TiO

2
based metal-semiconductor-metal ultraviolet photodetectors
Hailin Xue, Xiangzi Kong, Ziran Liu, Caixia Liu, Jingran Zhou, and Weiyou Chen
a
State Key Laboratory on Integrated Optoelectronics, Jilin University, Changchun 130023,
Peoples Republic of China
Shengping Ruan and Qian Xu
Department of Electronic Science and Engineering, Jilin University, Changchun 130023,
Peoples Republic of China
Received 8 March 2007; accepted 26 April 2007; published online 18 May 2007
Nanocrystalline TiO
2
thin lms were prepared by sol-gel method and were then used to fabricate
metal-semiconductor-metal ultraviolet photodetectors with Au Schottky contact. It was found that
dark current of the fabricated devices was only 1.9 nA at 5 V applied bias. High responsivity of
199 A/ W was achieved when it was irradiated by the ultraviolet light =260 nm. The low dark
current and high responsivity maybe attributed to the effect of Schottky barrier in company with
neutral semiconductor owing to the wide nger gap of 20 m. The devices show a slow time
response with a rise time of 6 s and a decay time of 15 s. The authors deduced that the slow time
response was caused by defect traps which were widely distributed in nanocrysal. 2007 American
Institute of Physics. DOI: 10.1063/1.2741128
Titanium dioxide is a wide band gap anatase 3.2 eV and
rutile 3.0 eV semiconductor and has been researched in
many aspects, such as photocatalysis and solar cell, due to its
outstanding physical and chemical properties.
14
UV photo-
detectors based on wide band gap semiconductors such as
GaN, ZnO, and diamond are widely reported
59
but a few
concerns with TiO
2
.
10
In this letter, metal-semiconductor-
metal MSM UV photodetector based on nanocrystalline
TiO
2
thin lms with Au Schottky contact was demonstrated.
TiO
2
thin lms were prepared by tetrabutyl titanate
Ti OC
4
H
9

4
through a sol-gel method. The procedure for
the preparation involved the dissolution of 10 ml of tetrabu-
tyl titanate Ti OC
4
H
9

