Вы находитесь на странице: 1из 6

Home Search Collections Journals About Contact us My IOPscience

Investigation of a p-CuO/n-ZnO thin film heterojunction for H2 gas-sensor applications

This content has been downloaded from IOPscience. Please scroll down to see the full text.

2006 Semicond. Sci. Technol. 21 928

(http://iopscience.iop.org/0268-1242/21/7/017)

View the table of contents for this issue, or go to the journal homepage for more

Download details:

IP Address: 143.233.248.101
This content was downloaded on 12/07/2017 at 08:41

Please note that terms and conditions apply.

You may also be interested in:

Fabrication and characterization of a CuO/ITO heterojunction with a graphene transparent electrode


K Mageshwari, Sanghoo Han and Jinsub Park

Effect of UV exposure on rectifying behavior of polyaniline/ZnO heterojunction


Bhupendra K Sharma and Neeraj Khare

Mechanism and prominent enhancement of sensing ability to reducing gases in p/n coreshell
nanofiber
Akash Katoch, Sun-Woo Choi, Gun-Joo Sun et al.

Study of luminescent centers in ZnO nanorods catalytically grown on 4H-p-SiC


N Bano, I Hussain, O Nur et al.

Solution-route low-temperature fabrication of thin-film p-n junctions


Gustavo Panam, Kevin Ayag and Hongdoo Kim

Structure, microstructure and physical properties of ZnO based materials in various forms
Shubra Singh, P Thiyagarajan, K Mohan Kant et al.

Excitonic electroluminescence from ZnO-based heterojunction light emitting diodes


J W Sun, Y M Lu, Y C Liu et al.

Semiconductor ultraviolet photodetectors based on ZnO and MgxZn1xO


Yaonan Hou, Zengxia Mei and Xiaolong Du
INSTITUTE OF PHYSICS PUBLISHING SEMICONDUCTOR SCIENCE AND TECHNOLOGY
Semicond. Sci. Technol. 21 (2006) 928932 doi:10.1088/0268-1242/21/7/017

Investigation of a p-CuO/n-ZnO thin film


heterojunction for H2 gas-sensor
applications
S Mridha and D Basak
Department of Solid State Physics, Indian Association for the Cultivation of Science,
Jadavpur, Kolkata 700032, India
E-mail: sspdb@iacs.res.in

Received 21 December 2005, in final form 11 May 2006


Published 7 June 2006
Online at stacks.iop.org/SST/21/928
Abstract
A p-CuO/n-ZnO thin film heterojunction is fabricated on a glass substrate
by the solgel technique. The crystallinity of the junction materials and
microstructure of the top p-layer are examined by an x-ray diffractometer
(XRD) and scanning electron microscope (SEM). The currentvoltage (IV)
characteristics of the pn heterojunction and its temperature dependence
have been investigated in air and H2 ambient. Although the junction
possesses linear IV characteristics from room temperature (RT) to 150 C
in air, at higher temperatures (200 C to 300 C), it shows nonlinear
rectifying behaviour. The forward current is greatly increased with
increasing temperature while the reverse current is increased slightly
resulting in a IF/IR ratio as high as 485. The ideality factor (n) is 4.88 at a
temperature of 300 C. The forward current is highly increased by the
introduction of H2 gas at 300 C. However, a simultaneous increase in the
reverse current makes the IF/IR ratio 8.4. It is observed that H2 sensitivity of
the heterojunction is increased with the increase in temperature as well as
the thickness of CuO film. A sensitivity value as high as 266.5 is observed at
300 C when biased at 3 V in the presence of approximately 3000 ppm
of H2.

