Journal of Electron Spectroscopy and Related Phenomena 173 (2009) 711

Contents lists available at ScienceDirect

Journal of Electron Spectroscopy and

Related Phenomena
journal homepage: www.elsevier.com/locate/elspec

X-ray photoelectron spectroscopy study and thermoelectric properties

of Al-doped ZnO thin lms
Li Li a , Liang Fang b, , Xian Ju Zhou a , Zi Yi Liu c , Liang Zhao c , Sha Jiang a
a
b
c

College of Mathematics and Physics, Chongqing University of Posts and Telecommunications, Chongqing, 400065, PR China
Department of Applied Physics, Chongqing University, Chongqing, 400044, PR China
College of Photoelectric Engineering, Chongqing University of Posts and Telecommunications, Chongqing, 400065, PR China

a r t i c l e

i n f o

Article history:
Received 23 October 2008
Received in revised form 26 February 2009
Accepted 2 March 2009
Available online 13 March 2009
PACS:
72.15.Jf
73.61.Ga
73.50.Lw
75.70.i
Keywords:
Al-doped ZnO (AZO) thin lms
XPS spectra
Thermoelectric power
Thermoelectromotive force

a b s t r a c t
In this paper, high quality Al-doped ZnO (AZO) thin lms were prepared by direct current (DC) reactive magnetron sputtering using a Zn target (99.99%) containing Al of 1.5 wt.%. The lms obtained were
characterized by X-ray photoelectron spectroscopy (XPS) and thermoelectric measurements. The XPS
results reveal that Zn and Al exist only in oxidized state, while there are dominant crystal lattice and
rare adsorbed oxygen for O in the annealed AZO thin lms. The studies of thermoelectric property show
a striking thermoelectric effect in the AZO thin lms. On the one hand, the thermoelectromotive and
magnetothermoelectromotive forces increase linearly with increasing temperature difference (T). On
the other hand, the thermoelectric power (TEP) decreases with the electrical resistance of the sample. But
the TEP increases with the increase of temperature below 300 K, and it nearly does not change around
room temperature. The experimental results also demonstrate that the annealing treatment increases
TEP, while the external magnetic eld degrades TEP.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Thermoelectric materials have attracted signicant interest as
useful materials in the eld of thermoelectric power generation
and cooling devices. Development of new oxide materials is still
the most important issue for practical applications of thermoelectric power generation. The performance of thermoelectric materials
can be evaluated by the gure of merit dened as Z = 2 / = 2 /,
where , ,  and  are the thermoelectric power (Seebeck coefcient), electrical conductivity, electrical resistivity and thermal
conductivity, respectively [1]. Consequently, large and , and
small  are essential for thermoelectric materials in practical thermoelectric generators.
ZnO is an n-type semiconducting oxide with wurtzite structure.
It has a wide direct band gap of 3.3 eV. Owing to outstanding physical and chemical properties, ZnO thin lms show a wide range
of scientic and technological applications such as surface acoustic wave devices, bulk acoustic resonators, gas and optical sensors

Corresponding author. Tel.: +86 23 62471434; fax: +86 23 62471434.

E-mail addresses: lili02004@126.com (L. Li), lilic@cqupt.edu.cn,
fangliangcqu@yahoo.com.cn (L. Fang).
0368-2048/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.elspec.2009.03.001

and transparent electrodes [24]. Recently, there are many studies on the Seebeck coefcient of ZnO ceramic in bulk [5,6]. Cai
et al. [7] investigated the thermoelectric properties of Al-doped
ZnO ceramics. They found that ZnO sample with 1 wt.% Al2 O3
possessed a Seebeck coefcient of about 70 V/K at room temperature. Although many experimental studies have been conducted
on the synthesis and electrical properties of AZO thin lms, there
are no detailed studies on their thermoelectric properties, which
are important parameters for conductive lms. In this work, the
thermoelectric power and magnetothermoelectric power of AZO
thin lms were investigated, and the chemical state of Zn, Al and O
in the annealed AZO thin lms was studied by XPS.
2. Experimental
AZO thin lms were deposited by direct current reactive magnetron sputtering. The Zn (99.99% in purity) containing 1.5 wt.% Al
(99.99% in purity) was used as target (diameter 60 mm). Plane glass
was used as substrates. The substrate materials were ultrasonically
cleaned in acetone, rinsed in alcohol, and then dried in hot air. High
purity argon (Ar) and oxygen (O2 ) were used as sputtering and reactive gases, respectively. The partial pressure was controlled by the
ow rates of both argon and oxygen. The optimal substrate-target

