Chinese Journal of Electronics

Vol.18, No.4, Oct. 2009

Synthesis and IR Vibrational Spectrum on GaN
Nanocrystalline Prepared by Sol-gel Method

LI Enling
1
, MA Deming
1
, WANG Xuewen
2
, QI Wei
1
and ZHU Hong
1
(1.Science School, Xian University of Technology, Xian 710048, China)
(2.Electronic Information Science and Engineering School, Northwestern University, Xian 710068, China)
Abstract High quality GaN nanocrystalline has been
prepared by sol-gel method. The results of X-ray dirac-
tion (XRD), Selected-area electron diraction (SAED)
and High-resolution transmission electron microscopy
(HRTEM) measurement indicate that as-prepared sample
is single crystalline GaN with wurtzite structure. Trans-
mission electron microscopy (TEM) displays that the di-
ameters of the grains of GaN nanocrystalline change from
30nm to 100nm. X-ray photoelectron spectroscopy (XPS)
conrms the formation of the bond between Ga and N
in the sample, and IR spectrum measurement showed
E1 (TO) vibrational modes at 570cm
1
. Vibrational fre-
quency of GaN small clusters has been calculated using
Density functional theory (DFT). Using the result, IR
spectrum of the sample has been analyzed further.
Key words GaN, Nanocrystalline, Sol-gel, Density
functional theory (DFT).
I. Introduction
Gallium nitride (GaN) is a promising optoelectronic ma-
terial because of the excellent property and direct wide band
gap (Eg = 3.45 eV at room temperature), so the electronic
and optoelectronic devices made of GaN and related mate-
rials have been developed in recent years, for example high-
temperature and high-power transistors, blue and ultraviolet
(UV) Light emitting diodes (LEDs), and so on
[13]
. Owing
to the great prospects of GaN nanomaterials in devices appli-
cations and the low-cost nanotechnology, GaN nanomaterials
have attracted extensive interests in the related study
[47]
.
Since direct application of the complex materials of high
molecular quantum dots and vapor synthesis of excellent one-
dimensional and bulk GaN materials are needed, it is the key
to synthesize well-crystallized GaN nanomaterials with even
grain diameter. GaN nanocrystalline has been synthesized
with Ga2O3 by Di Lello and his co-workers, as well as Cho
and his co-workers
[7,8]
, and has composed with GaAs by Ish-
erwood and his co-workers
[9]
, with GaP by Gao et al.
[10]
.
In this paper, GaN nanocrystalline with good quality
has been prepared by a simple and cost-eective sol-gel
method. The crude materials are Ga2O3 powder, the mix-
ture of concentrated HCl and HNO3, citric acid, acetone, am-
monium hydroxide, ethylenediamine and 99.99% free ammo-
nia. Structure, composition and vibrational spectrum of the
GaN nanocrystalline have been analyzed respectively in XRD,
TEM, XPS and IR spectrum. Vibrational frequency of GaN
small clusters has been calculated using Density functional the-
ory (DFT), IR spectrum of the sample has been analyzed fur-
ther.
II. Experimental
Firstly, about 7.25g Ga2O3 has been dissolved in the
mixture of concentrated HCl and HNO3, and the solution
has been neutralized to pH 7.58.0 by adding ammonium
hydroxide. Then an overdose Citric acid (CA) has been
added in the solution. The solution has been stirred with
a magnetic stirrer at 350K temperature for 2.5 hours to ob-
tain white shiny crystals which are Ga-citrate-amine crystals
((NH4)3[Ga(C6H5O7)2]4H2O). The crystals have been ltered,
then washed with acetone, and heated for drying at 400K
temperature in a vacuum desiccator. Having been entirely
grounded with a full ball-milling process, then the dried crys-
talline has been dissolved into ethylenediamine at room tem-
perature, and stirred with the magnetic stirrer for 2 hours to
ensure complete mixing. The uniformly transparent and light-
yellow sol thus formed and is rather stable. It took several days
to be gelated in the desiccator at room temperature. Subse-
quently, the gel has been dried in the desiccator at 423K for
4 hours, and calcined at 673K for 1 hour in a mue furnace,
then has been entirely grounded with a ball mill, and treated
for 3 hours after free ammonia in an atmosphere furnace with
a quartz tube. In the ammoniating period, the gas ow of free
ammonia is 300 ml/h, the temperature has been up to 950K
at 10K/min heating-up rate.
III. Results and Discussion
Fig.1 shows XRD pattern of the samples. All the dirac-

