Sensors and Actuators B 76 (2001) 624±628

Study on the temperature effect, hysteresis and drift of pH-ISFET

devices based on amorphous tungsten oxide
Jung-Lung Chianga, Shiun-Sheng Jana, Jung-Chuan Choub,*, Ying-Chung Chena
a
Department of Electrical Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan, ROC
b
Institute of Electronic and Information Engineering, National Yunlin University of Science and Technology, Touliu, Yunlin 640, Taiwan, ROC

Abstract

In this paper, the drift, hysteresis and temperature effect of ISFET devices have been studied. Drift behavior exists in the whole
measurement, and hysteresis behavior is affected by slow response. These two properties limit the accuracy of ISFET. Furthermore, some
characteristics such as pH sensitivity and drift are affected by operating temperature. The I±V curves of a-WO3 gate ISFET was obtained at
different temperatures and the pH sensitivities were calculated in the acid buffer solutions. In the measuring processes, the operating
temperatures were 25, 35, 45, 55 and 658C, respectively, and according to the experimental results, we can ®nd that the pH sensitivity
increases with increasing temperature, the hysteresis effect is dependent on measuring loop time and measuring path, and the drift increases
with increasing pH value. # 2001 Elsevier Science B.V. All rights reserved.

Keywords: Amorphous tungsten trioxide (a-WO3); ISFET; Temperature effects; Hysteresis; Drift

1. Introduction slow response with drift [6±9]. Consequently, we would also

In the recent year, the amorphous tungsten oxide (a-WO3)
thin ®lms were investigated and prepared by rf sputtering
system on the EIS (electrolyte±insulator±semiconductor)
structure and double layer structure of the a-WO3/SiO2 gate
ISFET device in our laboratory. In our study, the a-WO3 thin
®lms show that the pH sensitivity is very high and have a
linear response in the acid buffer solutions (pH ˆ 1 7)
[1,2]. Otherwise, owing to the ISFET has several advantages
(such as: small size, rapid initial pH response, high input
impedance and low output impedance) [3±5], pH-ISFETs
are attractive chemical sensors. However, it has been shown
that the temperature and time dependent effects are major
sources of measurement errors. These problems limit the
progress of developing a commercial device [6±9].
In this paper, the temperature is the most important factor
in ISFET. Likewise, the reference electrode, measured
electrolyte, surface potential and device threshold voltage
are related to temperature [10], so in this study, the a-WO3
gate ISFET was used to investigate the effects of operating
temperature on pH sensitivity. In addition, according to Hein
and Egger [11], the total response is composed of intrinsic
response and drift, and the hysteresis effect combines the
*
Corresponding author. Tel.: ‡886-55342601-2500;
fax: ‡886-55312029/55312063.
E-mail address: choujc@pine.yuntech.edu.tw (J.-C. Chou).
investigate the drift in the different buffer solutions and
hysteresis effect in the different loop time and paths.
2. Experimental
2.1. Devices fabrication
In this study, the substrate material of the ISFET was a p-
type silicon wafer of h1 0 0i orientation, and the doping
concentration was 1015 cm 3. The ISFET device has
W=L ˆ 1000 mm/50 mm (W is the channel width and L
the channel length), and dual dielectric composed of lower
layer of 1000 A Ê of SiO2 and an upper of a-WO3. The devices
with a-WO3 gate insulators fabricated by rf sputtering
system. The fabrication processes were the same as [1].
As shown in Table 1, the conditions of a-WO3 deposition
used a rf power of 90 W, a reactive pressure of 30 mTorr, an
Ar/O2 mixing ratio of 19:1, and a gas ¯ow rate of 50 sccm.
We ®nished the structure of the a-WO3/SiO2/p-Si/Al of pH-
ISFETs and packaged the devices with epoxy.
2.2. Packaging processes
For the measuring convenient and avoid the leakage
current to be generated during testing, in our experiment,
all devices were packaged with the resin epoxy. The several
steps of packaging processes were listed as follows:

