Journal of Alloys and Compounds 581 (2013) 196201

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Journal of Alloys and Compounds

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Fabrication of ZnO nanorods for NO2 sensor applications: Effect of dimensions and electrode position
Sadullah ztrk a, Necmettin Kln a,b,, Zafer Ziya ztrk a,c
a

Gebze Institute of Technology, Science Faculty, Department of Physics, 41400 Gebze, Kocaeli, Turkey Koc University, Electrical and Electronics Engineering, 34450 Sariyer, Istanbul, Turkey c _ Research Center, Materials Institute, 41470 Gebze, Kocaeli, Turkey TBITAK-Marmara
b

a r t i c l e

i n f o

a b s t r a c t
In this study, zinc oxide (ZnO) nanorods were fabricated by using hydrothermal method and resistive type nitrogen dioxide (NO2) sensing properties of the nanorods were investigated depending on temperature, NO2 concentration, electrode position and the dimension of the nanorods. To produce ZnO seed layer, zinc acetate solution was coated on a glass substrate by using spin-coater. ZnO nanorods were grown by changing concentration of solution at 90 C for 3 h onto seed layer coated substrate. ZnO nanorods were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was observed that the diameters of ZnO nanorods were approximately 30 nm, 60 nm and 120 nm depending on solution concentration. For gas sensing measurements, interdigitated Au electrodes were coated on top or bottom of ZnO nanorods by using thermal evaporator. All samples were tested against to NO2 in dry air ambient depending on concentration (100 ppb1 ppm) in the temperature range of 25200 C. The highest sensor response was observed for ZnO nanorods that were 60 nm in diameter. The response and recovery times for all sensors decreased with increasing temperature and the sensors were fully recovered above temperature of 100 C. 2013 Elsevier B.V. All rights reserved.

Article history: Received 17 March 2013 Received in revised form 8 July 2013 Accepted 10 July 2013 Available online 18 July 2013 Keywords: ZnO Nanorods Hydrothermal process NO2 sensor Gas sensor

1. Introduction Chemical and biological sensors have a profound inuence in the areas of personal safety, public security, medical diagnosis, detection of environmental toxins, semiconductor processing, agriculture, and the automotive and aerospace industries. The past few decades have seen the development of a multitude of simple, robust, solid-state sensors whose operation is based on the transduction of the binding of an analyte at the active surface of the sensor to a measurable signal that most often is a change in the resistance, capacitance, or temperature of the active element [1]. Semiconducting metal oxide materials (WO3, TiO2, SnO2, ZnO, etc.) have been studied in many research areas such as thin lm transistors, spintronics, solar cells, and gas sensors, due to the novel properties of [112]. Importance of gas sensors increases day by day depending on growing energy needs because a large part of energy needs is provided from fossil fuel. With consuming of fossil fuel, some of hazardous gases (SOx, NOx, etc.) release to the atmosphere and they have negative effects on the environment. Nitrogen dioxide (NO2) is one of the highly toxic gas species
Corresponding author. Address: Gebze Institute of Technology, Science Faculty, Department of Physics, P.O. Box 141, 41400 Gebze, Kocaeli, Turkey. Tel.: +90 262 6051312; fax: +90 262 6538490. E-mail address: nkilinc@gyte.edu.tr (N. Kln).
0925-8388/$ - see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jallcom.2013.07.063

that are colorful and odor. Moreover, to avoid harmful effects of NO2, maximum concentration in the air is expressed less than 3 ppm [13]. The main source of NO2 is man-made as combustion engines and industrial applications. Because of highly hazardous gas to human health and environment, highly reliable, selective and sensitive gas sensors are needed. Although metal oxide materials are resistant to unfavorable effects of ambient, they are highly sensitive to change in toxic gases especially above the temperature of 200 C [5]. For improving of sensor properties such as sensitivity, response time, recovery time and reducing optimal working temperatures to low temperatures, researchers have been focused on two ways. Firstly, doping of metal oxides with noble metals such as palladium (Pd), platinum (Pt) and secondly, nanostructures of metal oxides such as nanowires, nanotubes, nanorods [14,712]. Functionalization or doping of metal oxides with noble metals provides metal oxide based sensors as selective, operation at low temperature and sensitive due to catalytic properties of noble metals. Because of high aspect ratio, sensing area of the nanostructured materials is higher than their bulk and thin lm structures. Therefore, many groups have focused on fabricating nanostructured metal oxide gas sensor for improving their sensor parameters such as sensitivity and low temperature operation [112]. In general, the gas sensing mechanism of metal oxides at high temperature explained with transfer of electrons between the sensing material and target gases, with the

