Applied Surface Science 254 (2008) 57915795

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Applied Surface Science

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

The crystallization and physical properties of Al-doped ZnO nanoparticles

K.J. Chen a, T.H. Fang b, F.Y. Hung c,*, L.W. Ji b, S.J. Chang a, S.J. Young a, Y.J. Hsiao d
a

Institute of Microelectronics & Department of Electrical Engineering, Center for Micro/Nano Science and Engineering,
National Cheng Kung University, Tainan 701, Taiwan
b
Institute of Mechanical and Electromechanical Engineering, National Formosa University, Yunlin 632, Taiwan
c
Institute of Nanotechnology and Microsystems Engineering, Center for Micro/Nano Science and Engineering,
National Cheng Kung University, Tainan 701, Taiwan
d
Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 4 January 2008
Received in revised form 25 February 2008
Accepted 14 March 2008
Available online 26 March 2008

Un-doped Al (09 at.%) nanoparticles and doped ZnO powders were prepared by the solgel method. The
nanoparticles were heated at 700800 8C for 1 h in air and then analyzed by X-ray diffraction (XRD),
scanning electron microscopy (SEM), Raman spectra and photoluminescence (PL). The results of undoped (ZnO) and Al-doped ZnO (AZO) nanoparticles were also compared to investigate the structural
characteristics and physical properties. XRD patterns of AZO powders were similar to those of ZnO
powders, indicating that micro-Al ions were substituted for Zn atoms and there were no variations in the
structure of the ZnO nanoparticles. From the XRD and SEM data, the grain size of the AZO nanoparticles
increased from 34.41 to 40.14 nm when the annealing temperature was increased. The Raman intensity
of the AZO nanoparticles (Al = 5 at.%) increased when the annealing temperature was increased.
Increasing the degree of crystalline not only reduced the residual stress, but also improved the physical
properties of the nanoparticles.
2008 Elsevier B.V. All rights reserved.

Keywords:
Solgel
ZnO
Crystallization

1. Introduction
The applications of ZnO have attracted much attention in recent
years. With a wide direct bandgap energy (3.37 eV) and a larger
binding energy (60 meV), ZnO is potentially useful in various
optoelectronic applications such as optical sensors and light
emitters [1,2], etc. In addition, ZnO is also potentially useful in
surface acoustic wave (SAW) devices, gas sensing devices and
piezoelectric devices [37]. In fact, devices containing bulk ZnO,
ZnO lms, ZnO nanowires and ZnO nanoparticles have all been
demonstrated [17].
Recently, ZnO have been prepared by sputtering [8], chemical
vapor deposition (CVD) [9], molecular beam epitaxy (MBE) [10],
spry pyrolysis [11], pulse laser deposition [12] and the solgel
process [13,14]. Among these methods, the solgel process is
particularly attractive because of its simplicity and acceptable
costs, however the crystalline quality of the ZnO prepared by the
solgel process might be inferior to the other methods. Notably,
the solgel processes with an annealing treatment are intimately
affect the crystallization and physical properties. Previous
literature, Kuo et al. [14] have investigated the optical and
electrical properties of solgel derived ZnO thin lms with a low

* Corresponding author.
E-mail address: fyhung@mail.mse.ncku.edu.tw (F.Y. Hung).
0169-4332/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2008.03.080

annealing temperature. Also, Zhou et al. [15] have studied the

effect of annealing temperature on the microstructure, electrical
and optical properties of Al-doped ZnO lms. Notably, a low
annealing temperature cannot improve the crystallization, and the
effect of Al-doped concentration is worthy of further investigation.
In addition, relevant reports for ZnO doped with metals (Al3+,
3+
In , Ga3+, etc.) indicate that the doping effect increased the optical
and electrical properties of the ZnO [1618]. However, the
crystallization at high temperatures has still not been investigated.
Furthermore, the sols concentration also affects the crystalline,
optical and electrical properties of ZnO. Schuler and Aegerter [19]
have investigated the effects of sols concentration on the optical,
electrical and structural properties of ZnO: Al coatings. However,
higher concentration of sols has not been studied.
To understand the effect of high concentration sols with metal
dopant and heat treatment on the structural characteristics and
physical properties of ZnO nanoparticles, this study doped Al (0
9 at.%) into ZnO (2 M) nanoparticles by the solgel process to
investigate the microstructural variations and used different heat
treatment conditions to analyze the physical properties of AZO
nanoparticles.
2. Experiments
In addition to zinc acetate, it is possible to fabricate solgel ZnO
samples using zinc nitrate [20]. ZnO prepared with zinc acetate

