synthesis of nano-structured materials by laser-ablation and their application to sensors

8
Synthesis of nano-structured materials by laser-ablation and their application to sensors T. Okada * , J. Suehiro Department of Electrical and Electronic Systems Engineering, Kyushu University, Fukuoka 812-8581, Japan Available online 2 March 2007 Abstract We describe the synthesis of nano-structured materials of ZnO and Pd by laser ablation and their applications to sensors. The synthesis of ZnO nano-wires was performed by nano-particle assisted deposition (NPAD) where nano-crystals were grown with nano-particles generated by laser- ablating a ZnO sintered target in an Ar background gas. The synthesized ZnO nano-wires were characterized with a scanning electron microscopy and the photoluminescent characteristics were examined under an excitation with the third harmonics of a Nd:YAG laser. The nano-wires with a diameter in the range from 50 to 150 nm and a length of up to 5 mm were taken out of the substrate by laser blow-off technique and/or sonication. It was confirmed that the nano-wires showed the stimulated emission under optical pumping, indicating a high quality of the crystalinity. Pd nano- particles were generated by laser-ablating a Pd plate in pure water. The transmission electron microscope observation revealed that Pd nano- particles with a diameter in the range from 3 nm to several tens of nanometers were produced. Using these nano-structured materials, we successfully fabricated sensors by the dielectrophoresis techniques. In the case of the ultraviolet photosensor, a detection sensitivity of 10 nW/cm 2 was achieved and in the case of hydrogen sensing, the response time of less than 10 s has been demonstrated with Pd nano-particles. # 2007 Elsevier B.V. All rights reserved. Keywords: Nano-structure; Laser-ablation; Nd:YAG laser 1. Introduction Recently the synthesis and the applications of nano- structured materials have attracted a great attention. One of the interesting materials is zinc oxides (ZnO), which are a wide- band-gap II–VI semiconductor that has the direct band gap of about 3.37 eV at room temperature, and is well recognized as the functional material suitable for opto-electronic applica- tions. In the past few years, nano-structured ZnO crystals, such as nano-rods, nano-wires and nano-balls have been of growing interest due to their importance both in scientific and technological researches [1]. Considerable efforts have been paid on the synthesis and on the study of nano-structured ZnO crystals [2–4]. Several methods have been reported on the synthesis of the ZnO nano-structured crystals, including vapor- phase transport with a vapor–liquid–solid (VLS) growth mechanism [5], wet chemical route [3], chemical vapor deposition [6], nano-particle assisted deposition (NPAD) [7,8] and so on. One of the promising application field of these nano-structured ZnO crystals is the sensors, in which a large surface-to-volume ratio is essential for achieving higher sensitivity. So far, ZnO nano-wires have been applied to the ultraviolet photosensors [9], the ethanol sensors [10], the oxygen sensors [11], the hydrogen sensor [12], the pH sensors [13] and so on. Recently we have also successfully fabricated an ultraviolet photo sensor with a high sensitivity using ZnO nano-wires synthesized by NPAD [14]. From the viewpoint of gas sensor application, palladium (Pd) has an interesting characteristic for the hydrogen molecules, including the large capacity of hydrogen occlusion and the catalysis effect for the reaction between hydrogen and oxygen at room temperature. These characteristics of Pd are very attractive for the hydrogen sensor and their sensitivities are also enhanced by down-sizing into the nanometer range [15]. Therefore, preparation of nano-structured Pd or other noble metals is also an active research field, where chemical routes [15,16] and the laser ablation of noble metal in a solution [17–19] has attracted a great attention. More recently, Wang et al. reported the hydrogen sensors using ZnO nano-wires covered with Pd and other noble metals by sputtering deposition [20]. www.elsevier.com/locate/apsusc Applied Surface Science 253 (2007) 7840–7847 * Corresponding author. Tel.: +81 92 642 3913; fax: +81 92 642 3965. E-mail address: [email protected] (T. Okada). 0169-4332/$ – see front matter # 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2007.02.152

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www.elsevier.com/locate/apsusc

Applied Surface Science 253 (2007) 7840–7847

Synthesis of nano-structured materials by laser-ablation

and their application to sensors

T. Okada *, J. Suehiro

Department of Electrical and Electronic Systems Engineering, Kyushu University, Fukuoka 812-8581, Japan

