Films 2012, 520,
5191.
[13] D. J. As, D. Schikora, A. Greiner, M. Lübbers, J. Mimkes, K. Lischka,
Phys. Rev. B 1996, 54, R11118.
[14] G. Shimaoka, T. Aoki, Y. Nakanishi, Y. Hatanaka, T. Udagawa, Appl.
Surf. Sci. 2001, 175, 436.
[15] V. Hoffmann, F. Poser, C. Kaspari, S. Wecke, M. Pristovsek,
W. Richter, J. Cryst. Growth 2004, 272, 30.
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 a

solidi
physica

status
www.advancedsciencenews.com www.pss-a.com

[16] A. Escobosa, V. M. Sánchez-R, M. a. Avenda~ no, G. Navarro, Phys.
Status Solidi 2005, 242, 1883.
[17] M. He, I. Minus, P. Zhou, S. N. Mohammad, J. B. Halpern, R. Jacobs,
W. L. Sarney, L. Salamanca-Riba, R. D. Vispute, Appl. Phys. Lett. 2000,
77, 3731.
[18] V. Purushothaman, V. Ramakrishnan, K. Jeganathan, RSC Adv. 2012,
2, 4802.
[19] B. S. Simpkins, L. M. Ericson, R. M. Stroud, K. A. Pettigrew,
P. E. Pehrsson, J. Cryst. Growth 2006, 290, 115.
[20] D. D. Koleske, A. E. Wickenden, R. L. Henry, J. C. Culbertson,
M. E. Twigg, J. Cryst. Growth 2001, 223, 466.
[21] M. Q. He, I. Minus, P. Z. Zhou, S. N. Mohammed, J. B. Halpern,
R. Jacobs, W. L. Sarney, L. Salamanca-Riba, R. D. Vispute, J. Cryst.
Growth 2000, 77, 3731.

Phys. Status Solidi A 2018, 1700791 1700791 (5 of 5) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim