Journal of Alloys and Compounds 698 (2017) 147e151

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Annealing effects in ITO based ceramic thin film thermocouples

Xiaohui Zhao*, Haitao Li, Ke Yang, Shuwen Jiang, Hongchuan Jiang, Wanli Zhang
State Key Laboratory of Electronic Thin Film and Integrated Devices, University of Electronic Science and Technology of China, Chengdu 610054, China

a r t i c l e i n f o a b s t r a c t

Article history: Nitrogen doped indium oxide (InON) and indium tin oxide (ITON) thin films were fabricated with
Received 28 September 2016 reactive sputtering in nitrogen-rich plasmas for high temperature thermocouples. Different annealing
Received in revised form processes were applied to improve the performance of indium oxide-based thin film thermocouples. The
15 December 2016
microstructural changes in the films were revealed by X-ray photoelectron spectroscopy (XPS). Meta-
Accepted 17 December 2016
stably retained nitrogen in as-deposited film was transformed into In2O3 and/or oxynitrides after
Available online 19 December 2016
annealing. And significant improvement of linearity and high temperature stability was achieved in N2-
Air annealed ITO thin-film thermocouples.
Keywords:
ITO
© 2016 Elsevier B.V. All rights reserved.
Thin-film thermocouples
XPS
Oxynitride
Annealing

1. Introduction
The dramatic development of aeronautical materials and engine
designs has allowed turbines to be operated at temperature as high
as 1500
C. In order to improve fuel efficiency and reduce harmful
gas emissions, precise measurement of the surface temperature of
turbine engine components is required. Several techniques have
been applied for this purpose, including wire thermocouples,
infrared photography, thermal paints and so forth [1e3]. Among
them, thin film thermocouples (TFTCs) demonstrate significant
advantages over others. With the thickness on order of micrometer,
TFTC would not cause disturbance to gas flow patterns. Meanwhile,
they can withstand severe operating conditions of turbine engines
where supersonic nozzle velocities and over thousand g rotating
forces are present. Furthermore, TFTC can be directly deposited
onto the tested components with negligible weight and thus, it has
a minimal effect on the vibrational modes of rotating components
[4,5]. And due to small thermal mass, they also provide much faster
response than conventional wire thermocouples.
However, when prepared in thin film form, the materials used in
traditional metallic thermocouples suffer from reliability and sta-
bility issues at turbine engine environment [6,7]. For instance, se-
lective rhodium oxidation in type-S (Pt-Pt/Rh) TFTC at
temperatures between 600 and 800
C causes the drift or
degradation of the sensors [8,9]. In sharp contrast, In2O3 and ITO
(In2O3:SnO2) has been proven to be more stable as thermoelectric
elements in highly oxidizing environment. In recent years, these
materials have been used as high temperature strain sensor and
thermocouples due to their high melting point, excellent chemical
stability, phase stability and resistivity to oxidation at elevated
temperatures [10,11]. Meanwhile, ITO based TFTC has much larger
Seebeck coefficients with lower cost compared with precious metal
thermocouples.
Many approaches have been taken to optimize the process
conditions of ITO and In2O3 thin film for the application in high-
temperature strain sensor and thermocouples [12e15]. And nitro-
gen doping has been proven to improve the stability of In2O3-ITO
TFTCs at elevated temperatures [16,17]. In the present work, InON
and ITON thin film were prepared on alumina ceramic substrates by
r.f. magnetron sputtering in argon and nitrogen mixed gas. And
these films were post annealed with different annealing process.
The effect of annealing on the microstructure and chemical
composition of InON and ITON thin film was investigated. InON-
ITON thin-film thermocouples were fabricated on the alumina
ceramic substrates, and their thermoelectric response was char-
acterized and discussed.
2. Experimental details

InON and ITON thin film were deposited on the alumina ceramic
* Corresponding author. substrates (15 mm  10 mm) by reactive r.f. magnetron sputtering.
E-mail address: xhzhao@uestc.edu.cn (X. Zhao). High purity (99.997 wt %) ITO (In2O3: SnO2 ¼ 90: 10) and In2O3