0925-4005/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 5 - 4 0 0 5 ( 0 1 ) 0 0 6 5 7 - 8
 J.-L. Chiang et al. / Sensors and Actuators B 76 (2001) 624±628 625

Table 1
Manufacture conditions of a-WO3 gate ISFET

Fabrication conditions

RF power (W) 90
Sputtering pressure (mTorr) 30
Gas mixing ratio (Ar/O2) 19:1
Gas flow (SCCM) 50

1. Using D.I. water to clean ISFET devices.

2. Using N2 gas to dry and then baking in the oven (1208C,
5±10 min).
3. Bounding wire with Ag paste to connect Drain and
Source. Fig. 1. Measuring step of the hysteresis curve for 600 s loop time.
4. Baking Ag paste (1208C, 15 min), for connecting wire
and contact.
5. Packaging with resin epoxy, except that the gate region
without packaging, then baking 15±20 min at 1208C. and another testing loop for pH ˆ 4 ! 1 ! 4 ! 7 !
6. The WO 3 gate ISFET devices were packaged 4 ! 1. The evolution of pH as a function of time was shown
completely. in Fig. 1.

2.3. Measurements
3. Results and discussion
First, the current±voltage (I±V) curves of the a-WO3 gate
ISFET were accomplished by I±V measuring system of As shown in Fig. 2, the pH sensitivity of the a-WO3 gate
HP4145B Semiconductor Parameter Analyzer in the differ- ISFET was determined through the shift of the threshold
ent buffer solutions. The ISFET was immersed in the solu- voltage in the acid buffer solutions at 258C, afterwards, the
tions from pH ˆ 1 to 7, and the heater was utilized to raise same processes were performed at 35, 45, 55 and 658C,
testing temperature from 25 to 658C. respectively. The relationship between the gate voltage and
Secondary, the ISFET devices were operated in the feed- pH sensitivity of the a-WO3 gate ISFET under different
back mode which maintain a constant drain to source current temperatures were shown as in Fig. 3. At 25, 35, 45, 55,
as well as a constant drain to source voltage, then the 658C, the pH sensitivities are 44.85, 47.90, 50.10, 52.85 and
response will re¯ect on the gate of ISFETs. And all test 55.80 mV/pH, respectively. According to the experimental
instrumentation must be placed in the dark box. Therein, the results, the temperature is the most important effect on
read out circuit was set a drain-to-source current of sensing materials and devices. The surface potential of
I DS ˆ 60 mA with a constant drain-to-source voltage of ISFET is dependent on the temperature, and the pH sensi-
V DS ˆ 0:2 V as well as the condition of the I±V measure- tivity is a function of the temperature [10].
ment. The gate voltage of ISFET device was monitored and However, in Fig. 4, it is shown that the relationship
recorded by a V±T recorder (Data chart 3000 voltage±time between the temperature coef®cient (TC) and the pH value
recorder). The hysteresis effect and drift phenomenon were
obtained by the read out circuit [2].
In this study, we immerse the sensor in the pure water for
12 h at least to keep the device in stable state, and then the
drift of gate voltage in different pH of buffer solutions such
as pH ˆ 1, 3, 5 and 7 was recorded. The sampling rate of
recorder is 60 s. According to Yule et al. [12], the surface
response would be steady after 5 h from various pH values.
Therefore, we choose the data from 5 to 12 h as the drift rate.
Additionally, a measurement started when the sensor was
stable at pH ˆ 7 until its drift rate was below 10 4 mV/s [8],
the time needed was about 18 h. Then a pH loop started, with
increments of one pH unit and extreme values of pH ˆ 1 and
7. The measured direction is acid side. We measured the
hysteresis curve in different loop time such as 600, 1200 and
2400 s in the pH ˆ 3 ! 1 ! 5 ! 3 ! 1 measuring loop, Fig. 2. IDS versus VGS curves of the a-WO3 gate ISFET.