Available online 2 March 2007

Abstract

We describe the synthesis of nano-structured materials of ZnO and Pd by laser ablation and their applications to sensors. The synthesis of ZnO

nano-wires was performed by nano-particle assisted deposition (NPAD) where nano-crystals were grown with nano-particles generated by laser-

ablating a ZnO sintered target in an Ar background gas. The synthesized ZnO nano-wires were characterized with a scanning electron microscopy

and the photoluminescent characteristics were examined under an excitation with the third harmonics of a Nd:YAG laser. The nano-wires with a

diameter in the range from 50 to 150 nm and a length of up to 5 mm were taken out of the substrate by laser blow-off technique and/or sonication. It

was confirmed that the nano-wires showed the stimulated emission under optical pumping, indicating a high quality of the crystalinity. Pd nano-

particles were generated by laser-ablating a Pd plate in pure water. The transmission electron microscope observation revealed that Pd nano-

particles with a diameter in the range from 3 nm to several tens of nanometers were produced. Using these nano-structured materials, we

successfully fabricated sensors by the dielectrophoresis techniques. In the case of the ultraviolet photosensor, a detection sensitivity of 10 nW/cm2

was achieved and in the case of hydrogen sensing, the response time of less than 10 s has been demonstrated with Pd nano-particles.

# 2007 Elsevier B.V. All rights reserved.

Keywords: Nano-structure; Laser-ablation; Nd:YAG laser

1. Introduction

Recently the synthesis and the applications of nano-

structured materials have attracted a great attention. One of

the interesting materials is zinc oxides (ZnO), which are a wide-

band-gap II–VI semiconductor that has the direct band gap of

about 3.37 eV at room temperature, and is well recognized as

the functional material suitable for opto-electronic applica-

tions. In the past few years, nano-structured ZnO crystals, such

as nano-rods, nano-wires and nano-balls have been of growing

interest due to their importance both in scientific and

technological researches [1]. Considerable efforts have been

paid on the synthesis and on the study of nano-structured ZnO

crystals [2–4]. Several methods have been reported on the

synthesis of the ZnO nano-structured crystals, including vapor-

phase transport with a vapor–liquid–solid (VLS) growth

mechanism [5], wet chemical route [3], chemical vapor

deposition [6], nano-particle assisted deposition (NPAD)

* Corresponding author. Tel.: +81 92 642 3913; fax: +81 92 642 3965.

E-mail address: [email protected] (T. Okada).

0169-4332/$ – see front matter # 2007 Elsevier B.V. All rights reserved.

doi:10.1016/j.apsusc.2007.02.152

[7,8] and so on. One of the promising application field of

these nano-structured ZnO crystals is the sensors, in which a

large surface-to-volume ratio is essential for achieving higher

sensitivity. So far, ZnO nano-wires have been applied to the

ultraviolet photosensors [9], the ethanol sensors [10], the

oxygen sensors [11], the hydrogen sensor [12], the pH sensors

[13] and so on. Recently we have also successfully fabricated

an ultraviolet photo sensor with a high sensitivity using ZnO

nano-wires synthesized by NPAD [14].

From the viewpoint of gas sensor application, palladium (Pd)

has an interesting characteristic for the hydrogen molecules,

including the large capacity of hydrogen occlusion and the

catalysis effect for the reaction between hydrogen and oxygen at

room temperature. These characteristics of Pd are very attractive

for the hydrogen sensor and their sensitivities are also enhanced

by down-sizing into the nanometer range [15]. Therefore,

preparation of nano-structured Pd or other noble metals is also an

active research field, where chemical routes [15,16] and the laser

ablation of noble metal in a solution [17–19] has attracted a great

attention. More recently, Wang et al. reported the hydrogen

sensors using ZnO nano-wires covered with Pd and other noble

metals by sputtering deposition [20].

Fig. 2. SEM image of ZnO nano-wires grown on sapphire (0 0 0 1) substrates.

T. Okada, J. Suehiro / Applied Surface Science 253 (2007) 7840–7847 7841

Another subject, that should be considered in the application

of nano-structured materials to electronic devices like sensors,

is the handling of nano-materials in the fabrication of devices.

For instance, it is difficult task even to connect the electrodes

onto a nano-wire that is randomly placed on a substrate. One

sophisticated connection process includes the position sensing

of a nano-wire, the resist coating on it, the electron beam

lithography for the patterning of electrodes, the metal film

deposition and the lift-off [1]. They are the very complicated,

time consuming and expensive processes. We have recently

applied the dielectrophoresis technique (DEP) to collect the

carbon nano-tubes [21] and ZnO nano-wires onto the pattered

electrodes [14], demonstrating that the dielectrophoresis

technique is suitable for the mass production process.