K.J. Chen et al. / Applied Surface Science 254 (2008) 57915795

5792

exhibits a smoother texture, however nanostructured ne grains

are often observed when zinc nitrate is used. Bahadur et al. [21]
found that ZnO prepared using zinc nitrate shows a rapid and
random crystallization compared to that prepared using zinc
acetate. So, zinc nitrate was used as the precursor material in the
present study.
To prepare the un-doped ZnO (ZnO) nanoparticles, 0.1 M zinc
nitrate hexahydrate (N2O6Zn6H2O) was synthesized with the
stabilizer ethylene glycol (HOCH2CH2OH) in de-ionized water. For
the Al-doped ZnO (AZO) nanoparticles, aluminum nitrate 9hydrate (Al(NO3)39H2O) was added into the solution to serve as
the aluminum source. The amount of Al(NO3)39H2O was
controlled precisely and kept at the concentration of aluminum.
Three Al atomic contents of 5 at.%, 7 at.% and 9 at.% were
chosen, then stirred in clear solution at 80 8C for 1 h. Meanwhile,
citric acid (C6H8O7) was dropped into these solutions slowly until
the solutions had a uniform distribution and became transparent.
After that, the solutions were placed in an oven at 120 8C until the
solvent evaporated and the remainder was pulverized into
nanoparticles. Finally, the nanoparticles were put into an oxidizing
furnace to perform two heat treatments to understand the effect of
annealing temperature (including 700 8C1 h and 800 8C1 h). In
addition, a differential scanning calorimeter (DSC) and a thermo
gravimetric analyzer (TGA) were used to determine thermal
properties of the fabricated ZnO and AZO. The structural
characteristics were examined using X-ray diffraction (XRD),
scanning electron microscopy (SEM) and Raman spectra. Also, PL
was used to understand the relation between the Al concentration
and the optical properties.

3.2. X-ray diffraction and SEM observation

Fig. 2(a) shows the XRD patterns of ZnO nanoparticles annealed
at 700 and 800 8C for 1 h. Both of the ZnO samples were
polycrystalline and correspond to hexagonal structure. With
increasing the annealing temperature, the intensity of the major
diffraction peaks increased indicating that the crystallization of
ZnO nanoparticle was improved at higher temperatures. Notably,
this result was similar to that of AZO nanoparticles. After 5 at.%-Al
doping, AZO nanoparticles also appeared in the polycrystalline
structure and no diffraction peaks of Al2O3 or other impurities
were observed (Fig. 2(b)). However, the full-width at halfmaximum (FWHM) on the (0 0 2) peak had a tendency to decrease
with increasing the annealing temperature from 700 8C to 800 8C
(compare Fig. 2(a) with (b)). In other words, the crystalline degree
of AZO was larger than ZnO when the temperature was raised from
700 to 800 8C.
In addition, our results and previous reports [22,23] also show
that increasing the heat treatment temperature improves the
crystallization of ZnO nanoparticles. To understand the crystalline
mechanism of AZO, the grain size of the AZO nanoparticles has
been estimated from the FWHM of (0 0 2) the diffraction peak
using the Scherrer formula [24]
d

0:9l
b cos uB

where l is the X-ray wavelength of 1.54 A, u is the Bragg

diffraction angle of the (0 0 2) peak, and b is the FWHM of u. The

3. Results and discussion

3.1. TGA and DSC analysis
To determine the crystalline conditions, differential scanning
colorimetry (DSC) and TGA of ZnO gel nanoparticles were carried
out. The specimens were heated from room temperature to 900 8C
with an increment of 10 8C/min in air. Fig. 1 shows a combined plot
of DSC and TGA. Notably, the TGA data plots the weight loss of the
nanoparticles which is found to take place till 520 8C. For the DSC
curve (room temperature 400 8C), an exothermic peak and two
endothermic peaks are found at 270, 147 and 317 8C, respectively.
These peaks are attributed to the evaporation of water and
organics. A large exothermic peak is exhibited at 490 8C, due to the
crystallization of ZnO. Therefore, the crystallization of ZnO
nanoparticles occurred at temperatures over 520 8C. For this
reason, this study selected 700 and 800 8C to estimate the
crystallization of AZO nanoparticles.

Fig. 1. DTA-TGA curve of ZnO.

Fig. 2. (a) XRD patterns of un-doped ZnO powders sintered at 700 and 800 8C. (b)
XRD patterns of 5 at.% AZO powders sintered at 700 and 800 8C.

