Physica Status Solidi B: Basic Solid State Physics

Preparation of ZnO nanorod gas sensor and its ethanol gas sensing performance
--Manuscript Draft--

Manuscript Number: pssb.202100608

Article Type: Research Article

Corresponding Author: Yidong Zhang

Xuchang University
Xuchang, CHINA

Order of Authors: Yidong Zhang

Zhenwei Dong

Keywords: Hydrothermal method; ZnO nanorods; Aspect ratio; Gas sensor; Sensitivity

Abstract: ZnO nanorods were prepared by hydrothermal method using Zn(NO3)2·6H2O as

precursor, NaOH as precipitant, anhydrous ethanol as solvent and ethylenediamine as
active agent. The morphology, size and structure were observed by scanning electron
microscope (SEM) and X-ray diffraction (XRD). The gas sensitivity of ZnO nanorods in
ethanol environment was characterized by CGS-8 gas sensitivity analysis system. The
results show that the sensitivity of ZnO nanorods gas sensor increases with the
decrease of precursor concentration. The repeatability and concentration
characteristics are good. Especially, the sensitivity of ZnO nanorods gas sensor
reaches about 33 when the concentration is 0.1 mol·L-1. The optimal working
temperature is 275 ℃.

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7 Preparation of ZnO nanorod gas sensor and its ethanol gas sensing
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10 performance
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14 Yidong Zhang*, Zhenwei Dong
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College of Chemical and Materials Engineering, Xuchang University, Xuchang, 461000, P.R. China
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23 * Corresponding author. Tel.: +86 374 2968783
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26 *Address correspondence to these authors E-mail: zyd630@126.com (Y. D. Zhang)
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30 Abstract: ZnO nanorods were prepared by hydrothermal method using Zn(NO3)2·6H2O as precursor, NaOH as
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32 precipitant, anhydrous ethanol as solvent and ethylenediamine as active agent. The morphology, size and structure were
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34 observed by scanning electron microscope (SEM) and X-ray diffraction (XRD). The gas sensitivity of ZnO nanorods in
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36 ethanol environment was characterized by CGS-8 gas sensitivity analysis system. The results show that the sensitivity
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38 of ZnO nanorods gas sensor increases with the decrease of precursor concentration. The repeatability and concentration
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40 characteristics are good. Especially, the sensitivity of ZnO nanorods gas sensor reaches about 33 when the
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42 concentration is 0.1 mol·L-1. The optimal working temperature is 275 ℃.
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48 Keywords: Hydrothermal method; ZnO nanorods; Aspect ratio; Gas sensor; Sensitivity; Repeatability
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3 1. Introduction
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5 ZnO is a wide band gap (3.37 eV) n-type semiconductor metal oxide material widely used in the
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8 sensing field. It has high electron mobility, good chemical and thermal stability and diversified
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10 structure, morphology and size [1-3]. It is found that the properties of ZnO are closely related to their
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13 morphology and size. For example, two-dimensional ZnO thin film based gas sensor has attracted much
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16 attention earlier, but the poor gas selectivity of ZnO thin film limits its development. One dimensional
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19 ZnO nanomaterials have the characteristics of high specific surface area and aspect ratio, high
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21 mechanical strength and high thermal conductivity. The high aspect ratio of ZnO nanowires makes it
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24 bend under micro force to produce potential difference, which can be applied to nano generators. The
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27 large specific surface area of ZnO nanowires increases the number of surface dangling bonds and
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30 oxygen defects, has high surface activity and is sensitive to atmosphere, It is very suitable for preparing
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32 gas and photodetectors [4-7].
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35 Compared with two-dimensional, one-dimensional ZnO nanomaterials have high sensitivity, better
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38 selectivity and lower detection limits, so they are often used for the detection of toxic and explosive
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41 gases in the air [8], such as ethanol, methane, ammonia, hydrogen and nitrogen dioxide [9-15]. Among
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43 them, ethanol is widely used in national defense industry, medical and health care, organic synthesis,
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46 food industry, industrial and agricultural production and life, and the dosage requirements are strict. If it
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49 is careless, it will cause accidents such as explosion, disease and poisoning. Therefore, in order to
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52 ensure human safety, explore the ethanol environment, controlling the morphology and size of
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54 synthesized ZnO nano materials and effectively regulating their gas sensing properties have a wide
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57 application prospect [16, 17]. For example, Shaikh et al. fabricated ZnO nanorod-based gas sensor by