1. Introduction CuO/ZnO heterojunction made from two sintered metal oxide


pellets with their uneven surfaces pressed together using a
pn junctions are the key technology in many electronic mechanical press. The high hydrogen sensitivity of doped
and optoelectronic devices. Oxide semiconductors either CuO/ZnO heterocontacts to reducing gas species has been
exhibit n- or p-type conductivity. However, it is difficult to reported by Aygun and Cann [6]. The interfacial area is limited
change these semiconductors to the other type because of in such a structure due to a rough surface microstructure and
high intrinsic carrier concentration. Zinc oxide is an n-type mechanical pressing conditions. However, there are very few
semiconductor with an energy gap of about 3.3 eV and reports on CuO/ZnO thin film heterojunctions. Rectifying a
conductivities of about 107103 S cm1 [1, 2]. Obtaining a CuO/ZnO heterojunction by sputtering the p-type CuO thin
reproducible method to grow a p-type ZnO film which leads film on an n-type polycrystalline ZnO substrate has been
to the fabrication of a pn homojunction is still a problem reported [7, 8]. The effects of interface states on gas sensing
due to the deep acceptor levels, low solubility of the dopants properties of a CuO/ZnO thin film heterojunction have been
and the self-compensation process [1]. However, it is easier studied by Yanagida et al [9]. In this paper, we report on a
to form a heterojunction with copper oxide which is a p-type p-CuO/n-ZnO thin film heterojunction fabricated using a low-
semiconductor with an energy gap of about 1.5 eV [3] and cost solgel technique by depositing CuO on the ZnO layer
conductivities of 104 S cm1 [2]. When they are brought with a large common surface area. CuO deposited on the
together to form a pn contact, they show sensitivity to polycrystalline ZnO layer shows polycrystalline morphology
reducing gases. Previous works [4, 5] demonstrated a with grain boundaries. The IV characteristics show thermally

0268-1242/06/070928+05$30.00 2006 IOP Publishing Ltd Printed in the UK 928


Investigation of a p-CuO/n-ZnO thin film heterojunction for H2 gas-sensor applications

activated diode-like rectifying behaviour, and also a very high


H2 gas sensitivity. 200

CuO (-111)
(a)

CuO (111)
150
2. Experimental methods

ZnO (002)
ZnO (101)
Intensity (a.u.)
At first the ZnO thin film was deposited on a glass substrate 100
using the solgel drain coating technique described elsewhere

ZnO (100)
CuO (110)

CuO (-202)
ZnO (102)
[10]. In brief, sol was prepared by adding zinc acetate- 50
2-hydrate [Zn(CH3COO)22H2O] to dehydrated isopropyl
alcohol containing diethanolamine as sol stabilizer followed by 0
thorough mixing. The glass substrate was cleaned by acetone,
methanol and finally with deionized water. Each coating on 20 25 30 35 40 45 50
the substrate was first dried at 120 C for 15 min and then 2 (degrees)
decomposed at 550 C for 30 min. This process of coating
and subsequent heat treatment was repeated ten times to get the (b)
desired film thickness. Next, we deposited the CuO layer on
ZnO. To deposit CuO thin film, we followed the path described
by Orel et al [3]. In brief, 9.5 g cupric acetate was dissolved in
80 ml double distilled water at 75 C. During dissolution 3 M
citric acid was added to the cupric acetate solution resulting in
a blue-greenish precipitate, which was washed several times
with double distilled water. The precipitate was peptized by
slow addition of a 14 M ammonia solution and heated at 70 C
to get a deep blue coloured stable sol. To prepare CuO/ZnO
heterojunction, the ZnO-deposited glass substrate was coated
with this sol by the drain-coating method. After each coat the Figure 1. (a) XRD pattern of the p-CuO/n-ZnO heterojunction on
sample was heat treated at 480 C for 10 min. The process the glass substrate. (b) Scanning electron microscope image of the
top CuO layer.
was repeated several times to get a desired film thickness. The
film thickness was measured by the precession measurement 0
system (model: Form Talysurf 120, UK). 4 CuO
30 C
ZnO
The crystalline phase of the CuO/ZnO heterojunction was
determined by an x-ray diffractometer (model: Seifert XDAL 2
7
Current, A*10

3000). The microstructure of the top CuO layer was examined


by a field emission scanning electron microscope (FE-SEM, 0
model: JEOL JSM-6700F). Several gold electrodes of about
100 nm thickness in circular form of diameter 1 mm separated -2
by 3 mm were evaporated on CuO and also on the exposed ZnO
film. For IV measurements, dc currents between two contacts -4
were measured using a Keithley source meter (Model 2400). -20 -10 0 10 20
For temperature variation, the heterojunction was inserted in Voltage (V)
a temperature-controlled furnace and the temperature of the
junction was monitored with the help of a thermocouple. For CuO 300 C
0

gas sensitivity measurements, H2 gas was inserted into the 4


ZnO
sample chamber in approximately 3000 ppm diluted with air.
4

2
Current, A*10

3. Results and discussion 0

The XRD pattern of the heterojunction is shown in figure 1(a).