http://dx.doi.org/10.1016/j.jallcom.2016.12.234
0925-8388/© 2016 Elsevier B.V. All rights reserved.
148 X. Zhao et al. / Journal of Alloys and Compounds 698 (2017) 147e151
ceramic disk were used as the targets and the distance between
target and substrate is 110 mm. The base pressure in the chamber
was 8  104 Pa, argon and nitrogen mixed gas with ratio of 7:3 and
9:1 was used as sputtering media for ITON and InON films
respectively. Detailed process conditions were shown in Table 1.
The films were deposited for 60 min to achieve 1 mm in thickness.
Then the samples were post annealed through different 2-step
annealing processes (named as N2-Air and Vacuum-Air, respec-
tively) and the parameters of annealing were shown in Table 2. The
first annealing is supposed to reduce point defects in the films,
while the second annealing is to avoid inhomogeneities between
hot and cold junction produced during thermoelectric measure-
ments of TFTCs [15].
The microstructure of the samples was measured by X-ray
diffraction (XRD). X-ray photoelectron spectroscopy (XPS) was
recorded with a Thermo Scientific K-Alpha spectrometer. The
thickness of the film was obtained with Dektak surface profil-
ometer. The resistivity of thin films was measured by four-probe
tester. InON-ITON thin film thermocouples were fabricated with
above process and patterned with stencil mask on
80 mm  30 mm  1 mm alumina ceramic substrates. The tem-
perature of hot junction and bond pad of TFTC was respectively
characterized with standard type-S and type-K wire thermocouples
mounted on the back of the substrates. The bond pad of TFTC was
chilled with water-cooled clamps. Platinum wires were fixed at
bond pad by high temperature sliver paste to acquire the voltage
signals. The electro-motive force (EMF) was measured by a digital
multi-meter. The TFTC was thermally cycled in air up to 1000
C for
multiple cycles. Each calibration temperature was held for at least
1 h to reach thermal equilibrium.
3. Results and discussion
3.1. Microstructure and chemical analysis
XRD patterns of all ITON films were shown in Fig. 1. Except peaks
from alumina substrate, As-deposited ITON film presents no
obvious diffraction peak, indicating amorphous nature of that. On
the contrary, the annealed ITON films showed strong diffraction
peaks of polycrystalline cubic bixbyite In2O3 phase with no
preferred orientation. None of the patterns showed any diffraction
peaks of Sn and corresponding oxide, indicating that tin atoms
were substitutionally doped into the In2O3 lattice and complete
solid solution of In2O3 and SnO2 was formed [18]. At the same time,
(400) peak of In2O3 shifts to lower angle in the N2-Air annealed
ITON films relative to Vacuum-Air annealed ITON films. This peak
shift has also been found previously in other oxynitride materials
and can be associated with increased nitrogen doping concentra-
tion in the film [15,19].
X-ray photoelectron spectroscopy (XPS) of ITON films at N (1s)
region was shown in Fig. 2. The binding energy (BE) was calibrated
with respect to the C 1s level 284.80 eV of the contaminated carbon.
As-deposited ITON film contains two peaks with binding energy of
396.7 eV and 398.3 eV, which corresponds to indium- and/or tin-
nitrides and indium oxynitrides, respectively [16]. While in the
annealed samples, the peak at 396.7 eV disappeared and the peak
represents oxynitrides shifted to higher binding energy region,
Table 1
Sputtering conditions of ITON and InON films.
Parameters Target Pressure(Pa)
ITON ITO ceramic disk 0.4
InON In2O3 ceramic disk 0.4
indicating that metal nitrides has been depleted and more stable
oxynitrides was formed in ITON films. In particular, oxynitrides in
N2-Air annealed ITON film has even higher binding energy than
that of Vacuum-Air annealed films.
The O (1s) spectra of ITON films are shown in Fig. 3. All of the
spectra exhibited two peaks which represented two types of O2
ions in the film, O1 and O2. The O1 peak, which has relative higher
binding energy, is supposed to represents the O2 ions in oxygen-
deficient region and O2 peak represents O2 ions which have full
complement of six nearest-neighbor O2 ions [20]. Compared with
as-deposited ITON film, the peak intensity of O1 and O2 peak of all
annealed ITON films increased substantially, indicating that oxygen
content in the films increased after annealing. Meanwhile, noting
that in the spectra of Vacuum-Air annealed sample, both O1 and O2
peak shift to higher binding energy region. And this shift becomes
more obvious in N2-Air annealed sample. Taking Vacuum-Air
annealed sample for comparison, the ratio of O1 and O2 peak in-
tensity in N2-Air annealed sample also increased.
The resistivity of the films was also measured, as shown in
Table 3. The resistivity of ITON film increased significantly after
annealing. And N2-Air annealed sample has even larger resistivity
than Vacuum-Air annealed ITON films. We believe that these re-
sults are associated with chemical bonding conditions in the ITON
films.
ITO is a degenerated n-type semiconductor in which oxygen
vacancy is the main source of current carriers. High temperature
annealing in oxygen-rich gas environment introduced more oxygen
atoms into the film, which has been proved by the intensity
enhancement of O2 peak of annealed films. Thereby the oxygen
vacancies in the film should be reduced and the resistivity of the
film arises. However, O1 peak, which is said to be linearly related
with the concentration of oxygen vacancy, increased significantly
after annealing. We suggest that besides oxygen ions in oxygen-
deficient region, any oxygen ions whose nearest-neighbors are
not all oxygen ions could contribute to the intensity of O1 peak. In
annealed ITON films, nitrogen could not only occupy some of the
oxygen vacancies, but also replace existed oxygen ions. As a result,
oxynitride with different binding energies were formed due to
multiple chemical bonding possibilities between metal ions and
oxygen/nitrogen ions. The nearest-neighbor of some oxygen ions
may be changed from oxygen ions to the mixture of oxygen and
nitrogen ions. This well explains the enhancement of O1 peak of
ITON films after annealing. More evidence could be found in N2-Air
annealed films, in which more nitrogen was introduced into the
film during first annealing and the ratio of O1 and O2 peak intensity
was further increased. Meanwhile, the shift of O 1s peaks of ITON
films to higher binding energy region after annealing also indicates
that more oxynitrides with stable structure has been formed,
especially in N2-Air annealed films.
Fig. 4 showed Sn 3d peaks from ITON films. Compared with as-
deposited sample, Sn 3d peaks shift to higher binding energy re-
gion in both annealed samples. This result is coincident with pre-
vious observations, which indicates that more stable oxynitrides of
Sn has been formed. In addition, In/Sn atomic ratio measured by
XPS is 10.15 for as-deposited film, 4.07 for Vacuum-Air annealed
film and 9.67 for the N2-Air annealed film, respectively. The In/Sn
atomic ratio in the surface of Vacuum-Air annealed ITON films was
Temperature Power density(W/cm2) Nitrogen ratio
RT 1.91 30%
RT 2.17 10%
 X. Zhao et al. / Journal of Alloys and Compounds 698 (2017) 147e151 149