Manuscript Received June 2008; Accepted Mar. 2009. This work is supported by Xian Science and Technology Fund (No.Y07064),
Xian Applied Materials Innovation Fund Application (No.XA-AM-200812), Doctor Startup Fund of Xian University of Technology
(No.108-210904).
616 Chinese Journal of Electronics 2009
tion peaks are completely consistent with the standard card
of GaN, and the peaks can be indexed to a hexagonal
wurtzite GaN with lattice constants of a = 0.3186nm and
c = 0.5178nm. There is no diraction peaks from other impu-
rities in any of our samples, which indicates that the sample is
of high purity, and the sharp diraction peaks also reveal that
the sample is highly crystallized.
Fig. 1. XRD pattern of the GaN nanocrystalline
The TEM images of the samples are given in Fig.2. In
Fig.2(a), the diameters of the grains of the powder change
from 30nm to 100nm. A High resolution TEM (HRTEM) lat-
tice image and the corresponding Selected area electron dirac-
tion (SAED) of an individual grain are shown in Fig.2(b). The
regular and order diraction spots correspond with the dif-
ferent planes of hexagonal wurtzite GaN, which explains that
the sample is single crystal and is in accordance with the pre-
ceded XRD result. The spacing between adjacent fringes is
about 0.246 nm which is similar to the spacing of 0.243 nm
between two (101) lattice planes, which further indicates that
the growth direction of the GaN nanograin is perpendicular to
the (101) plane.
Fig. 2. (a) Typical TEM image of the GaN nanocrystalline;
(b) HRTEM lattice image of an individual grain of the
GaN nanocrystalline, inset is the SAED pattern
Fig. 3. IR spectrum of GaN
nanocrystalline
Fig.3 shows IR spec-
trum of GaN nanocrys-
talline. The peak at
570cm
1
is E1 (TO) vibra-
tional modes
[11]
, and the
peak has shift to high en-
ergy because of the small
size eects, surface and in-
terface eects or stress and
strain of GaN nanocrys-
talline. The peak at 996
cm
1
is close to Ga-N stretch vibrational frequency of GaN.
Vibrational frequencies of GanN (n = 2 8) and GanN2
(n = 3 7), GaNm (m = 2 7) and Ga2Nm (m = 3 6),
GanNn (n = 2 6) clusters have been calculated using Den-
sity functional theory (DFT), B3LYP/631G level in Gaus-
sian03. The frequencies of single Ga-Ga bond, Ga-N bond
and N-N bond are 200.0 cm
1
(from Ga2 cluster), 761.5 cm
1
(from GaN cluster) and 2457.6 cm
1
(from N2 cluster) re-
spectively. The rst three intensity vibrational frequencies
of the clusters are showed in Table 1 and Table 2 (inten-
sity I1 > I2 > I3). The geometric structure of ground state
and lower state of the clusters are showed in Refs.[1214].
The vibrational frequencies of the Ga reached clusters in Ta-
ble 1 are close to the peaks of the phonon vibration modes
of the wurtzite structure GaN. The most intensively vibra-
tional frequencies of N reached clusters in Table 2 are all near
to 2200 cm
1
, some of the vibrational frequencies of GanNn
(n = 2 6) clusters are also close to 2200 cm
1
. Then 2200
cm
1
is an intensive vibrational frequency of N-N bond stretch
in N reached GaN. In addition, some of the vibrational fre-
quencies in Table 2 are close to 1300 cm
1
, this is a weak
vibrational frequency of N-N bond stretch in GaN. The peak
at 1384 cm
1
in Fig.3 is close to this frequency. The peak at
1630 cm
1
in Fig.3 is a multiple or sum frequency of other
vibrational frequencies.
The full scanning spectrum of XPS has been showed in
Fig.4(a). In the XPS spectrum, the main elements contained
in GaN nanocrystalline are Ga, N, C and O. The correspond-
ing photoelectron emission peaks are of Ga3d (19.6eV), Ga3p
Fig. 4. XPS spectra of the GaN nanocrystalline
Synthesis and IR Vibrational Spectrum on GaN Nanocrystalline Prepared by Sol-gel Method 617
Table 1. The vibrational frequencies of the ground state and lower
state of GanN (n = 2 8) and GanN
2
(n = 3 7) clusters
Clusters (I
1
) (cm
1
) (I
2
) (cm
1
) (I
3
) (cm
1
) Clusters (I
1
) (cm
1
) (I
2
)(cm
1
) (I
3
) (cm
1
)
Ga
2
N 158.0(a
1
) 892.2(b
2
) Ga
5
N
2
820 (a
1
) 545.9(a
1
) 633.9(b
1
)
127.0(a
1
) 315.4(a
1
) 884.0(b
2
) 733.7(a

) 688.3(a

) 624.7(a

)
Ga
3
N 677.2(b
2
) 674.0(a
1
) 263.0(a
1
) Ga
6
N 531.6(b
2
) 513.2(b
1
) 200.1(a
1
)
1043.3(sg) 316.3(sg) 186.2(p
i
) 672.4(b
2
) 376.3(a
1
) 336.7(b
1
)
Ga
3
N
2
553.4(a

) 316.6(a

) 1477.1(a

) Ga
6
N
2
602.8(a) 467.0(a) 165.3(a)
570.1(b
2
) 425.6(a
1
) 320.5(b
2
) 735.8(a