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60 chemical bath deposition showing high selectivity toward NO2 due to the high surface area for the
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sensing mechanism [18]. Zhao et al. synthesized ZnO nanorods by a complex-surfactant-assisted
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6 hydrothermal method using a mixture of sodium dodecylsulfate (SDS) and polyethylene glycol 400
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9 (PEG 400) as the complex surfactant, exhibiting excellent ethanol sensing performance thanks to the
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12 large length-to-diameter and the numerous crystal defects of the oxygen vacancies existed in the surface
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region of ZnO nanorods [19]. Hassan et al. also prepared ZnO nanorods arrays on quartz substrate using
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17 PVA-Zn(OH)2 as seed layer showing good sensitivity at room temperature to H2 gas [20]. However, in
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20 the above research reports, the aspect ratio of ZnO nanorods is not controllable , the effects of different
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23 aspect ratio, size and optimal working temperature on the experimental results are not explored, and the
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test process of the sensor is cumbersome.
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28 In this work, ZnO nanorods were prepared by a simple and low-cost hydrothermal method. ZnO
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31 nanorods were prepared by zinc nitrate hexahydrate and sodium hydroxide; The aspect ratio of ZnO
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34 nanorods was adjusted by changing the precursor concentration, and the effects of different aspect ratio
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on its gas sensing properties were studied.
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42 2. Experimental section
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45 2.1 Chemicals
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All reagents used in this work were purchased at analytical reagent grade and used for synthesis without
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50 further purification.
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53 2.2 Synthesis of ZnO nanorods
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56 A certain amount of Zn (NO3)2.6H2O and NaOH were dissolved in deionized water to prepare 10 ml
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59 zinc alkali solution. Then, 3 ml of the above solution was transferred to add deionized water, absolute
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61 ethanol and ethylenediamine. After stirring evenly, the solution mixture was put into the ultrasonic
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3 cleaning machine for 40 min, then pour it into the reactor to made a hydrothermal reaction at 180 ℃
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6 for 20 h in oven. After the experiment, it was washed with deionized water and absolute ethanol by
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9 centrifuge. Finally, the centrifugal product was placed in a blast drying oven at 80 ℃ for 12 h to
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12 obtain ZnO crystalline products. Then ZnO nanorods were prepared at the concentrations of 1 mol L-1,
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0.5 mol L-1, 0.2 mol L-1 and 0.1 mol L-1. Reagent dosage is shown in Table 1
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17 2.3 Preparation of gas sensor
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20 As shown in Fig. 1, the white powder of ZnO nanorods is placed in the agate mortar, dripped into a
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23 suitable amount of ethanol to form paste (Fig. 1a), and then the tweezers are used to evacuate the four Pt
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electrode leads of the ceramic tube (Fig. 1b). The product of Fig. 1a is coated on the surface of the
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28 ceramic tube by drawing pen (Fig. 1c), and the base is fixed on the foam board (Fig. 1d). The four Pt
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31 leads of the ceramic tube were welded using electric soldering iron and solder wire according to the
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34 position in Fig. 1e, stretching the Ni-Cr heating wire to a length similar to that of the ceramic tube (Fig.
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1f), penetrating into the central hole of the ceramic tube (Fig. 1g), welding both ends to the base, cutting
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39 off the excess Pt lead and heating wire (Fig. 1h) to prevent short circuit of the device during the test,
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42 using a multimeter to measure whether each circuit forms a circuit, and finally covering the dust cap
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45 (gas can enter, dust cannot enter). Finally, the gas sensor is prepared and aged for 24 h in CGS-8
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intelligent gas sensing analysis system. The aging temperature is half of the optimal working
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53 2.4 Characterization and gas sensing performance test
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56 The crystal form of the product was analyzed by X-ray diffractometer (D8 advance). The morphology,
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59 size and structure were observed by scanning electron microscope (Nova nano sem450). CGS-8
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intelligent gas sensing analysis system was used to test the optimal working temperature, sensitivity,
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6 repeatability and concentration characteristics of ZnO based gas sensor in ethanol environment.
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9 3. Results and discussion