L. Li et al. / Journal of Electron Spectroscopy and Related Phenomena 173 (2009) 711

Fig. 1. The apparatus of the thermoelectromotive force measurements.

distance, substrate temperature, working pressure, oxygen argon

ratio, working power and depositional time was 75 mm, 200 C,
5 Pa, 0.3/27, 60 W and 45 min, respectively. The thickness of the AZO
thin lms was about 103 nm measured by Alpha 100 step-scan TENCOR instrument. The AZO thin lms were put into a quartz furnace
to anneal in nitrogen at 400 C for 1 h.
X-ray photoelectron spectroscopy (XPS) was utilized to analyze
the composition and the chemical states of the AZO thin lms.
XPS measurements were carried out by a PHI-5400 X-ray photoemission spectrometer with a monochromatic Mg K (1253.6 eV)
radiation source. The operating pressure of the XPS analysis chamber was approximately 5 108 Torr. Ar+ ion etching treatment was
performed for 15 min to reduce the surface contamination on the
annealed AZO thin lms. The binding energies were calibrated by
taking carbon C1s peak (284.6 eV) as reference. The measurements
accuracy for the electron binding energy was about 0.1 eV.
The apparatus to measure the thermoelectric effect of AZO thin
lms is shown in Fig. 1. Two copper-constantan thermocouples
closely attached to the ends of the sample were used to measure
the temperature difference (T). The reference points of the thermocouples were electrically insulated and put in an ice water. The
Cu electrodes on the AZO thin lms were prepared by electron
beam evaporation. The thermoelectromotive force (thermo e.m.f.)
was measured with voltmeter by changing the temperature at the
hot edge, while keeping the other edge (the cold edge) at a constant temperature. In order to investigate the effect of the magnetic
eld on the thermoelectromotive force (hereafter referred to as
magnetothermoelectromotice force), a magnetic eld of 2.0 T was
perpendicularly applied to the surface of the AZO thin lms sample.
3. Results and discussion
3.1. XPS properties
An XPS survey spectrum (01100 eV) of the annealed AZO thin
lms with Ar+ etching was produced before performing highresolution scan for Al, Zn and O. The result is shown in Fig. 2. The
elements of Zn, O and C were detected in the spectrum, and Auger
peaks such as Zn LMM and O KVV were also observed. The presence of C1s peak in spectra can be attributed to contamination
which resulted from the oil diffusion pump in sputtering process
and the samples being exposed to ambient atmosphere [8]. Carbon
contamination cannot be removed thoroughly after Ar+ ion sputtering. This result suggests that part of the carbon may originate
from the AZO bulk [9]. In Fig. 2, the element Al was not detected
because of its low concentration in the ZnO matrix and its low ionization cross-section value [10]. According to the high-resolution
scan spectrum, the atomic concentrations of elements are computed from the measured peak area together with the sensitivity
factors [11]. The obtained atomic concentrations of C, Zn, O and Al
are 30.3, 25.6, 40.5 and 3.6 at.%, respectively. The corresponding XPS
results of the annealed AZO thin lms with Ar+ ion sputtering are
summarized in Table 1.
Fig. 3 shows high-resolution XPS spectra of Zn2p (Fig. 3a), O1s
(Fig. 3b) and Al2p (Fig. 3c) for the annealed AZO thin lms. To
investigate the change of chemical state in the AZO thin lms, the

Fig. 2. The XPS survey spectrum of the annealed AZO thin lms with Ar+ etching.
Table 1
The XPS results of the annealed AZO thin lms with Ar+ ion sputtering.
Element

Area

Sensitivity factor

Atomic concentration (%)