K.J. Chen et al. / Applied Surface Science 254 (2008) 57915795

average grain size of AZO nanoparticles increased from 34.41 to

40.14 nm when the annealing temperature was increased from
700 to 800 8C. Fig. 3 shows the SEM images of 5 at.% Al-doped ZnO
nanoparticles at 700 and 800 8C. The grain size of the AZO
nanoparticles increased with increasing the temperature. This
result is associated not only with the grains growing more easily
when the temperature is higher, but also with the Al dopants. To
understand how the content of Al-doped ZnO powders affect
related properties, three Al atomic contents of 5 at.%, 7 at.% and
9 at.% were used to perform a heat treatment of 800 8C in air for 1 h.
In Fig. 4, we see the major diffraction peaks decreased with
increasing the Al concentration, which indicates Al-doping
resulted in a decrease in the crystalline quality. Comparing the
crystallization of ZnO with AZO, a large amount of Al dopants
resulted in lattice disorder, which is associated with the stress
generated. Besides the stress problem, the grains grew more easily
when Al dopants were incorporated with ZnO.

5793

Fig. 4. XRD patterns of un-doped and Al-doped ZnO powders with various
concentrations. The samples were prepared at 800 8C.

3.3. Raman spectra of ZnO powders

The structure of ZnO belongs to the C6V symmetry group, which
predicts two A1, two E1, two E2 and two B1 modes [25]. Among
these, A1 and E1 modes are polar and split into transverse (TO) and
longitudinal optical (LO) phonons, all being Raman and infrared
active. E2 modes are only Raman active, and B1 modes are infrared
and Raman inactive (silent modes).
Fig. 5(a) shows the Raman spectra of ZnO nanoparticles with
different Al concentration that were heated at 800 8C in air for 1 h
(using a solid-state laser (532 nm)). ZnO nanoparticles showed
the usual modes that were observed at 331 cm1 (second-order

Fig. 3. SEM images of the 5 at.% Al-doped ZnO powders sintered at (a) 700 8C and (b)
800 8C.

vibration corresponding to the E2 (high)E2 (low)), 380 cm1 (A1

(TO)), 409 cm1 (E1 (TO)), 438 cm1 (E2 (high)), 537 cm1
TO + TA(M), 581 cm1 (E1 (LO)), and 658 cm1 E2 (low)B1 (high),
respectively. The results were the same with the previous reports
[2529]. The 331 cm1 mode could be observed by enhancement of
Raman active and inactive phonons with lattice symmetry due to
disorder-activated Raman scattering (DARS) [30,31]. In addition, the
Raman band was at around the M point of the Brillouin zone [32].

Fig. 5. (a) Raman spectra of un-doped and Al-doped ZnO powders with various
concentrations. The ZnO powders were prepared at 800 8C. (b) Raman spectra of
5 at.% Al-doped ZnO powders with different annealed temperature.