) 654.8(a

) 604.2(a

)
Ga
4
N 517.6(a) Ga
7
N 526.1(a

) 507.8(a

) 158.4(a)
737.9(a
1
) 460.0(b
1
) 549.6(b
2
) 507.2(a

) 550.9(a

) 358.3(a

)
Ga
4
N
2
812.0(b
1u
) 402.7(b
2u
) 285.3(b
3u
) Ga
7
N
2
687.2(a

) 742.7(a

) 712.1(a

)
422.8(a

) 489.6(a

) 251.4(a

) 663.2(a

) 616.9(a

) 567.5(a

)
Ga
5
N 672.5(a

) 610.3(a

) 247.5(a

) Ga
8
N 538.6(a) 370.7(a) 136.7(a)
524.0(a

) 798.3(a

) 203.0(a

) 548.7(a
1
) 526.1(b
2
) 215.6(a
1
)
Table 2. The vibrational frequencies of the ground state of GaNm (m = 2 7)
and Ga
2
Nm (m = 3 6) clusters, the vibrational frequencies
of the ground state and lower state of GanNn (n = 2 6) clusters
Clusters (I
1
) (cm
1
) (I
2
) (cm
1
) (I
3
) (cm
1
) Clusters (I
1
) (cm
1
) (I
2
) (cm
1
) (I
3
) (cm
1
)
GaN2 2141.3(sg) 214.4(a) 148.3(a) Ga2N2 1858.0(a

) 387.3(a

) 249.6(a)
GaN3 2279.9(sg) 1454.6(sg) 374.6(sg) 493.7 (b
1u
) 137.0(b
2u
) 127.6(b
3u
)
GaN4 2194.6(b
2
) 2276.9(a
1
) 239.7(a
1
) Ga3N3 1216.0(a) 542.8(a) 412.5(a)
GaN5 2004.3(a

) 2469.0(a) 1274.0(a

) 2252.7(a

) 1317.1(a

) 275.8(a

)
GaN6 2225.1(b
2
) 1356.7(b
2
) 458.7(b
2
) Ga4N4 2094.2(a) 617.0(a) 418.5(a)
GaN7 2251.2(a) 1014.6(a

) 1455.8(a) 1469.3(a) 353.1(a) 309.5(a)

Ga2N3 2247.3(a
1
) 1338.8(a
1
) 274.9(a
1
) Ga5N5 2246.7(a

) 682.7(a

) 806.1(a

)
Ga2N4 2277.4(a

) 1041.3(a

) 1363.4(a

) 735.1 (b
2
) 403.8(a
2
) 2026.6(b
1
)
Ga2N5 2239.6(a
1
) 1913.2(a
1
) 1318.0(a
1
) Ga6N6 2142.4(b
2
) 708.5(a
1
) 725.7(b
2
)
Ga2N6 2251.8(b
1u
) 1347.6(b
1u
) 386.9(b
2u
) 713.8 (a) 2075.6(a) 508.0(a)
(105.6 eV), Ga3s (160.0 eV), Ga2p
1/2
(1144.5 eV), Ga2p
3/2
(1116.8 eV) and N1s (397.9 eV), and also GaLMM auger peak.
The peaks of Ga and N are corresponding with the standard
Ga peaks and N peak of GaN, which conrms the formation
of the bond between Ga and N. The binding energies of Ga2p,
Ga2d, N1s and O1s are shown in Fig.4(b), (c), (d) and (e). The
widened and asymmetric peak of N1s is due to NH2 and N
H3 resulting from the reaction of the samples and NH3
[15]
. At
the same time, the binding energies of C1s (284.6 eV) and O1s
(530.8 eV) are of C and O elements from surface adsorption
[16]
.
IV. Conclusion
The characteristics on as-prepared GaN nanocrystalline
have been analyzed above. The results demonstrate the GaN
nanocrystalline have been successfully synthesized by the sol-
gel method. Firstly, the diameters of the grains of the GaN
nanocrystalline change from 30 nm to 100 nm in TEM pat-
tern, and the powder is single crystal with hexagonal wurtzite
structure from SAED and XRD analysis. Secondly, Vibra-
tional frequency of GaN small clusters has been calculated
using Density functional theory (DFT). IR spectrum of the
sample has been analyzed further. Thirdly, the formation of
the bond between Ga and N has been conrmed in XPS spec-
tra.
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LI Enling doctor, professor in Xian
University of Technology. Her research in-
terests are in preparation and simulation
of nano-semiconductor materials. (Email:
lienling@xaut.edu.cn)
MA Deming master, lecturer in
Xian University of Technology. His re-
search interests are in photoelectron de-
vices and photoelectron materials. (E-
mail: mademing@xaut.edu.cn)
WANG Xuewen doctor, professor
in Northwestern University. Her research
interests are semiconductor devices and
materials. (E-mail: wxw-001@163.com)
QI Wei graduate student in Xian
University of Technology. His research in-
terests are in preparation and simulation of
nano-semiconductor materials.
ZHU Hong graduate student in Xian University of Tech-
nology. Her research interests are in preparation and simulation of
nano-semiconductor materials.