626 J.-L. Chiang et al. / Sensors and Actuators B 76 (2001) 624±628
Fig. 3. Relationship between the gate voltage and the pH sensitivity of the
a-WO3 gate ISFET under different temperatures.
of the a-WO3 gate ISFET. The experimental results have
shown that the temperature coef®cient of the a-WO3 gate
ISFET detected in the pH ˆ 1, 3, 5, 7, were 3.35, 2.85,
2.10 and 1.81 mV/8C, respectively, and it is also found
that the temperature coef®cient increases with increasing pH
value, which agrees with the [10].
However, for the applications, the hysteresis curves of a-
WO3 gate ISFET were ®rst investigated in our laboratory [2].
The sensor is directly to be placed in pH ˆ 3 ! 1 ! 3 !
5 ! 3 and 3 ! 5 ! 3 ! 1 ! 3 at 600 s loop time, respec-
tively, in order to prevent the a-WO3 thin ®lm dissolves in
the solutions during the measuring processes [1,2]. Accord-
ing to the experimental results, and shown as Fig. 5, we can
obtain that the hysteresis amounts of the pH ˆ 3 ! 1 !
3 ! 5 ! 3 and 3 ! 5 ! 3 ! 1 ! 3 loops are 7.2 and
12.5 mV, respectively, the acid-side hysteresis is smaller
than basic-side hysteresis. Otherwise, the hysteresis width in
pH ˆ 3 ! 1 ! 3 ! 5 ! 3 at various loop time such as
600, 1200 and 2400 s are 7.2, 9.7 and 15.4 mV, respectively.
It shows that the hysteresis width increases with increasing
loop time. The experimental results are the same as the
Fig. 4. Relationship between the temperature coefficient and the pH of the
a-WO3 gate ISFET.
Fig. 5. Hysteresis width of the a-WO3 gate ISFET during the
pH ˆ 3 ! 1 ! 3 ! 5 ! 3 and 3 ! 5 ! 3 ! 1 ! 3 loops.
Si3N4 [8], Al2O3 [13], Ta2O5 [8] and a-Si:H [14] gate
ISFETs.
The same processes are performed on the pH ˆ 4 ! 1 !
4 ! 7 ! 4 and 4 ! 7 ! 4 ! 1 ! 4 loops. In Fig. 6, it is
shown that the hysteresis widths are 12 and 26 mV, respec-
tively. We can also ®nd that the acid-side hysteresis is less
than basic-side hysteresis. Afterwards, the hysteresis curves
of the a-WO3 gate ISFET in pH ˆ 3 ! 1 ! 3 ! 5 ! 3
and 4 ! 1 ! 4 ! 7 ! 4 at 600 s loop time. It is found that
the hysteresis width increases with increasing pH loop path,
and the hysteresis widths are 7.2 and 12 mV, respectively.
Finally, the drift rate of the a-WO3 gate ISFET was
measured in pH ˆ 1, 3, 5, 7 buffer solutions at the room
temperature (258C) as shown in Fig. 7. According to the
experimental results, we found that the drift rate had an
exponential increasing tendency with increasing the pH
value. The drift rates are 1.5, 3.6, 6.6, 15.7 mV/h at
pH ˆ 1, 3, 5, 7 buffer solutions, respectively.
In this study, we should also have obtained the data of
a-WO3 thin ®lm to compare with standard gate materials
(such as: SiO2 [5], Si3N4 [5,8], Al2O3 [5,13], Ta2O5 [5,8]).
Fig. 6. Hysteresis width of the a-WO3 gate ISFET during the pH ˆ 4 !
1 ! 4 ! 7 ! 4 and 4 ! 7 ! 4 ! 1 ! 4 loops.
 J.-L. Chiang et al. / Sensors and Actuators B 76 (2001) 624±628
Fig. 7. Relationship between the drift rate and the pH value of the a-WO3
gate ISFET.
Therein, the sensitivity of SiO2 is 25 48 mV/pH between
pH ˆ 4 and 10, and Si3N4, Al2O3, Ta2O5 have a higher
response, which are 46±56, 53±57 and 56±57 mV/pH
between pH ˆ 1 and 13, respectively. The sensitivity of
a-WO3 is 45±56 mV/pH between pH ˆ 1 and 7.
Furthermore, according to Bousse and coworkers [8,13]
and our results, the hysteresis effect of a-WO3 gate ISFETs
will be compared with those of SiO2, Si3N4, Al2O3, Ta2O5
and a-Si:H [14] in the different measuring cycles. Therein,
the Ta2O5 has the best performance of hysteresis character-
istic than the other sensing materials, the hysteresis width is
less than 2 mV. The Si3N4 is 6.29±10.92 mV, the Al2O3 is
3.73±4.4 mV, a-Si:H is 1.5±17.9 mV, and a-WO3 is about
7.2±26 mV. The SiO2 exists an unstable experimental result