In this paper, we describe our recent progresses of synthesis

of nano-structured materials of ZnO and Pd by laser ablation for

their applications to sensors. In Section 2, the preparations of

ZnO nano-wires by NPAD and of the Pd nano-particles by the

laser-ablation in pure water are described. In Section 3, the

handling of ZnO nano-wires and the sensor device fabrication

by DEP are described. Finally in Section 4, the characteristics

of an ultraviolet photosensor made by the ZnO nano-wires and

the possible application of the Pd nano-particles to the

hydrogen sensors are described.

2. Preparation of nano-structured materials

2.1. Preparation of ZnO nano-wires and their fluorescence

property

The apparatus used for ZnO growth is shown in Fig. 1 and it

is similar to that used for the synthesis of carbon nano-tubes by

laser ablation. It is a laser-ablation system in a high-temperature

background gas that has also been used to synthesize various

types of semiconductor nano-wires. A rotating ZnO sintered

target was laser-ablated by a KrF excimer laser in a quartz

furnace. The temperature of the furnace was varied in the range

from 870 K to 1470 K, which were measured by a thermo-

couple at an outer wall of the quartz tube. The KrF laser was

operated with an irradiation fluence of about 4 J/cm2 at a

repetition rate of 20 Hz. During the deposition, Ar gas at a

pressure in the range from about 30 and 60 kPa were flew with a

flow rate of 15 sccm. ZnO crystals were grown on the substrates

placed in front of the ZnO target, as shown in Fig. 1. ZnO

crystals were grown on sapphire (0 0 0 1) and (1 1 0 0)

substrates. Only when the substrates were placed between 10

and 30 mm in front of the target, appreciable amount of white

Fig. 1. Experimental appratus for synthesis of ZnO nano-structured crystals.

deposits was observed on the substrates. A variety of nano-

structured crystals was obtained by changing a kind of substrate

and the deposition conditions such as the furnace temperature,

gas pressure and so on [22].

ZnO nano-wires with a diameter of about 50 nm were

synthesized on sapphire (0 0 0 1) substrates. A SEM image of

the crystals is shown in Fig. 2 which was synthesized at an Ar

gas pressure of 34 kPa at 1070 K. It cannot be seen in the SEM

image, but hexagonal-shaped crystals exist between the nano-

wires and the substrate. When the (1 1 0 0) sapphire substrate

was used instead of (0 0 0 1) substrates, the ZnO cone-shaped

crystals perpendicular to the substrate surface was obtained at

an Ar pressure of 30 kPa and a substrate temperature of 1070 K,

as shown in Fig. 3. The similar effect of differently oriented

substrates on the ZnO crystal growth has been reported [23].

The ZnO cone-shaped crystals are very much interesting for the

application to the field emission [24], because of their unique

geometry for the field enhancement.

In the above studies, no catalyst was used to grow the ZnO

nano-wires and the relatively large hexagonal crystals always

exist between the nano-wires and the substrate. Therefore, it is

thought that the growth mechanism of ZnO nano-wires in the

present experiments is different from the VLS mechanism

with a help of catalyst. In the VLS mechanism, on the other

hand, the nano-wires grow directly from the substrate with the

catalysts on the other edge of the nano-wires. We believe that

Fig. 3. SEM image of ZnO nano-cone grown on sapphire (1 1 0 0) substrate.

Fig. 4. Growth model of nano-particle assisted deposition (NPAD). (a) Nano-

particles are formed in gas phase. (b) Nano-particles are transported on

substrate, where nano-particles melt and relatively large crystals grow. (c)

At the tips of the crystals grown on substrate, nano-wires start to grow with self-

catalyst effect. (d) Nano-particles that reach the self-catalysis point are fused

into nano-wire due to low melting temperature and precipitate as the solid nano-

wires due to high melting temperature of the larger structure.