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Fig. 1. Schematic illustrations of contact electrodes for ZnO nanorod sensor structures (top (a) and bottom (b) contact electrodes) and a schematic diagram for NO2 gas sensing measurement system.

formation or deformation of the depletion layer depending on the material [5]. But the gas sensing mechanism of metal oxide sensors at low temperature could be elucidated with a thin layer of condensed humidity on the surface of the metal oxide [14,15]. This is similar to hydrogenated diamond and/or silicon based sensors. Joshi and Kumar discussed gas sensing mechanism of Si nanowires at room temperature in details [16]. Different forms of nanostructures such as nanowires and nanorods have been fabricated with different methods such as electrochemical deposition, chemical vapor deposition, and hydrothermal. In this study, hydrothermal method is used for producing ZnO nanorods due to its low cost. ZnO is one of the most attractive semiconductors, and has wide band gap (3.37 eV) with hexagonal wurtzite structure, high exciton binding energy (60 meV), and a wide range of applications such as sensors, optoelectronic devices, photonic detectors, polarized light emitting devices, catalysis, and photovoltaics [17]. Many researchers have focused on gas sensor based on nanostructured ZnO and typical examples for ZnO based gas sensor are summarized as follow. Hsueh et al. fabricated ZnO nanowires by chemical vapor

deposition technique on ZnO:Ga/Si substrate for sensing ethanol at a temperature range of 180300 C [18]. Wu et al. fabricated ZnO nanowires using an electrospinning method and used in gas sensors for the detection of ethanol at 220 C. They found that ZnO nanowires showed an excellent sensitivity of nearly 90% was obtained at a low ethanol concentration of 10 ppm [19]. Lee et al. fabricated ZnO nanobarbed nanobers by electrospinning and chemical bath deposition technique for investigation of gas sensing properties of these nanostructures and sensing mechanism. In their works, fabricated samples were tested to different
Table 1 The abbreviations of ZnO nanorod devices with their preparation conditions and diameters. Devices Z1 Z2 Z3 Z4 Concentration (M) 0.001 0.01 0.1 0.01 Electrode position Top of the nanorod Top of the nanorod Top of the nanorod Bottom of the nanorod Diameters (nm) 30 60 120 60

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S. ztrk et al. / Journal of Alloys and Compounds 581 (2013) 196201 nanorod, zinc nitrate hexahydrate (Zn(NO3)26H2O) and hexamethylenetetramine (HMTA; C6H12N4) were used as reagents in equi-molar. ZnO nanorods were synthesized on the seed layer by using hydrothermal process at 90 C for 3 h. For controlling dimensions of the nanorods, solutions were prepared with various concentrations (0.1 M, 0.01 M and 0.001 M). ZnO nanorods that synthesized in 0.1 M, 0.01 M and 0.001 M equi-molar Zinc nitrate and HMTA aqueous solutions were called as abbreviations Z1, Z2, and Z3 respectively. After hydrothermal deposition, all samples were cleaned with deionized water and then, annealed at 500 C for 2 h in dry air. After annealing of ZnO nanorods, we used X-ray diffraction (XRD, Cu Ka, k = 0.154 nm), and scanning electron microscopy (SEM; Jeol JSM 6335) to determine crystalline structure and morphologies of ZnO nanorods. For gas sensing measurements, two different electrode structures were used as shown in Fig. 1a and b. First one is an interdigitated (IDT) gold electrodes were coated on top (Fig. 1a) of ZnO nanorods (synthesized in 0.1 M, 0.01 M and 0.001 M equi-molar Zinc nitrate and HMTA aqueous solutions) and other is IDT gold electrodes coated on ZnO seed layer and then ZnO nanorods synthesized in only 0.01 M equi-molar Zinc nitrate and HMTA aqueous solution on this structure that called with abbreviation Z4. Table 1 shows the abbreviation of ZnO nanorods according to production conditions. The IDT gold electrodes were coated by using a Leybold Univex 450 evaporator system. Schematic illustration of fabricated sensor structures was shown in Fig. 1a and b. The thickness of Au electrodes was 100 nm. All samples were tested against to NO2 in concentration range of 100 ppb1 ppm and at the temperature range from room temperature to 200 C. A schematic diagram of gas sensing measurement system was given in Fig. 1c. The temperature of the sensor devices was controlled with a Lakeshore 340 temperature controller in order to measure temperature dependent sensor parameters. The effect of the NO2 gas on the resistance of ZnO nanorod sensors was measured in a homemade chamber with volume of 1 L. High purity dry air was used as carrier gas in the experiments. Diluted NO2 gas (1%) in high purity dry air was used as target gas. First, the test chamber was purged with high purity dry air ow (ow rate: 200 sccm) until the resistance reached a steady value and then the chamber was closed. Then diluted NO2 gas in high purity dry air was injected with a gas tight micro syringe to reach the concentration of 100 ppb (10 lL), and the resistance was recorded during a period of time necessary to calculate the response time of the sensor. Then, the test chamber was opened and was cleaned with high purity dry air ow for recovery. The procedure was repeated for all concentration levels. The resistance was monitored continuously and recorded using an IEEE 488 data acquisition system incorporated to a personal computer during the measurements.