C1s
O1s
Zn2p3/2
Al2p

33,662
108,010
358,470
3,115

0.296
0.711
3.726
0.234

30.3
40.5
25.6
3.6

core line of Zn2p3/2 that exhibits with high symmetry on the surface of AZO thin lms was investigated. The binding energy of the
Zn2p3/2 remains to be 1021.7 0.10 eV, which is larger than the
value of Zn2p3/2 in bulk ZnO. No metallic Zn with a binding energy
of 1021.5 eV [12] was observed. This shows that Zn exists only in
the oxidized state.
The O1s peak in Fig. 3b before Gaussian tting centers at
530.45 0.10 eV. The corresponding tting results of O1s spectra
is given in Table 2. The O1s peak can be consistently tted by
three components, centered at 530.47 0.10, 531.82 0.10 and
532.41 0.10 eV, respectively. The tted results indicate that each
tted component has a FWHM less than 1.9 eV. The low binding
energy component centered at 530.47 0.10 eV of the O1s spectra
is attributed to O2 ions on the wurtzite structure of a hexagonal
Zn2+ ion array, surrounded by Zn (or substitutional Al) atoms
with their full complement of nearest-neighbor O2 ions [13].
The high binding energy component located at 531.82 0.10 and
532.41 0.10 eV is probably attributed to the either presence of
loosely bound oxygen on the surface of AZO thin lms belonging to
a specic species, e.g., CO3 , or corresponds to hydroxides [1418].
It shows that this component cannot be completely removed even
though the lms were annealed in N2 at 400 C. From Tables 1 and 2,
the stoichiometric ratio of OL (removed adsorbed oxygen of the
O1s peak) and Zn for annealed AZO thin lms in nitrogen can be
obtained by using the empirical equation of Boudeville [19] as
IO /O
[OL ]
= L
= 0.847
[Zn]
IZn /Zn

(1)

where IOL and IZn are the integral areas of the OL and Zn peaks,
respectively, and  Zn = 500,000 and  O = 142,500 are the ionization
Table 2
The tted results of O1s spectra for annealed AZO thin lms.
Position (O)

Area

FWHM (eV)

% of total

530.47
531.82
532.41

81,536
4,986
15,491

1.82
1.06
1.70

79.9
4.9
15.2

L. Li et al. / Journal of Electron Spectroscopy and Related Phenomena 173 (2009) 711

Fig. 4. Dependence of thermoelectromotive force on temperature difference.

states, i.e., oxygen-decient state and oxygen-sufcient state. The

large oxygen deciency, or in other words, the zinc enrichment on
the surface was found to be helpful for the stability of AZO thin
lms exposed to plasmas [24].
Fig. 3c shows that the binding energy values of Al2p are
73.95 0.10 eV. The component centered at 73.95 0.10 eV based
on Gaussian tting is a characteristic of Al2 O3 . No metallic aluminum peak centered at 72.7 0.06 eV [25] appears in the XPS
results. Hence, the XPS results of AZO thin lms indicate that high
quality AZO thin lms were obtained.
3.2. Thermoelectric power (TEP) measurement

Fig. 3. The high-resolution scan XPS spectra of Zn2p (a), O1s (b) and Al2p (c) for
annealed AZO thin lms (solid line: experimental, dotted line: tted).

cross-sections of Zn2p3/2 and O1s, respectively [20]. Therefore,

the annealed AZO thin lms are oxygen-decient according to the
above results. It is known that the stoichiometry of O and Zn in
the AZO thin lms is related to deposition conditions [21]. More
oxygen-decient lms commonly exhibit a lower resistivity. AZO
thin lms are n-type semiconductor. The high conductivity of AZO
thin lms mainly originates from stoichiometric deviation. The
results indicate that the conduction characteristics of AZO thin
lms are primarily dominated by electrons generated by the O2
vacancy, which are in agreement with our previous report [22].
According to the theory of Fan [23], the O1s spectrum contains two