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12 In Fig. 2, compared with the standard card JCPDS card (No. 36-1451), the crystal phase of the
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prepared ZnO nanorods is belonged to hexagonal wurtzite type. XRD patterns showed that there were 7
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17 characteristic peaks, showing good crystallinity, without other heteropeaks. In Fig. 3, different precursor
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20 concentrations have a significant impact on the aspect ratio of ZnO nanorods, but the dispersion is
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23 relatively uniform. The morphology of ZnO nanorods in Fig. 3a is the worst and the yield is the lowest.
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When the concentration is 0.1 mol L-1, the diameter is about 150 nm and the yield is the highest, as
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28 shown in Fig. 3d. The anisotropy is a necessary condition for the growth of nanorods. Through
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31 hydrothermal method, ZnO nanorods first exist in the form of Zn (OH)2 colloid, hydrolyzing in alkaline
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34 solution to form growth unit [Zn (OH)4]2 -. Then, through the oxygen bridge between growth units and
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the protonation reaction of anion groups, a crystal nucleus with a certain structure is formed. Then, the
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39 growth units grow directly along a certain crystal plane on the crystal nucleus to form ZnO nanorods.
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42 In Fig. 4, when the operating temperature is 275 ℃, the sensitivity of the four gas sensors reaches
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45 the highest point. Therefore, 275 ℃ is determined as the optimal working temperature of ZnO nanorod
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gas sensor. It is necessary to choose the best working temperature correctly. Under the condition of
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50 appropriate temperature, the sensor has sufficient adsorption capacity for gas molecules, which can
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53 diffuse on the material surface, resulting in the change in resistance of ZnO nanorod during the process
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56 of adsorption and diffusion. Too low temperature will lead to low activity of chemically adsorbed
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59 oxygen on the surface and affect the response speed of the atmosphere to be measured. Too high
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temperature may affect the diffusion and adsorption of the measured gas molecules to reduce the
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9 When ethanol vapor with the concentration of 500 ppm is added to the air environment at the working
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12 temperature of 275 ℃, the sensitivity of ZnO nanorod gas sensor increases rapidly and reaches stability
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after a period of response time, as shown in Fig. 5 .When the desorption begins, the gas sensor recovers
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17 rapidly and gradually recovers to the resistance value when it starts in the air environment. The response
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20 speed is slower than the recovery speed. After the ethanol vapor is added, the sensitivity value fluctuates
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23 obviously, for the concentration of ethanol vapor evaporated by the evaporator is not uniform, when the
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ethanol liquid is injected. The fan wind force is small, and the ethanol gas is not evenly distributed in
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28 time, or when the ethanol is injected, the ethanol is sputtered on the sensor due to jitter, resulting in
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31 sensitivity fluctuation. Response and recovery times are the basic parameters of gas sensors, which are
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34 defined as the time required to reach 90% of the final resistance [21]. Compared with the recovery time,
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the recovery time (~ 12 s) is significantly faster than the response time (~ 25 s). The response time and
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39 recovery time of the gas sensor correspond to different processes. The recovery time depends on the
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42 ability and the rate to take away electrons , so the ability to gain and lose electrons is different for
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45 different semiconductor materials, The response time depends on the amount of adsorbed oxygen and
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the speed of electron return, so the response time is different from the recovery time. The fast recovery
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50 time indicates that ZnO nanorods adsorb oxygen molecules faster than ethanol molecules.
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53 In Fig. 6, when the concentration is 0.1 mol L-1 and the ethanol concentration is 500 ppm, the
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56 repeatability of ZnO nanorod gas sensor is good without fluctuation. In Fig. 7, under the conditions of
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the precursor concentration of 0.1 mol L-1 and the optimal operating temperature of 275 ℃, with the
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61 increase of the ethanol concentration, the sensitivity of the sensor increases as well. The sensitivity
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basically increases linearly with the increase of concentration, as shown in the embedded diagram in