3. Results and discussion The SEM images of ZnO nanorods fabricated in different solution concentrations were given in Fig. 2. It is clearly seen that density and diameters of ZnO nanorods increase with increasing concentration of solution used in hydrothermal process. The diameters of ZnO nanorods fabricated in 0.001 M, 0.01 M and 0.1 M (called sample Z1, Z2 and Z3 respectively) equi-molar Zinc nitrate and HMTA aqueous solutions are approximately 30 nm, 60 nm and 120 nm respectively as seen as a list in Table 1. ZnO nanorods were approximately 250 nm in length, sparse, not contact with each other and not entirely vertical to substrate for low concentration of solution (0.001 M) as seen in Fig. 2a. ZnO nanorods fabricated
Fig. 2. The SEM images of ZnO nanorods with different concentration of equi-molar zinc nitrate and HMTA solution, a) 0.001M, b) 0.01M, c) 0.1M.

concentration of NO2 depending on temperatures from 140 C to 210 C [20]. Moreover, Park et al. fabricated ZnO nanorods by sonochemical process for detecting NO2. ZnO nanorods were showed low response and recovery time and detection limit was 50 ppb at 300 C [21]. In this study, we synthesized vertically aligned ZnO nanorods with different dimensions by hydrothermal method. Then, NO2 gas sensing properties of the nanorods were investigated depending on concentration at the temperature range of 25200 C. Also, effects of ZnO nanorod dimensions and electrode position (on top or bottom of ZnO nanorods) were examined.
2. Experimental details Firstly, ZnO thin lms as seed layer were coated on pre-cleaned glass substrate by solgel deposition technique using zinc acetate dihydrate (Zn(CH3COO)22H2O) solution [2224]. The glass substrates were cleaned with acetone, methanol and deionized water in an ultrasonic bath for 10 min each. In order to fabricate ZnO

Fig. 3. XRD spectrum of ZnO nanorods.

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Fig. 5. The dependence of sensor response on concentrations of NO2 for ZnO nanorods fabricated in different concentration solution at 200 C (a) and sensor response versus temperature for Z2 nanorod sample exposed to 100 ppb NO2 (b).

0.01 M equi-molar Zinc nitrate and HMTA aqueous solution, was calculated as 3.31 eV with using from sharply decreasing in absorbance was observed at 374 nm [22]. ZnO nanorods growing process in hydrothermal method is based on reactant species and the crystallographic habits of wurtzite hexagonal ZnO. In hydrothermal growing process, zinc nitrate hexahydrate (Zn(NO3)26H2O) and hexamethylenetetramine (C6H12N4)(HMTA) were used. HMTA was used to protect pH value of solution at pH 7. Chemical reactions in this process can be explained as below:
Fig. 4. Resistance versus time graphs for Z2 sample at indicated temperature: (a) at 25 C, 50 C and 100 C exposed to 100 ppb NO2, (b) at 150 C exposed to 100 ppb 1 ppm NO2, and (c) at 200 C exposed to 100 ppb1 ppm NO2.