-2
It shows the peaks that can be assigned either to hexagonal
wurtzite ZnO [11] or monoclinic tenorite CuO [12] phase.
-4
No other impurity peak is observed. Figure 1(b) shows the
surface morphology of CuO film on ZnO. It shows granular -20 -10 0 10 20
morphology with a grain size of about 34 nm. The film Voltage (V)
is porous with many grain boundaries. Unless otherwise Figure 2. IV characteristics between two contacts both on CuO
mentioned, the film thicknesses of CuO and ZnO films are and on ZnO at room temperature (30 C) and 300 C.
1.2 m and 0.4 m respectively.
The solgel-deposited CuO and ZnO films show characteristics between two contacts both on CuO and on ZnO.
unintentionally doped p-type and n-type conductivities In both cases, linear dependence of the current on the voltage
respectively. The resistivities are 8.5  cm and 65  cm is obtained confirming the ohmic behaviour of the contacts.
for CuO and ZnO films respectively. Figure 2 shows the IV Considering the work function value, gold should form ohmic

929
S Mridha and D Basak

Table 1. Forward current (IF), reverse current (IR), ratio of the forward current to the reverse current (IF/IR) at 16 V, and ideality factor (n) at
different temperatures in air and hydrogen ambients.
Air Hydrogen
Temperature ( C) IF (A) IR (A) IF/IR n IF (A) IR (A) IF/IR n
300 2.0 103 4.12 106 485 4.88 11.97 103 1.42 103 8.4 4.96
250 5.45 104 1.97 106 277 5.52 3.31 104 1.02 104 3.2 5.28
200 7.36 105 1.9 106 39 6.03 1.45 104 2.65 105 5.5 6.12
150 4.51 107 3.16 107 1.5 7.2
100 3.26 108 3.28 108 0.99 9.91
RT 3.57 109 3.47 109 1.02

32 15
Au

Current (A*10 )
4
0
CuO 0
3.0 250 C
24 300 C
4

ZnO 1.5
Current, A*10

Substrate

Current, A*103
10 0.0
16 0 0
200 C 300 C
-1.5
0 -14 -7 0 7 14
250 C Voltage (V)
8
5
0 0
200 C
0
-20 -10 0 10 20 250 C
Voltage (V)
0
Figure 3. IV characteristics of the CuO/ZnO heterojunction in air 0
200 C
at 300 C, 250 C and 200 C. The inset shows a schematic diagram
of the device. -15 -10 -5 0 5 10 15
Voltage (V)
contact on p-CuO and many earlier studies have also reported
Figure 4. IV characteristics of the CuO/ZnO heterojunction in H2
gold to form ohmic contacts on n-ZnO [10, 13].
at 300 C, 250 C and 200 C. The inset shows current magnitudes
A schematic diagram of the device is shown in the inset of 250 C and 200 C.
of figure 3. Figure 3 shows the typical IV characteristics
of the CuO/ZnO heterojunction at different temperatures in where A is the diode area, A is the effective Richardson
air. From room temperature (RT) to 150 C, it shows a constant and B is the apparent barrier height.
very small current conduction through the circuit and the IV The ideality factor values (n) are obtained from the
characteristics are linear (not shown). In the temperature slope of the plot of lnI versus V and are given in table 1.
region from 200 C to 300 C, a rectifying characteristic At lower temperature, the values of n are quite large indicating
similar to a conventional pn junction is observed with the heterojunction to be far from an ideal pn junction.
very reproducible characteristics. At higher temperatures, At temperatures of 250 C and 300 C, the n values are
the forward current is increased exponentially while the quite improved, but still greater than 2. Therefore, the
reverse current shows a very little increment. Since ohmic ideal model cannot explain the current transport mechanism
characteristics of two Au contacts on both CuO and ZnO through the heterojunction. It appears that there is multiple
are observed (in figure 2), the diode-like IV characteristics transport mechanism such as defect-assisted tunnelling and
confirm the formation of the pn heterojunction at the interface carrier recombination in the space charge region via interface
of ZnO and CuO thin film and are consistent with the p-type states [4]. This is because both CuO and ZnO phases have
and n-type conductivities of CuO and ZnO respectively. The lattice defects and surface adsorbates. Although our ideality
ratio of the forward current (IF) to the reverse current (IR) at 16 factor of 4.88 is slightly higher than the value obtained in the
V bias in air is given in table 1. The ratio of the forward current sputtered CuO/ZnO junction [7], it is much better than the
to the reverse current (IF/IR) is increased as the temperature is value obtained in the CuO/ZnO junction made by sputtering
increased. The table shows that at 300 C, IF/IR is as large as [8]. This result points out that our microstructure of p and n
485. Therefore, it is clear that the IV characteristic through layers is of better quality resulting in a heterojunction which
the heterojunction is dominated by the thermal process. The is closer to the ideal pn junction.
forward currentvoltage relationship [14] is given by Generally, the adsorption and chemical reactions of gas
I = Is [exp(qV /nKT ) 1], (1) species at the interface produce a change in the rectifying IV
characteristics. Therefore, we have investigated the change
where q is the electronic charge, V is the applied voltage, K
in the current by introducing a reducing gas like H2 in order
is the Boltzmann constant, n is the ideality factor and Is is the
to examine its potential use for the development of a H2 gas
reverse saturation current which is given by
sensor. Figure 4 shows the IV characteristics at different
Is = AA T 2 exp(qB /KT ), (2) temperatures in the presence of H2 gas. At room temperature,