Table 2
Different annealing conditions of all samples.

Annealing method Step 1 Step 2

Atmosphere Temperature Time Atmosphere Temperature Time

Vacuum-Air Vacuum 600 C 5h Air 1000 C 2h
N2-Air Nitrogen 1000
C 5h Air 1000
C 2h

3.2. Thermoelectric analysis

InON-ITON thin film thermocouples (TFTCs) were statically

calibrated for three thermal cycles in the thermocouple calibration
furnace. Different thermal gradients were applied between the hot
junction and bond pad of TFTCs. And the calibration result is shown
in Fig. 5. As the temperature sensor, large Seebeck coefficient with
high temperature stability and reproducibility is desired for TFTCs.
As-deposited TFTC has minimal thermoelectric response, and the
electric-motive force (EMF) of TFTC increased rapidly with
increasing temperature, especially at high temperature range.
Compared with as-deposited TFTC, EMF of both annealed TFTC
increased significantly. As for Vacuum-Air annealed TFTC, EMF has
increased almost one order of magnitude. However, the linearity of
EMF is not substantially improved. While in N2-Air annealed TFTC,
significant improvement of linearity of thermoelectric response has
been achieved. It should be noted that N2-Air annealed TFTC
demonstrates much better high temperature stability and repro-
ducibility than others. Fig. 6 showed the variation of Seebeck co-
efficients of TFTCs with temperature difference. Compared with
other two TFTCs, N2-Air annealed TFTC exhibits more stable See-
Fig. 1. X-ray diffraction patterns of ITON films.
beck coefficients than others during the whole calibration range.
For ITO-based thermocouples, the relationship between ther-
moelectric response and temperature difference can be described
according to the following polynomial expression:

E(DT) ¼ A(DT)3 þ B(DT)2 þ C(DT)þD (1)

where DT is the applied temperature difference between hot

Fig. 2. XPS narrow scan spectra of N 1s peak from ITON film.
significantly reduced, and this can be associated with the segre-
gation of Sn atoms at the surface of the film. However, in sharp
contrast, the In/Sn atomic ratio is well retained in N2-Air annealed
films. Obviously the segregation of Sn in the N2-Air annealed film
has been effectively inhibited. This observation also proves that
annealing in N2 has introduced more nitrogen into the film and the
formation of oxynitrides with more stable structure results in sig-
nificant improvement of the chemical homogeneity and stability of
ITO films at high temperature.
junction and bond pad of TFTCs, and A, B, C and D are polynomial
constants. D is arbitrarily set to zero since the boundary condition
(E(DT) ¼ 0 if DT ¼ 0) must be satisfied. The data of all three cali-
bration cycles were applied for the fitting and the results are shown
in Table 4. Minimal root mean square error (RMSE) demonstrates
that N2-Air annealed TFTC has much better stability and repro-
ducibility. We believe the performance of TFTCs can be certainly
related with oxynitrides in ITON and InON films.
In as-deposited ITON films, although certain amount of nitrogen
is incorporated into the film during the sputtering, it only forms
metastable nitrides with metal ions. As n-type semiconductor, the
magnitude of Seebeck coefficient of InN is close to that of In2O3
whereas much larger than that of ITO [21]. Thereby, owing to the
formation of InN in both InON and ITON films, the as-deposited
InON-ITON TFTC exhibits reduced thermoelectric response. After
vacuum annealing, most of InN decomposes and transforms into
In2O3 while few of them forms oxynitrides instead. As a result, the
thermoelectric response of TFTC becomes comparable to that of
In2O3-ITO TFTC [22]. Meanwhile, vacuum annealing also induces
surface segregation of Sn in ITO films, resulting in chemical het-
erogeneity of ITON films and leading to unstable thermoelectric
performance of the TFTC.
In N2-Air annealed films, more stable oxynitrides has been
formed. And the chemical homogeneity of the film is well retained.
As non-degenerate semiconductor, the Seebeck coefficient of In2O3
can be described by:
150 X. Zhao et al. / Journal of Alloys and Compounds 698 (2017) 147e151