CH2 6 N4 6H2 O ! 6HCHO 4NH3 NH3 H2 O

! NH 4 OH

1 2

in 0.01 M equi-molar zinc nitrate and HMTA aqueous solution. ZnO nanorods were dense, contact with each other and partially vertical to substrate as given in Fig. 2b. For high concentration of solution (0.1 M), ZnO nanorods were fully vertical to substrate and contact to each other. XRD analysis was carried out in order to investigate crystal structure of fabricated ZnO nanorods. XRD spectrum of Z2 was given in Fig. 3. Two peaks were observed belonging to (0 0 2) and (1 0 3) planes and both of them indexed to hexagonal wurtzite structures of ZnO. The strong peak (0 0 2) implies highly oriented ZnO nanorods in c-axis. In our previous works, for determining electronic structure of ZnO nanorods, UVvisible analysis were used and band gap of ZnO nanorods, which synthesized by using

As the concentration of these Zn+2 and OH ions exceeds a critical value, the precipitation of ZnO nuclei starts. The Zn(OH)2 can be
Table 2 Summary of sensor response at indicated temperature for 100 ppb NO2 exposure and response time at 200 C for 1 ppm NO2 exposure. Sensors

DR/R0 for 100 ppb NO2

25 C 50 C 0.21 12.8 0.43 0.43 100 C 0.17 12.4 0.49 0.57 150 C 0.13 1.14 0.069 0.37 200 C 0.018 0.075 0.032 0.3

tm (s) at 200 C

Z1 Z2 Z3 Z4

0.18 2.85 0.145 0.32

30 20 36 84

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transformed into ZnO crystals via these simple chemical reactions [25]:

Zn2 2OH ! ZnOH2 ZnOH2 ! ZnO H2 O

3 4

In our experiment, it is found that ZnO nanorods can be grown any concentrations, but molarity of Zn(NO3)2 and HMTA must be equal. If their molarity is not equal, then ZnO nanorods cannot be observed. When ZnO is formed, the ZnO nuclei starts and produce nal products formation is like building blocks type. It is clear in Fig. 2 that the concentration of Zn+2 and OH in solution remarkably affects the number of nanorods and their diameters. With decreasing the amount of Zn+2 and OH ions in solution, the size of formed ZnO nuclei minimize, moreover the number of ZnO nuclei decrease. After ZnO nuclei forms, Zn+2 and OH ions start to build up at this local position. Due to the crystal structure of ZnO, building up is bigger in [0 0 0 1] crystal plane direction than other crystal plane [25]. Fig. 4a shows the resistance versus time curves for Z2 at 25 C, 50 C and 100 C exposed to 100 ppb NO2 in high purity dry. After the resistance of the sample of Z2 was measured under dry air ow for 10 min to obtain base line, the measurement chamber was closed and then, 100 ppb NO2 was injected into the chamber. After the sample was exposed to100 ppb NO2, the resistance of Z2 sample is increased to a maximum. When the sample was purged with dry air ow, the resistance of the sample was decreased slowly and did not recover to the base line for 1h at 25 C, 50 C and 100 C as seen in Fig. 4a. It can be clearly seen in Fig. 4a that sensor reached a maximum value approximately 8 min, 5 min, 2 min at 25 C, 50 C and 100 C, respectively. However recovery times of Z2 sample is too long at 25 C, 50 C and 100 C, and it can be said that these temperatures are not suitable for using as NO2 sensor. Similar behaviors were observed for other sensor devices (Z1, Z3 and Z4). Fig. 4b and c shows the resistance versus time curves for Z2 sample at 150 C and 200 C exposed to 100 ppb1 ppm NO2 in high purity dry. It can be clearly seen in Fig. 4b and c that the sensor was fully recovered, and the change in the resistance was increased with increasing concentration of NO2 gas at 150 C and 200 C. After every indicated concentration of NO2 gas was injected into the test chamber, the resistance of Z2 sample increased to a maximum, and then, decreased slowly. When the sample was purged with dry air ow, the resistance of the sample was decreased to its base line for a few minutes as seen in Fig. 4b and c. The response times of Z2 sample at 150 C and 200 C were approximately 60 s and 20 s respectively. The response and recovery times of Z2 sample decreased with increasing temperature. Similar behaviors were observed for other sensor devices (Z1, Z3 and Z4). The increase in resistivity of ZnO nanorod sensor devices can be explained as follows. It is a well known fact that ZnO is an n-type semiconductor. It is also well established that electron donor or electron acceptor molecules can reduce or oxidize the ZnO. NO2 is a well-known oxidizing gas which, on contact with ZnO nanorod surface, causes the transfer of an electron from the ZnO to the NO2 gas molecule. Hence, the resistance of ZnO nanorods increases with NO2 adsorption. Consequently, the decrease in the n-type oxide material justies the increased resistivity of the material. Adsorption of NO2 acts as an acceptor in the oxide in accordance with the following reversible doping process [26,27]:

DR refers to change in resistance of ZnO nanorods, and R0 is the reference value as baseline. Fig. 5a shows concentration dependence of sensor response for ZnO nanorods with different diameter and density at 200 C. The sensor response increases linearly with increasing the concentration of NO2 at 200 C for all samples. It is clear from Fig. 5a that maximum response is observed for Z4 sample. Although Z2 and Z4 samples were prepared in same hydrothermal conditions, Z4 sample showed higher responses than Z2 sample and the differences in responses can be referred to electrode position. In Z4 sample, Au IDT electrode was between ZnO seed layer and ZnO nanorods. On the other hand, to compare sensor responses of Z1, Z2 and Z3 samples, Z2 sample showed higher sensor response than the others. The diameters of Z1, Z2, and Z3 nanorod samples were 30, 60, and 120 nm as seen in Fig. 2 respectively. Yamazoe and Shimanoe have recently developed a new model on the roles of shape and size of component crystals in semiconductor gas sensors on the basis of electron-depleted conditions in component crystals [2830]. The model conrms that the gas sensitivity increases with decreasing the crystal size. It is expected that the highest sensor response should be observed for Z1 sample because Z1 nanorods has the lowest diameter. But Z1 nanorods were rare, not contact with each other and have low surface area due to the nanorods density. So, the major and minor contributions in sensor response came from the seed layer of Z1 and nanorods of Z1 sample respectively. In addition, sensor response versus temperatures curve for Z2 sample was shown in Fig. 5b. Sensor response increases with increasing temperature from 25 to 100 C and then decreases sharply over 100 C. Similar behavior was observed for other sensor devices (Z1, Z3 and Z4). The response time (tm) was dened as the time for resistance to reach a maximum. Table 2 shows the sensor response parameter at the indicated temperature and response time parameter at 200 C for all ZnO nanorods. It is clearly seen from the table that the lowest response time was observed for Z2 sample, and the highest sensor response was obtained for Z4 sample at 200 C. The sensor response rst increases with increasing temperature and then decreases for all ZnO nanorod samples (see Table 2).

4. Conclusions As a conclusion, ZnO nanorods were fabricated by using hydrothermal process, and the number of nanorods on the substrate was controlled with changing concentration of equi-molar zinc nitrate and HMTA aqueous solution. It was found that ZnO nanorods became denser, contact to each other and vertical by increasing concentration of the solution. On the other hand, NO2 sensing properties of ZnO nanorods were investigated depending on temperature, concentration and electrode position. It was observed that the highest sensor response was observed for Z4 sample at 200 C. The lowest response and recovery times were obtained for Z2 sample at 200 C. So, ZnO nanorods could be suitable candidates with high and quick sensitivity to NO2 sensing.

Acknowledgements This study was partially supported by Ministry of Development of Turkey (DPT) entitled Nanomagnetism and Spintronics Research Center (Project No. 2009K120730) and by Scientic and _ Technological Research Council of Turkey (TUBITAK) entitled Development of Automotive Gas Sensors Based on Nano-Metal Oxide Semiconductor with increased Selectivity, Sensitivity and Stability (Project No. 111M261).

NO2 gas $ NO2 ads e NO2 ads $ NO 2 ads

Sensor response was calculated as below:

5 6

Sensor Response

DR R0

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