T. Okada, J. Suehiro / Applied Surface Science 253 (2007) 7840–78477842

the nano-particles play an important role in the growth of the

nano-structured crystals. A proposed growth mechanism is

summarized in Fig. 4. After the laser ablation, ZnO nano-

particles are formed in the gas phase. The nano-particles are

transported onto the heated substrates, where the nano-

particles melted and the crystals grow. When the large crystals

grow to some extent, the nano-wires suddenly start to grow. It

is not understood what triggers the growth of the nano-wires,

but it is likely that the tip of the initially grown crystals acts as

self-catalyst. Since the nano-particles have low melting

temperature, each nano-particle melts on the self-catalyst

just as it occurs on the catalysts in the VLS mechanism. After

the nano-particles are fused on a nano-wire, they precipitate as

a solid nano-wire due to its high melting temperature.

Even in NPAD, the site-selective growth of ZnO nano-wires

was also possible, as already reported by another groups for the

Fig. 5. Site selected growth of ZnO nano-wires with Au nano-particles as cat

VLS mechanism [1], when a catalyst on a Si wafer was used.

Fig. 5 shows the SEM images of ZnO nano-wires grown on a Si

wafer with Au nano-particles as the catalyst. Au nano-particles

were produced by laser-ablating micron-sized Au particles in

water with a surfactant. A part of the Si wafer was covered by

colloidal solution of Au nano-particles and dried. As shown in

Fig. 5(a), ZnO nano-wires grew only on the site with Au nano-

particles. Fig. 5(b) shows the magnified image of nano-wires

and it is found that nano-wires grew directly on the substrate

without the rod crystals which can be seen in Figs. 2 and 3.

Photoluminescence spectra were observed with a multi-

channel spectrometer by exciting the ZnO crystals with the

third harmonics of a Q-switched Nd:YAG laser. Firstly the

ZnO crystals as gown on the substrate in Fig. 2 were examined

by exciting an unfocused laser beam. In this case, many

crystals were excited simultaneously and the sum of the

photoluminescence light from many crystals was observed.

Fig. 6(a) shows the photoluminescence spectrum from the

crystals shown in Fig. 2(b) at a fluence of 0.6 mJ/cm2. In this

case, just broad spectrum was observed near the band gap of

ZnO and no stimulated emission was observed at a fluence of

0.6 mJ/cm2. When the crystals were taken out of the substrate

by the laser blow-off technique that is described below, a

narrow spectral peak shown in Fig. 6(b) was observed on a

broad fluorescence spectrum even at a fluence of 0.6 mJ/cm2,

indicating the on-set of the stimulated emission. In the case of

Fig. 6(b), the photoluminescence signal only from the lump of

the crystals shown in the inset was observed by an optical

microscope.

2.2. Synthesis of Pd nano-particles

The Pd nano-particles were synthesized by the laser-ablation

in pure water. A Pd disk plate in pure water was laser-ablated by

the second harmonics from a Q-switched Nd:YAG laser with an

energy fluence in the range from 5 to 70 J/cm2. No surfactant

which was often added to prevent the aggregation was used. As

the ablation proceeded for about 30 min, the color of the

solution turned to brown probably due to the plasmon

resonance in the ultraviolet region, depending on the fluence.

In a sample solution prepared at a low irradiation fluence, no

precipitation was observed even after several days.

alyst on Si wafer. SEM images with low (a) and high (b) magnifications.

Fig. 6. Photoluminescence spectra of ZnO crystals shown in Fig. 2(b) and of micro ZnO crystals in the inset.

Fig. 7. TEM images of Pd nano-particles (a) and high magnification image (b).

Fig. 8. Size distribution of Pd nano-particles prepared by laser ablation in

water.

T. Okada, J. Suehiro / Applied Surface Science 253 (2007) 7840–7847 7843

The TEM images of Pd nano-particles are shown in Fig. 7(a)

and a high magnification image (b). Pd nano-particles with a

diameter of in the range of 2–10 nm were observed, and their

size distribution is shown in Fig. 8. The lattice structure can be

seen in the high magnification image, indicating the Pd nano-

particles are crystallized. The measured lattice spacing of

0.24 nm corresponds to the spacing along the (1 1 0) plane. In

some samples, a unique structure was observed, as shown in

Fig. 9. The string-like structure with a diameter of in the range

3–5 nm was observed. The diameter of the string is as small as

that of nano-particles observed in Fig. 7. It is though that the

strings were made by nano-soldering of the primary nano-

particles during the successive ablation.