Fig. 3. XPS narrow scan spectra of O 1s peak from ITON film.

Table 3
The resistivity of ITON films with different annealing.

Annealing process As-deposited Vacuum-Air N2-Air

Resistivity (U$cm) 2.44  103 9.51  103 1.92  102

Fig. 6. Seebeck coefficients of ITON-InON TFTCs.

 2=3 !
Ak k 2pm*e KT
SðND Þ ¼   ln (2)
e e ħ3 ND

where “S (ND)” is Seebeck coefficient, ND is the carrier concentra-

tion, “k” is the Boltzmann constant, “e” is the electron elementary
Fig. 4. XPS narrow scan spectra of Sn 3d doublet from ITON films. charge, “m” is the effective mass, “ħ” is the reduced Planck constant,
and “A” is the transport constant. Gregory suggested that the
oxynitride films has a significantly reduced Seebeck coefficient

Fig. 5. Thermoelectric response of ITON-InON TFTCs for multiple calibration cycles.

 X. Zhao et al. / Journal of Alloys and Compounds 698 (2017) 147e151
Table 4
Polynomials used to describe the thermoelectric response of ITON-InON TFTCs.
Annealing process Coefficients of polynomial E(DT) ¼ A(DT)3 þ B(DT)2 þ C(DT)þD
A(mV/
C3) B(mV/
C2)
7 4
As-deposited 2.1375  10 2.1040  10
Vacuum-Air 3.3100  107 3.9134  104
N2-Air 1.8640  108 5.2015  105
since nitrogen acts as valence band acceptor in conducting oxides,
making the thermoelectric power more positive (smaller magni-
tude) [15].
While the Seebeck coefficient of ITO, which is degenerate
semiconductor, can be expressed by Eq. (3):
   
p 2=3 8k2 m* T 3
SðND Þ ¼  A þ
3ND 3eħ2 2 [3] H. Wang, M. Yu, Y.X. Zhang, X. Guo, Q.X. Lin, Temperature measure of rotary
This is the same expression used for metals because of the free
electron-like behavior in degenerate semiconductors. Incorpora-
tion of nitrogen into ITO would reduce the carrier concentration as
well as the Fermi level due to an increase in activation energy,
leading to the increment of Seebeck coefficient of ITO [15]. All of
these factors results in the decrease of average thermoelectric
output of N2-Air annealed InON-ITON TFTC [15,20]. However,
regardless of its low thermoelectric output, the N2-Air annealed
InON-ITON TFTC had significantly improved linearity and high
temperature stability. We believe this can be ascribed to the for-
mation of oxynitrides in both InON and ITON films. By forming
chemically stable oxynitrides, the oxygen diffusion from the envi-
ronment is minimized and the carrier concentration of the films is
well controlled, which results in more stable Seebeck coefficient of
TFTC. And this makes ITO based TFTC more suitable for high tem-
perature measurements.
4. Conclusions
ITON-InON ceramic thin film thermocouples were fabricated by
reactive magnetron sputtering for surface temperature measure-
ments of hot components of turbine engines. Two different
annealing processes were applied in order to improve thermo-
electric properties of the films. Nitrogen was metastably retained
into the films as nitrides before annealing. After vacuum annealing,
most of the nitrides were transformed into oxides, leading to
increment of the thermoelectric output of TFTC. In sharp contrast,
oxynitrides with higher binding energy were formed after N2-Air
annealing with the consumption of nitrides. Significant improve-
ment of linearity and high temperature stability was realized for
N2-Air annealed TFTC.
Acknowledgements
We gratefully acknowledge the support of National Natural
Science Foundation of China (61223002) and Program for Cooper-
ation of Industry, Education and Academy of Guangdong Province,
China (Grant No. 2013B090400001).
151
RMSE Average Seebeck coefficient (uV/
C)
C(mV/
C) D(mV)
0.0430 0 2.3902 52.1
0.0647 0 5.5275 143.4
0.0322 0 0.6371 64.7
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