930
Investigation of a p-CuO/n-ZnO thin film heterojunction for H2 gas-sensor applications

300 80
(a) H2 off
H2 off
250
60

H2 Sensitivity (S)
200 O
300 C
H2 sensitivity (S)

40
150
H2 in H2 in
20
100
O
250 C
50 0
0 500 1000 1500 2000
0 O
200 C Time (S)
0 4 8 12 16 Figure 6. Transient response of the CuO/ZnO heterojunction with
Bias voltage (V) CuO of thickness 0.72 m at 300 C and 3 V bias.
300
(b)
the enhanced H2 adsorption. This value is higher than
250
the sensitivity of Ni-CuO/ZnO at 400 C [6]. The higher
200
sensitivity value implies that the undoped solgel CuO/ZnO
1.2 m
thin film heterojunction can be used as a hydrogen sensor
H2 Sensitivity (S)

150 while operated at low bias voltage. A change in the CuO


layer thickness on H2 sensitivity is shown in figure 5(b). It
100 shows that when the layer thickness increases from 0.43 m to
1.2 m the sensitivity is increased by 40 times. This result also
0.72 m
50 supports that hydrogen is interacting directly with the adsorbed
oxygen molecules, the amount of which increases largely with
0 the increase in the porous CuO layer thickness. However, the
0.43 m
heterojunction is not stable above 300 C. Further, doping of
0 4 8 12 16 the CuO layer is expected to improve the sensitivity, which is
Voltage (V) currently under investigation.
Figure 5. (a) Hydrogen gas sensitivity of the CuO/ZnO Figure 6 shows the typical transient response at 3 V of
heterojunction as a function of bias voltage at different temperatures. one of the heterojunctions with CuO of thickness 0.72 m
(b) Hydrogen gas sensitivity of the CuO/ZnO heterojunction as a at 300 C for 3000 ppm H2 gas concentration. The rise
function of bias voltage for different thicknesses of CuO at 300 C. time in the transient response is in the order of 1 min.
However, a slight reduction in the sensitivity after first cycle of
100 C and 150 C, there is a very small current conduction hydrogen gas exposure probably indicates device instability.
and the IV characteristics are very much similar to those The reversibility as well as sensitivity in figure 6 shows that
obtained in air (not shown). From 200 C onwards, the forward this solgel CuO/ZnO heterojunction might be used for the
current increases in the presence of H2 though the current development of the H2 gas sensor.
magnitudes at 200 C and 250 C are still in the order of 104 A
(figure 4 inset). Table 1 shows that at 300 C, the forward
current at 16 V increases about six times that of in air. This 4. Conclusions
is because of the reaction of the H2 gas molecules with the
already adsorbed oxygen molecules at the interface states, In conclusion, a p-CuO/n-ZnO thin film heterojunction has
altering the potential barrier height of the junction. As a result been fabricated. It shows rectifying diode characteristics
the current across the junction increases. However, the reverse at and above 200 C, and a thermal process dominates the
current also increases due to leakage, thereby decreasing current conduction through the junction. The IF/IR ratio when
the IF/IR ratio to 8.4, which is much smaller compared to measured in air is 485 and the ideality factor is 4.88 at 300