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6 Fig. 7. The concentration characteristic curve shows good response and recovery characteristics. The
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9 time required for the rise of sensitivity to stability is the response time; The time required to fall to
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12 stability is the recovery time. The response and recovery characteristics are good, indicating a large test
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range, but there is a significant difference between the recovery time and the response time.
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17 Before contacting the ethanol vapor, O2 in the air is adsorbed on the surface of ZnO nanorods and
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20 forms chemisorbed oxygen (O2-, O- and O2-) with the electrons in the ZnO conduction band. Therefore,
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23 an electron depletion layer (high resistance region) is formed on the surface of ZnO nanorods, resulting
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in an increase in its resistance. As shown in Figure 8a. The chemisorbed oxygen mainly exists in the
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28 form of O- at the operating temperature of 275 ℃. When encountering ethanol vapor, the highly
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31 active O- can react with ethanol steam to generate CO2, O2 and H2O, so as to return the electrons to the
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34 conduction band of ZnO nanorods. The depletion layer disappears and the resistance decreases, as
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shown in Fig. 8b. The chemical reaction equation is:
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39 C2 H 5OH ( g )  O  (ads) 275
 ℃
 CO2 ( g )  H 2O( g )  O2  e 
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42 The ratio of sensor resistance in air (Ra) and ethanol vapor (Rg) is defined as sensitivity (s):
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Ra
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46 Rg
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49 The aspect ratio of ZnO nanorods has a great impact on the generation of electron depletion layer. The
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52 greater the aspect ratio, the greater the ratio of surface depletion layer area to non depletion layer area,
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4. Conclusion
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7 ZnO nanorods with aspect ratio of 3.1~20 were synthesized by hydrothermal method with Zn
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10 (NO3)2.6H2O as precursor. With the increase of the concentration, the aspect ratio of ZnO nanorod
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13 increased and the growth was more uniform. When the concentration was 0.1 mol .L-1, the diameter of
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15 ZnO nanorods with good crystallinity reached 150 nm, the aspect ratio was 20. When the working
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18 temperature is 275 ℃ and the ethanol concentration is 500 ppm, the sensitivity of ZnO nanorod gas
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21 sensor increases with the decrease of precursor concentration, showing good repeatability and response
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24 recovery characteristics.
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27 Acknowledgments
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31 This work was financially supported by the Foundation of the National Natural Science Foundation of
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34 China (Grant No.21901218).
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Table 1 Reagent dosage for preparing ZnO nanorods.
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21 Figure captions
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23 Fig. 1 Physical flow chart of gas sensor preparation.
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26 Fig. 2 XRD patterns of ZnO nanorods with different concentrations, (a) 1 mol·L-1, (b) 0.5 mol·L-1, (c)
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28 0.2 mol·L-1, (d) 0.1 mol·L-1
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30 Fig. 3 SEM images of ZnO nanorods with different concentrations, (a) 1 mol·L-1, (b) 0.5 mol·L-1, (c) 0.2
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32 mol·L-1, (d) 0.1 mol·L-1
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34 Fig. 4 Optimal operating temperature curves of ZnO nanorod-based gas sensors with different
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Fig. 5 Sensitivity curves of ZnO nanorods-based gas sensors with different concentrations.
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41 Fig. 6 Repeatability curve of ZnO nanorods-based gas sensor with concentration of 0.1 mol L-1.
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Fig. 7 Concentration characteristic curve of ZnO nanorods-based gas sensor with concentration of 0.1
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mol .L-1; The embedding diagram shows the change of sensitivity with ethanol vapour concentration.
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Fig. 8 Schematic diagram of gas sensing mechanism of ZnO nanorod-based gas sensor: (a) in air; (b) In
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ethanol vapor.
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25 Table 1
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30 Concentration Zn(NO3)2·6H2O/g NaOH/g Deionized Absolute Ethylenedia
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32 /mol·L-1 water/mL ethanol/mL mine/mL
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34 1.0 1.4832 4.0020 3.0 25.0 5.0
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36 0.5 0.7600 2.0100 1.5 12.5 2.5
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38 0.2 0.2976 0.8024 1.0 5.0 1.0
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40 0.1 0.1450 0.4100 0.5 3.0 0.5
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