3. Device fabrication

In order to fabricate electronic devices such as sensors using

nano-wires, the electrodes have to be properly connected to the

nano-wires. One of the simple approaches is to deposit metal

electrodes just on the substrate where nano-wires are

synthesized [20]. In this scheme, however, the characteristics

of the devices depend on the in-plane structure or the

connection between nano-wires, and it results in unreliable

reproducibility in the device operation. More reliable devices

can be fabricated by directly connecting each nano-wires to the

electrodes. In this case, first of all, nano-wires have to be taken

Fig. 9. TEM image of Pd nano-strings.

T. Okada, J. Suehiro / Applied Surface Science 253 (2007) 7840–78477844

off from the substrate and transferred to a proper substrate. We

have examined the laser brow-off and the sonication for the

purpose. In the laser brow-off technique, the nano-wires on the

substrate are irradiated from the back-side through the substrate

and the brown-off nano-wires are collected on another

substrate. However, it was difficult to obtain isolated nano-

wires by the laser brow-off and a typical species collected on a

substrate was similar to those shown in the inset of Fig. 6(b).

The sonication is more convenient to take the nano-wires out

of the substrate. The substrate was immersed in ethanol solution

and sonicated in a water bath. Fig. 10(a) shows the SEM images

of the nano-wire substrate after sonication of 5 min. Comparing

with the SEM image in Fig. 2 before the sonication, it was

found that all of nano-wires were taken out of the substrate by

5 min. sonication. By dropping the ethanolic solution on

another substrate, an isolated nano-wire can be obtained, as

shown in Fig. 10(b).

In order to fabricate the electrodes on nano-wires, there are

several methods for connecting nano-wires to the electrodes.

One sophisticated method is a patterned deposition of metal

films with a help of the electron beam lithography. In

this method, the position of a nano-wire dispersed on a

substrate is recorded by an aligner in a lithographic system,

Fig. 10. SEM images of ZnO nano-wire after sonication (a)

and the resist pattern is created by pattering the resist coated

on the substrate by irradiation of electron beam. Then metal

films were deposited on the etched resist pattern. This method

is the best for a complicated device, but it is expensive and

time-consuming process and not suitable for the real

production. In order to fabricate sensor devices with high

production rate, we have adopted electrodiphletic manipula-

tion of nano-wires.

Electrokinetic manipulation has been recognized as a

useful technique for separation, alignment and positioning of

carbon nano-tubes (CNTs) and nano-wires composed of

semiconductor or metal. The authors have previously

demonstrated a new fabrication method of a CNT-based

gas sensor using positive DEP [25–27]. DEP is the

electrokinetic motion of dielectrically polarized materials

in non-uniform electric fields. The polarized material is

driven towards (positive DEP) or away from (negative DEP)

the high field region depending on the complex dielectric

permittivity of the particle and its surrounding medium.

Under action of positive DEP, CNTs are trapped in the

microelectrode gap establishing an electrical connection,

which provides a way to measure the sensor impedance using

an external measuring circuit. In the present study, we further

extended the possibility of the DEP manipulation technique

to ZnO nano-wires and Pd nano-particles, which were

synthesized by the laser ablation method, as described before.

The DEP manipulation system is schematically depicted in

Fig. 11. The same system has been successfully employed for

DEP fabrication of a CNT-based gas sensor in the authors’

previous studies [25–27]. The equipment was based on the

DEPIM system, which has been developed by the authors for

electrical inspection of bacteria or microorganisms [28]. An

interdigitated microelectrode of thin chrome film was

patterned on a glass substrate by a photolithography

technique. Each electrode finger had 5 mm length and

5 mm minimum clearance. Fig. 12(a) illustrates a numerical

calculation result of the electric field distribution in the

castellated electrode. Since higher electric field appears

around the electrode corners, one can expect to trap the nano

materials at these sites by positive DEP. The castle-wall

electrode was surrounded by a silicone rubber spacer to form

a sealed chamber through which the nano materials

suspension was forced to flow by a peristaltic pump. The

and single ZnO nano-wire transferred on substrate (b).

Fig. 11. Schematic diagram of the experimental set-up for ZnO nano-wire

photosensor fabrication using positive DEP.

T. Okada, J. Suehiro / Applied Surface Science 253 (2007) 7840–7847 7845

ZnO nano-wires were suspended in ethanol, whereas Pd

nano-particles were suspended in deionized water. The DEP

trapping of the nano materials to the microelectrode was

performed with an ac voltage of 100 kHz frequency and 20 V

amplitude (peak to peak value). This ac voltage was also

used to simultaneously measure the electrode impedance by

using a lock-in amplifier controlled by a PC. After 60 min, the

DEP process was stopped and the ethanol was gently

evaporated at room temperature. The thus prepared micro-

electrode retaining the nano materials was observed using a

Fig. 12. (a) Calculation result of the electric field distribution in castellated

microelectrode gaps (FEMLAB). (b) SEM images of ZnO nano-wires trapped

in castellated microelectrode gaps by positive DEP.

scanning electron microscope and tested as a UV photosensor

or a hydrogen gas sensor.