the value obtained in air (table 1). The n value is improved with C in air. The junction shows an increase in the forward
the increase in temperature but is still greater than 2, indicating current in H2 ambient by six times that of in air. However,
also a multiple current conduction mechanism through the increase in the reverse current reduces the IF/IR ratio to 8.4.
junction in the presence of H2 gas. The H2 gas sensitivity At 300 C, the junction shows very high sensitivity towards
S, which is defined as the current ratio IH2/Iair at different H2 gas. This work demonstrates the potential of fabrication of
bias voltages and temperatures is shown in figure 5. An a low-cost undoped CuO/ZnO thin film heterojunction for the
insignificant change in sensitivity is observed with the bias development of the H2 gas sensor.
voltage at temperatures 200 C and 250 C. However, at
300 C, the junction shows a very high sensitivity reaching
References
a maximum value of 266.5 at 3 V and thereafter a decrease
in the value. The increase in sensitivity with temperature [1] Alivov Y I, Ozgur U, Dogan S, Johnstone D, Avrutin V,
is due to the increase in the forward current resulting from Onojima N, Liu C, Xie J, Fan Q and Morkoc H 2005

931
S Mridha and D Basak

Photoresponse of n-ZnO/p-SiC heterojunction diodes [8] Ushio Y, Miyayama M and Yanagida H 1993 Fabrication of
grown by plasma-assisted molecular-beam epitaxy thin-film CuO/ZnO heterojunction and its humidity-
Appl. Phys. Lett. 86 241108 sensing properties Sensors Actuators B 12 1359
[2] Tongpool R, Leach C and Freer R 2000 Temperature and [9] Ushio Y, Miyayama M and Yanagida H 1994 Effect of
microstructural dependence of the sensitivity of hetero interface states on gas sensing properties of a CuO/ZnO
contacts between zinc oxide and copper oxide in reducing thin film heterojunction Sensors Actuators B 17 2216
environments J. Mater. Sci. Lett. 19 11923 [10] Basak D, Amin G, Mallik B, Paul G K and Sen S K 2003
[3] Orel B, Svegl F, Bukovec N and Kosec M 1993 Structural and Photoconductive UV detectors on solgel-synthesized ZnO
optical characterization of CuO particulate solid films and films J. Cryst. Growth 256 737
the corresponding gels and xerogels J. Non-Cryst. Solids [11] Ghosh R, Fujihara S and Basak D 2004 Effect of
159 4964 substrate-induced strain on the structural, electrical and
[4] Nakamura Y, Yoshioka H, Miyayama M, Yanagida H, optical properties of polycrystalline ZnO thin films
Tsurutani T and Nakamura Y 1990 Selective CO gas J. Appl. Phys. 96 268992
sensing mechanism with CuO/ZnO heterocontact [12] Selected Powder Diffraction Data for Metals and Alloys Data
J. Electrochem. Soc. 137 9403 Book 1978 vol 1 (Newtown Square, PA: International
[5] Nakamura Y, Ando A, Tsurutani T, Okada O, Miyayama M, Centre for Diffraction Data) p 107
Koumoto K and Yanagida H 1986 Gas sensitivity of [13] Kaminska E, Piotrowska A, Golaszeswka K, Kruszka R,
CuO/ZnO hetero-contact Chem. Lett. 15 4136 Kuchuk A, Szade J, Winiarski A, Barcz A, Jasinski J and
[6] Aygun S and Cann D 2005 Hydrogen sensitivity of doped Weber Z L 2003 Engineering ZnO/GaN interfaces for
CuO/ZnO heterocontact sensors Sensors Actuators tunneling ohmic contacts to GaN Mater. Res. Soc. Symp.
B 106 83742 Proc. 747 V6.7.16
[7] Baek K K and Tuller H L 1995 Atmosphere sensitive [14] Sze S M 1981 Physics of Semiconductor Devices (New York:
CuO/ZnO junctions Solid State Ion. 75 17986 Wiley)

932