The temperature difference (T) dependence of the thermoelectromotive force of AZO thin lms samples at room temperature is
shown in Fig. 4, which is drawn using the absolute value of thermoelectromotive force for convenience. The TEP of the copperAZO
thin lms thermocouple is Cu f , since Cu is very small, in the
order of a few microvolts per Kelvin, the TEP of the AZO thin lms
was calculated by f = V/T, where V is the thermoelectromotive force and T is the temperature difference of between the two
edges of the sample. The TEP of the AZO thin lms was determined
by analyzing the thermoelectromotive force data.
It is found that the thermoelectromotive force of AZO thin lms
increase almost linearly with increasing temperature difference.
The TEP is related to the electrical resistance of samples for the
same AZO thin lms. With increasing electrical resistance of the
samples, the TEP decreases. All the samples have negative TEP, so
AZO thin lms can be used as an n-type semiconductor. Based on
the experimental data, the TEP of the three AZO thin lms samples
with the electrical resistance of 325, 856 and 1472  was calculated
to be about 68, 48 and 27 V/K, respectively. The polarity of the
thermoelectromotive force at the hot end is positive with respect
to cold end, which conrms that the AZO thin lms are n-type.
To further examine the thermoelectric effect in the AZO thin
lms, the TEP of the AZO thin lms with the electrical resistance of
325  was measured in the temperature range of 25289 K. Typical
plots of the TEP on the temperature for AZO thin lms are shown in
Fig. 5. They exhibit a striking thermoelectric effect in the AZO thin
lms, and their TEP increases with increasing temperature. The TEP
was approximately 68 V/K when temperature approaches room
temperature.
The temperature difference dependence of the thermoelectromotive force of AZO thin lms samples near room temperature is
shown in Fig. 6. It can be seen that the TEP did not change near
room temperature, such as 16, 25, 31 C. As mentioned above, it can

10

L. Li et al. / Journal of Electron Spectroscopy and Related Phenomena 173 (2009) 711

Fig. 7. The relationship between thermoelectromotive force and temperature difference before and after annealing at 400 C for AZO thin lms.

Fig. 5. Variation of thermoelectric power () as a function of temperature.

be known that the TEP was proportional to the temperature, such a

linear temperature behaviors of can be ascribed to the diffusion
thermoelectric power [2628]. The diffusion thermoelectric power
at temperatures well below the Debye temperature  D is given by
=

2 kB2 T
3e|EF |

(2)

where EF is the Fermi energy of free carriers. According to the free

electron model, the Fermi energy is related to the carrier concentration n by
2

EF =

(3n)2/3 .4/3 .h
2m

(3)

Considering various scattering mechanisms, Eq. (2) can be

adapted into
=

2 kB2 T
e|EF |

1
2

1
P ,
3

(4)

where k is the Boltzmans constant, m* is the electron effective mass

and P is the scattering parameter related to the relaxation time. By
combining Eqs. (3) and (4), the thermoelectric power can be given
by the following expression:
=

23/2 B2 m (1/2 + 1/3)T

2

|e| h
(3n)2/3

(5)

Fig. 6. The relationship between thermoelectromotive force and temperature difference near room temperature.

Eq. (5) shows that TEP depends on the temperature. This is consistent with the experimental results.
The temperature difference dependence of the thermoelectromotive force of AZO thin lms samples after annealed at room
temperature is shown in Fig. 7. It is apparent that the annealing
treatment enhances thermoelectric effect in the AZO lms. The TEP
increases because annealing treatment can decrease the stress and
increase the electrical conductivity of AZO thin lms.
Magnetic eld is an important factor on the properties of thermoelectric materials. One magnetic eld of 2 T was perpendicularly
applied to the sample surface, and then one edge of the samples
was heated to measure the thermoelectromotive force. The temperature difference dependence of the thermoelectromotive force
and magnetothermoelectromotive force of AZO thin lms samples
at room temperature is shown in Fig. 8. The experimental evidences
indicate that the magntoelectromotive force is smaller than the
thermoelectromotive force at the same temperature difference, so
the magnetothermoelectric power values are less than the thermoelectric power, indicating that the magnetic eld has negative
effect on the thermoelectromotive force. Under external magnetic
eld, electrons deect from their original path by Lorentz force.
This leads to the increase of the electrical resistance. Thus, the TEP
decreases.

Fig. 8. The relationship between magnetothermoelectromotive force and temperature difference.