The SEM images of the ZnO nano-wires trapped onto the

castellated microelectrode are shown in Fig. 12(b). The ZnO

nano-wires were trapped around the electrode corner, where the

electric field became higher as theoretically predicted (see

Fig. 12(a)). This implies that the ZnO nano-wires were trapped

under action of positive DEP. The trapped ZnO nano-wires

were aligned along the electric field line and bridged the

electrode gap. The DEP trapping process was little influenced

by the field frequency in the range 1 kHz–1 MHz. The SEM

images also revealed that DEP-trapped ZnO nano-wires could

be firmly immobilized on the microelectrode even after ethanol

evaporation. The impedance measurement revealed that both

the conductance and capacitance components increased with

elapsed time, namely, with more ZnO nano-wires trapped onto

the electrode. The impedance change implies that ZnO nano-

wires establish an electrical connection between the micro-

electrode, which has implications for nano-device self-

assembly using positive DEP. Similar results were obtained

for Pd nano-particles.

4. Device performance

4.1. Photoresponse of the DEP-trapped ZnO nano-wires

Considering the bandgap of ZnO (3.37 eV), it is expected

that the trapped ZnO nano-wires respond to UV light of

wavelength shorter than 380 nm. According to this prediction,

characterization of the DEP-fabricated ZnO nano-wire photo-

sensor was conducted mainly at 365 nm. When the ZnO nano-

wire photosensor was illuminated by 365 nm UV light, the

conductance exponentially increased with a time constant of a

few minutes and then gradually saturated as shown in Fig. 13.

When the UV light was turned off, the conductance

exponentially decreased back to the initial value. At higher

UV intensity, the conductance response became larger. The

Fig. 13. Transient conductance responses of the DEP-fabricated ZnO nano-

wire photosensor to 365 nm UV of various intensities.

T. Okada, J. Suehiro / Applied Surface Science 253 (2007) 7840–78477846

ZnO nano-wire photosensor could detect UV down to the

10 nW/cm2 range. Similar slow UV responses have been

reported for ZnO thin films fabricated by various methods [29].

It has been widely accepted that the slow response could be

attributed to adsorption and UV-triggered photodesorption of

ambient gas molecules such as O2 or H2O. Since the present

experiments were conducted in open air, the slow UV response

of ZnO nano-wires also seemed to be governed by the same

mechanism. According to this mechanism, the conduction

increase of the ZnO nano-wire photosensor is triggered by UV

light-induced photodesorption of the ambient gas. This can be

confirmed from Fig. 14, which shows the spectral response of

the ZnO nano-wire photosensor. The sharp cut-off near 390 nm

agrees with the critical wavelength predicted from the ZnO

bandgap.

Although the UV response mechanism of the DEP-

fabricated ZnO nano-wire photosensor was basically same as

that of ZnO thin film, the DEP-fabricated ZnO nano-wire

photosensor had a considerably higher UV sensitivity than ZnO

thin films as well as ZnO nano-wires assembled between metal

electrodes by other methods. For example, Sharma et al.

investigated the UV response of ZnO thin films prepared by

magnetron sputtering down to 0.6 mW/cm2 intensity at 365 nm

[29]. Photoresponse of ZnO nano-wires was measured using

UV light of 0.3 mW/cm2 intensity [30]. Since the minimum

detection limit of UV intensity was not clearly mentioned in

these literatures, precise comparison of UV detection limit was

difficult. However, the DEP-fabricated ZnO nano-wire photo-

sensor could detect UV light with an intensity as low as 10 nW/

cm2, which has not been detected by using conventional ZnO

photosensors. The possible reason for such a high sensitivity

may be explained as follows. First, the large surface area to

volume ratio of a ZnO nano-wire can enhance UV light

absorption. As shown in Fig. 12(b), DEP-trapped ZnO nano-

wires lie on the surface of the electrode substrate. This

geometry allows the ZnO nano-wire surface to be fully exposed

to the incident light when the photosensor is placed so that the

electrode plane is normal to the light beam. Another advantage

Fig. 14. Spectral response of the DEP-fabricated ZnO nano-wire photosensor

measured at an identical intensity.