to compare with other materials.
4. Conclusion
The temperature effect and hysteresis, drift phenomenon
of the a-WO3 gate ISFET device has been investigated in this
study. We can summarize experimental data to induce some
summary and as follows:
1. We can find that the pH sensitivity increases with
increasing the temperature during 25±658C, and the
temperature coefficient is dependent on pH value.
2. The drift rate has an exponential increasing tendency
with increasing pH value, and the drift rates of the
experiment in pH ˆ 1, 3, 5 and 7 at 258C have different
values.
3. The acid-side hysteresis is smaller than basic-side
hysteresis, the hysteresis width increases with increasing
loop time, and we also finds that the hysteresis width is
dependent on measuring loop time and measuring path.
4. According to above the statement and our experimental
results, the a-WO3 thin film has a better sensitive
property than SiO2, and their sensitivity close to Si3N4,
627
Al2O3 and Ta2O5. Consequently, the thin film suits to
application for the ISFET devices.
Acknowledgements
This study is supported by National Science Council, the
Republic of China under the Contract no. NSC 89-2215-E-
224-003.
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Biographies
Jung-Lung Chiang was born in Yuan-Lin, Chang-Hua, Taiwan, Republic of
China, on 29 April 1972. He received BS and MS degrees in Electronics
and Information Engineering from National Yunlin University of Science
and Technology, Touliu, Yunlin, Taiwan, in 1995 and 1997, respectively.
Since 1997, he has been working toward a PhD degree in the Department
of Electrical Engineering at National Sun Yat-Sen University, Taiwan. His
research interests include semiconductor materials and devices, VLSI
technology, thin films technology, and applications for ISFET sensors.
Shiun-Sheng Jan was born in Ta-Chia, Taiwan, Republic of China, in
January 1971. He received BS and MS degrees in Electronics and
628 J.-L. Chiang et al. / Sensors and Actuators B 76 (2001) 624±628
Information Engineering from National Yunlin University of Science and
Technology, Touliu, Yunlin, Taiwan, in 1994 and 1996, respectively. Since
1996, he has been studying toward a PhD degree in the Department of
Electrical Engineering at National Sun Yat-Sen University, Taiwan. His
research interests include semiconductor devices, sensor devices, the
electrographic photoreceptor materials and devices.
Jung-Chuan Chou was born in Tainan, Taiwan, Republic of China, on 13
July 1954. He received the BS degree in Physics from Kaohsiung Normal
College, Kaohsiung, Taiwan, in 1976; the MS degree in Applied Physics
from Chung Yuan Christian University, Chung-Li, Taiwan, in 1979; and
the PhD degree in Electronics from National Chiao Tung University,
Hsinchu, Taiwan, in 1988. He taught at Chung Yung Christian University
from 1979 to 1991. Since 1991 he has worked as an Associate Professor in
the Department of Electronic Engineering at the National Yunlin
University of Science and Technology. His research interests are in the
areas of amorphous materials and devices, electrographic photoreceptor
materials and devices, electronic materials and devices, sensor devices and
science education.
Ying-Chung Chen was born in Tainan, Taiwan, ROC on 4 November 1956.
He received the MS and PhD degrees in electrical engineering from
National Cheng Kung University in 1981 and 1985, respectively. Since
1983, he has been at National Sun Yat-Sen University. Currently, he is a
Professor of Electrical Engineering at National Sun Yat-Sen University.
His current research interests are in the areas of electronic devices, surface
acoustic wave devices, thin-film technology, electronic ceramics, and
super-conductive devices.