4
in 100 ml of ethanol C
2
H
5
OH with
the purity of 99.8% which was used as a solvent, followed by
adding of 10 ml CH
3
COOH, then 10 ml of acetylacetone,
and lastly 10 ml of de-ionized water. The mixture was stirred
at room temperature for 30 min before each reagent was
added. The solution was smeared on Si 110 substrates and
rotated at 3000 rpm for 20 s to ensure the uniformity. The
surface of substrates used for the deposition of the TiO
2
lms
was oxidized, and the thickness of the SiO
2
layers was cho-
sen to be high enough 1 m in order to ensure good iso-
lation of the TiO
2
layers from silicon substrate. The samples
were then annealed for 2 h at 650 C in a mufe furnace,
leading to polycrystalline oxide lm structures. The proce-
dures from coating to annealing were repeated ve times.
The thickness of the lms was measured with a Woollam
M2000UI spectroscopic ellipsometer, and the total thickness
was about 0.15 m.
Interdigitated Au/ TiO
2
/ Au circular structure was de-
signed and fabricated. Au lm was deposited by rf magne-
tron sputtering. The thickness of the metal lms was deter-
mined by a XP-2 prolometer which indicated 260 nm for
Au lm. The planar interdigitated electrodes were prepared
by standard photolithography and lift-off technique. Both the
nger width and spacing are 20 m and the total active area
is 0.38 mm
2
.
A 30 W deuterium lamp and a monochromator were
used to measure spectral responsivity and the monochro-
matic light was calibrated with a UV-enhanced Si photode-
tector and optical power meter. The dark current and current-
voltage I-V characteristics under different wavelength
lights were measured by a Keithley 2400 source meter. An
oscilloscope was used to record the time response of the
devices.
Figure 1 shows the x-ray diffraction XRD pattern of
TiO
2
lms annealed at 650 C by sol-gel method. The lms
are composed of anatase TiO
2
as indicated by the reection
peak at 25.15. The crystallite size of TiO
2
thin lms can be
deduced from XRD line broadening using the Scherrer equa-
tion and the average crystallite size of TiO
2
was 38.02 nm.
11
Figure 2 shows the I-V characteristics of TiO
2
MSM
photodetectors under different wavelengths of UV light. The
dark current is at 10
9
magnitude and is only 1.9 nA at 5 V
bias. Obvious photoresponse can be seen when the UV light
a
Author to whom correspondence should be addressed; electronic mail:
jluxhl@163.com
FIG. 1. XRD pattern of a TiO
2
thin lm annealed at 650 C by sol-gel
method.
APPLIED PHYSICS LETTERS 90, 201118 2007
0003-6951/2007/9020/201118/3/$23.00 2007 American Institute of Physics 90, 201118-1
Downloaded 08 Oct 2007 to 59.72.114.25. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp
irradiated on the devices; the photocurrent increased to
2.77 A at 5 V under irradiation of 250 nm UV light.
Figure 3 is the spectral response of the TiO
2
MSM pho-
todetectors with Au Schottky contacts, measured at the bias
of 5 V. The photoresponse was at over the band gap and
has a cutoff at wavelength around the absorption edge of
TiO
2
330 nm. The photoresponse exhibited obvious
blueshift caused by nanometer effect. The sample was irra-
diated by the UV light with power density of 6.1 w/ cm
2
at
260 nm and the photocurrent was 2.3 A. Considering the
effective area of the device, the maximum responsivity of
199 A/ W at 260 nm was obtained, which was much higher
than most of other wide band gap photovoltaic photodectors
with MSM structure. The high responsivity may owe not
only to the decrease of the height of Schottky barrier under
UV light but also to the neutral semiconductor between the
two back to back Schottky barriers. Katz et al. proposed that
the trapping states introduced by surface defects reduce the
height of Schoottky barrier under UV light irradiation, and
the reduction causes more carriers getting across the barrier
and then enlarges the current.
1214
Moreover, the wide gap
between the electrodes induced long neutral region. The neu-
tral region works in the photoconductive mode as photosen-
sitive resistance.
15
The reduction of Schoottky barrier and the
neutral region introduces high gain, which is responsible for
the high photoresponsivity. Assuming all the photons are ab-
sorbed by the semiconductor, we calculate the total gain and
nd that it is 47.3.
Figure 4 displays the time response of the devices. The
devices show a slow time response with a rise time of 6 s
and a decay time of 15 s. We deduce that the slow time
response is attributed to the defect traps, which were widely
distributed in nanocrystal, acting as recombination centers in
the neutral region. The response time will be shorter if the
crystal grows better and the nger space becomes
smaller.
1517
The improvement of TiO
2
lms in crystalline
quality will reduce the recombination induced by the defects
and then reduce the response time. Smaller nger space may
reduce the neutral region, even making all the areas between
the electrodes to become exhausted region, where the photo-
generated carriers will be separated by the build-in eld
quickly.
In conclusion, high responsivity TiO
2
based photodetec-
tos have been fabricated. The dark current is only 1.9 nA at
5 V bias and the photoresponsivity is 199 A/ W under
260 nm irradiation. The high responsivity mainly comes
from the high gain induced by the reduction of Schottky
barrier and the existence of neutral photoconductor region.
The slow photoresponse is mainly caused by the defect in the
nonocrystalline neutral region, and the performance of de-
vices could be enhanced further by some improvements on
material and structure. The low dark current and high photo-
responsevity in such devices show extensive potential in
wide band gap photodetctor.
The authors are grateful to National Natural Science
Foundation of China No. 60374048, Jilin Province Tech-
nology Development Plan No. 2006528, and Changchun
Technology Plan No. 05GG24 for the support to the work.
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FIG. 2. I-V characteristics of TiO
2
MSM photodetectors under different UV
light wavelengths.
FIG. 3. Spectral response of the TiO
2
MSM photodetectors with Au
Schottky contacts.
FIG. 4. Time response of the devices measured under the irradiation of a
deuterium lamp at 5 V bias. An oscilloscope was used to record the voltage
change of the series resistance of 5.1 M.
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