is obtained by the DEP fabrication technique demonstrated in

the present study. The authors have previously shown that the

DEP manipulation could realize controlled fabrication of a

CNT-based gas sensor [26]. Although the normalized sensor

response was not dependent on the number of CNTs, the

absolute sensor response DG increased linearly with the sensor

initial conductance G0 or the number of trapped CNTs, which

formed parallel connections on the microelectrode. This

realized a higher signal-to-noise ratio in the gas sensing and

improved the effective sensitivity. Similarly to this, the

photoresponse of the DEP-fabricated ZnO nano-wire photo-

sensor can be regarded as a sum of each nano-wire response.

Considering the number of the electrode gap (DEP sites) on the

sensor electrode (about 2000), the absolute response of the

DEP-fabricated ZnO nano-wire photosensor can be increased

by four orders of magnitude if several nano-wires are trapped in

each gap as shown in Fig. 12(b). By optimizing the electrode

configuration, more nano-wires will be assembled onto one

electrode chip, further increasing the photoresponse.

4.2. Hydrogen gas sensing using DEP-trapped Pd nano-

particles

Pd has been widely used in hydrogen gas sensors because of

the catalytic properties and high hydrogen absorption capacity.

Pd nano-particles are expected to enhance these advantages

because of the large surface area to volume ratio. For example,

Walter et al. demonstrated arrays of mesoscopic Pd wires could

form the basis for hydrogen sensors and hydrogen-actuated

switches [15]. These devices were constructed by electro-

depositing Pd mesowires on a highly oriented pyrolytic

graphite surface and then transferring these mesowires to a

cyanoacrylate film. After an exposure to hydrogen, Pd lattice

expands so that nano-scopic gaps in each mesowire close

decreasing the sensor resistance. It was expected that Pd nano-

particles trapped onto a microelectrode by positive DEP might

Fig. 15. Transient conductance responses of the DEP-fabricated Pd nano-

particle gas sensor to hydrogen gas (1% in dry air). The measurement was

conducted at room temperature.

T. Okada, J. Suehiro / Applied Surface Science 253 (2007) 7840–7847 7847

also serve as a hydrogen sensor according to a similar

mechanism. Fig. 15 shows the conductance response of a DEP-

trapped Pd nano-particle array after an exposure to hydrogen

(1% in dry air) at room temperature. The conductance abruptly

increased at hydrogen exposure with a response time of a few

seconds. The result implies that the DEP-trapped Pd nano-

particle array is potentially applicable to a hydrogen sensor

with a fast response time. At the moment, however, the gas

sensor operation is not reversible, that is, the conductance does

not recover to the initial value when it is purged with pure air.

More detail investigation are under way to improve the sensor

response as well as to understand the hydrogen sensing

mechanism.

5. Conclusion

We successfully synthesized ZnO nano-wires and other

nano-structured ZnO crystals by the nano-particle assisted

deposition (NPAD) with a help of laser ablation in a high

pressure Ar gas. In NPAD, nano-particles were generated in situ

by laser ablation, and they are transported onto a substrate for

the crystal growth. It is thought that a lower melting

temperature of nano-particles which is lower than the melting

temperature of grown nano-structured crystal, plays an

important role in the crystal growth. Pd nano-particles have

been generated by laser-ablation of Pd metal disk in pure water.

Pd nano-particles with a diameter in the range from 3 to 10 nm

and Pd nano-strings have been obtained. These nano-structured

materials were used to fabricate sensor devices, where the

electrodiphletic manipulation was successfully used to collect

the nano-materials onto the electrodes. In the case of the

ultraviolet photosensor made by ZnO nano-wire, a detection

sensitivity of 10 nW/cm2 was achieved and in the case of

hydrogen sensing, the response time of less than 10 s has been

demonstrated with Pd nano-particles.

Acknowledgements

The authors would like to thank Prof. M. Shiratani and Dr. K.

Koga for TEM observation, and Dr. K. Imasaka, Messrs M.

Higashihata, J. Nishimura, K. Kawashima, N. Nakagawa, S.

Hidaka, S. Yamane for their help in performing the experiments.

A part of this work was supported by Grant-in-Aid for Scientific

Research from the Japan Society of Promotion of Sciences (no.

18360151 and no. 18360200).

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