L. Li et al. / Journal of Electron Spectroscopy and Related Phenomena 173 (2009) 711

To sum up, the AZO thin lms have relatively large thermoelectric power (68 V/K), small electrical resistivity (104  cm)
[22] and small thermal conductivity (30 W/MK) [29]. According to Z = 2 /, AZO thin lms possess relatively good gure
of merit (1.5 104 W m1 K2 ), which is important for thermoelectric materials. AZO thin lms is promising for thermoelectric
applications at room temperature.
4. Conclusions
The XPS spectra and thermoelectric power of AZO thin lms
were investigated. The XPS results indicate that Zn and Al are
solely in oxidized state, while there are dominant crystal lattice
and rare adsorbed oxygen for O. The TEP of samples is negative
and its absolute value decreases with increasing electrical resistance, and increases after annealing treatment. The TEP increases
with increasing temperature but barely changes near room temperature. The experimental results also show that the TEP degrades
under external magnetic eld. AZO thin lms have the potential
for thermoelectric applications as novel thermoelectric materials.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant no.10704090) and the Youth Foundation
of Chongqing University of Posts and Telecommunications (Grant
no.A2007-37). The authors would like to express their thanks to
Doctor Li Xiaoyu for his assistance in the XPS experiments.

11

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]

[26]
[27]
[28]
[29]

Z.Q. Li, J.J. Lin, J. Appl. Phys. 96 (2004) 5918.

H. Ko, W.P. Tai, K.C. Kim, et al., J. Cryst. Growth 277 (2005) 352.
H. Kim, C.M. Gilmore, J.S. Horwitz, et al., Appl. Phys. Lett. 76 (2000) 259.
J.C. Sun, T.P. Yang, G.T. Du, et al., Appl. Surf. Sci. 253 (2006) 2066.
K. Park, K.Y. Ko, W.S. Seo, et al., J. Eur. Ceram. Soc. 27 (2007) 813.
M. Ohtaki, T. Tsubota, K. Eguchi, et al., J. Appl. Phys. 79 (1996) 1816.
F. Cai, E. Muller, C. Drasar, et al., Mater. Sci. Eng. B 104 (2003) 45.
O.A. Fouad, A.A. Ismail, Z.I. Zaki, et al., Appl. Catal. B: Environ. 62 (2006) 144.
W. Song, S.K. So, L. Cao, Appl. Phys. A 72 (2001) 361.
M. Chen, Z.L. Pei, C. Sun, et al., Mater. Lett. 48 (2001) 194.
X.Q. Wei, B.Y. Man, M. Liu, et al., Physica B 388 (2007) 145.
M.N. Islam, T.B. Ghosh, K.L. Chopra, H.N. Acharya, Thin Solid Films 280 (1996)
20.
R. Cebulla, R. Wendt, K. Ellmer, J. Appl. Phys. 83 (1998) 1087.
B.J. Coppa, C.C. Fulton, P.J. Hartlieb, et al., J. Appl. Phys. 95 (2004) 5856.
S.H. Jeong, J.H. Boo, Thin Solid Films 447/448 (2004) 105.
M. Chen, X. Wang, Y.H. Yu, et al., Appl. Surf. Sci. 158 (2000) 134.
J. Ma, F. Ji, D.H. Zhang, et al., Thin Solid Films 357 (1999) 98.
W. Eisele, A. Ennaoui, P. Schubert-Bischoff, et al., Sol. Energy Mater. Sol. Cells
75 (2003) 17.
Y. Boudeville, F. Figueras, M. Forissier, et al., J. Catal. 58 (1979) 52.
D.W. Ma, Ph.D. Thesis, Zhejiang University, PR China, December 2003.
S.S. Lin, J.L. Huang, P. Sajgalik, Surf. Coat. Technol. 190 (2005) 39.
L. Li, L. Fang, X.M. Chen, et al., Rare Metals 26 (2007) 247.
J.C.C. Fan, J.B. Goodenough, J. Appl. Phys. 48 (1977) 3524.
H.C. Weller, R.H. Mauch, G.H. Bauer, Sol. Energy Mater. Sol. Cells 27 (1992) 217.
C.D. Wagner, W.M. Riggs, L.E. Davis, J.F. Moulder, G.E. Muilenberg, Handbook of
X-ray Photoelectron Spectroscopy, PerkinElmer Corporation, Eden Prairie, MN,
1979, pp. 5051.
R. Maity, S. Kundoo, K.K. Chattopadhyay, Sol. Energy Mater. Sol. Cells 86 (2005)
217.
G.K. Paul, S.K. Sen, Mater. Lett. 57 (2002) 742.
D.K.C. MacDonald, Thermoelectricity: An Introduction to the Principles, John
Wiley & Sons, Inc., New York/London, 1962.
M. Ohtaki, T. Tsubota, K. Eguchi, H. Arai, J. Appl. Phys. 79 (1996) 1816.