5794

K.J. Chen et al. / Applied Surface Science 254 (2008) 57915795

The 380 cm1 mode was lifted the degeneracy of infrared active
optical phonons into a transverse (TO) branch, as is well known by
the LyddaneSachsTeller relation [23]. The 409 cm1 mode is
associated with lattice disorder along the c-axis of the ZnO crystal,
the 438 cm1 mode corresponds to E2 mode of wurtzite ZnO and a
very sharp feature. The 582 cm1 E1 (LO) corresponds to wellresolved Raman peaks due to multiphonon and resonance
processes and are related to oxygen deciency [25,30]. According
to the results of Li et al. [31], the 537 cm1 peak is a ZnC mode,
and the 658 cm1 peak was a ZnCH2 mode, which are associated
with the precursor materials in the solgel process. Relevant
studies [3234] also show that the 537 cm1 mode being very
close to the 540 cm1 mode, could most likely be assigned to
TO + TA(M) second order vibration, since the 2B1 (low) mode is
around 510520 cm1, while the contribution of the rst-order
B1(high) mode is around 560 cm1. In addition, the 658 cm1 mode
is very close to the mode near 645650 cm1, which is likely due to
the 101 cm1 E2 (low) + 521 cm1 B1 (high) [32].
Comparing the AZO with the ZnO nanoparticles (Fig. 5(a)), A1
(TO) and E1 (LO) modes are shifted to the high frequency side. With
increasing the Al dopant concentration, the intensity of E2 (high)
E2 (low), E2 (high), A1 (TO) and E1 (LO) modes decreased. The 438
and 582 cm1 modes decreased with an increased Al concentration, which contributed to Al ions in the ZnO lattice substituting for
Al in the Zn position. The intensity of the 331, 385, 438 and
582 cm1 modes decreased with increasing the Al concentration.
Fig. 5(b) shows the room temperature Raman spectra for 5 at.%
Al-doped ZnO powders at 700 and 800 8C for 1 h in air. From the
results, all peak intensities increased clearly when the temperature
was increased. The same tendency was also observed in Al-doped
ZnO samples using spray pyrolysis [35], and shows that the
crystalline quality of the lms had been improved. Notably, the
spray pyrolysis [35] is different from the solgel method; our
present solgel method was able to avoid surface point defects at
higher annealing temperatures.
According to a relevant study [26], an increase in Raman peak
intensity indicates that the residual stress had reduced leading to
higher crystalline quality. In addition, the reduction of the relative
peak-intensity 385 cm1 A1 (TO) to 414 cm1 E1 (TO) at low
temperature is associated with lattice disorder along the c-axis of
the ZnO crystal [36]. However, the intensity ratio of 385 cm1 A1
(TO) to 414 cm1 E1 (TO) increased from 0.944 to 0.956 with
increasing the annealing temperature. On the other hand, the
increase of the second-order modes to the rst-order modes
decrease with increasing annealing temperature, due to the better
crystallization of the thin lms and this again supports the secondorder nature of the 537 and 658 cm1 mode.
3.4. Optical properties of ZnO powders
Photoluminescence (PL) was used to check the optical quality
and the possible effects of Al doping. Fig. 6 shows the PL spectra of
the AZO nanoparticles using 325 nm UV light from a He-Cd laser at
room temperature. In Fig. 6(a), the ZnO and AZO nanoparticles
were heat treated at 800 8C for 1 h in air. In this spectrum, the ZnO
powders contain a UV emission band at 375 and 386 nm, and a
strong and broad green emission band occurs at about 533 nm
(inset in Fig. 6(a)). Hsieh et al. [37] showed that the near band
emission of 375 nm was caused by the transition from conduction
band to valence band. Another UV emission of 386 nm was
attributed to the free exciton recombination in ZnO. On the other
hand, the strong green emission (533 nm) resulted primarily from
intrinsic defects. The intrinsic defects are associated with deep
level emissions such as oxygen vacancies or zinc interstitials [38].
Notably, the oxygen vacancies and interstitials were induced by

Fig. 6. PL spectra of ZnO powders (a) with different Al concentration annealed at

800 8C and (b) with 5 at.% Al concentration under various annealing temperatures.

the thermal treatment process and solgel method. After Al

doping, the UV emission peak position of AZO nanoparticles
exhibited a slight blue-shift from 3.21 to 3.26 eV, and the intensity
deceased with increasing the Al concentration, which is attributed
to an increase in nonradiative recombination.
The PL spectrum of 5 at.% Al-doped ZnO nanoparticles is
presented in Fig. 6(b). UV emission peaks are observed at 382 and
380 nm, and the full width at the half maximum (FWHM)
decreased slightly from 169 to 167 meV with increasing the
temperature. The intensity of the UV emission peak increased
when the temperature was raised from 700 to 800 8C. This should
be one reason why the increased intensity of UV emission is
associated with the grain size and crystal orientation [37]. The
results are consistent with the XRD and SEM data (Fig. 2(b) and
Fig. 3). According to a report by Choi et al. [39], the Zn atoms not
only reacted with O atoms easily but also increased the amount of
coupled Zn atoms and O atoms at a higher heat treatment
temperature. For Raman measurements in AZO nanoparticles with
different annealing temperatures, the AZO nanoparticles at 800 8C
show the best crystallize quality suggesting that increasing the
annealing temperature not only raised the crystalline quality but
also improved the optical properties.
4. Conclusion
For AZO powders, the crystallized temperature of ZnO
nanoparticles is above 520 8C and the grain size increased with
an increase in the heat treatment temperature. With increasing the

K.J. Chen et al. / Applied Surface Science 254 (2008) 57915795

Al concentration, the crystalline quality of ZnO degenerated, which

is associated with the stress generated which resulted in lattice
disorder. For Raman spectroscopy, the 438 and 582 cm1 modes
decreased with increasing Al concentration, which is attributed to
Al ions bonding with oxygen or Al ions substituting for oxygen
deciency. In addition, the two peaks at 543 and 658 cm1 were
assigned as ZnC and ZnCH2 modes, respectively. The PL
characteristics show that the optical quality degenerated gradually
with increasing the Al concentration. 5 at.% Al-doped ZnO powders
had the best characteristics and optical properties in this study.

[14]
[15]
[16]
[17]

Acknowledgement

[24]

The authors are grateful to the Chinese National Science Council

for its nancial support (Contract: NSC 962221-E-006103-MY2;
NSC 972218-E-006011).

[25]

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