Accepted Manuscript

Studies on Acetone Sensing Characteristics of ZnO Thin film Prepared by sol-gel dip
coating

Karthika Muthukrishnan, Manoj Vanaraja, Shanmugam Boomadevi, Rakesh Kumar

Karn, Vijay Singh, Pramod K. Singh, Krishnamoorthy Pandiyan

PII: S0925-8388(16)30500-X
DOI: 10.1016/j.jallcom.2016.02.222
Reference: JALCOM 36840

To appear in: Journal of Alloys and Compounds

Received Date: 17 November 2015

Revised Date: 9 February 2016
Accepted Date: 28 February 2016

Please cite this article as: K. Muthukrishnan, M. Vanaraja, S. Boomadevi, R.K. Karn, V. Singh, P.K.
Singh, K. Pandiyan, Studies on Acetone Sensing Characteristics of ZnO Thin film Prepared by sol-gel
dip coating, Journal of Alloys and Compounds (2016), doi: 10.1016/j.jallcom.2016.02.222.

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 ACCEPTED MANUSCRIPT
Studies on Acetone Sensing Characteristics of ZnO Thin film
Prepared by sol-gel dip coating

Karthika Muthukrishnan1, Manoj Vanaraja1, Shanmugam Boomadevi2, Rakesh Kumar

Karn1, Vijay Singh3, Pramod K Singh4,5 and Krishnamoorthy Pandiyan1

1
School of Electrical & Electronics Engineering, SASTRA University, Thanjavur - 613401,

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India.

2
Department of Physics, National Institute of Technology, Tiruchirappalli - 620015, India.

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3
Department of Chemical Engineering, Konkuk University, Seoul 143-701, Republic of

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Korea.
4
Solar Energy Institute, Ege University, Bornova 35100, Izmir, Turkey.

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Material Research Laboratory, School of Basic Sciences and Research, Sharda University,

Greater Noida 201310,U. P., India.

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*Corresponding author:
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Contact No.: +91- 9942115131

Email: krishpandiyan@ece.sastra.edu
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Abstract:

Acetone sensing characteristics of Zinc Oxide thin films prepared by dip coating

method are discussed in this paper. The sol for dip coating was synthesized using Zinc nitrate

hexahydrate (Zn (NO3)2. 6H2O) and organic polymer sodium carboxy methyl cellulose (Na-

CMC) as a starting material. Crystallinity and crystallite size of the prepared thin film was

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characterised by X-ray diffraction (XRD). Morphology was studied using field emission

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scanning electron microscopy (FESEM). The gas sensing characteristics was studied using

chemiresistive method, by exposing the film to various concentrations of acetone at room

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temperature. Further, for comparative study ethanol and acetaldehyde has also been tested.

Gas sensing parameters such us response, selectivity, lowest detection limit,

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response/recovery time of the thin film towards acetone were also reported.
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Keywords: ZnO, Na-CMC, sol-gel dip coating, thin film, acetone gas sensor.
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1. Introduction

In recent years, nano materials with size <100nm are widely investigated by

researchers because of its interesting surface, volume effects[1], large surface to volume

ratio, reduced particle size etc., [2]. These nano materials have unique physical, chemical

and optical properties [3] which leads to its application in numerous fields. Nowadays use of

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nano materials in the field of gas sensor has gained interest as it helps in detection of toxic

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and combustible gases [4]. The excess of toxic and combustible gases cause degradation to

environment and are hazardous to human health. Hence fabrication of gas sensor with good

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sensitivity, selectivity, quick response and recovery time to the lowest concentration of target

gas together with low operating temperature is an art of interest. From the various materials

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(metal oxides, organic compounds, polymers, metals) semiconducting metal oxide nano
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particles are extensively studied for gas sensing application due to small dimension, suitable
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operating temperature, more surface sites available for gas adsorption, high response towards

many gases, low cost, portability, non-toxicity etc., [5,6].

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Zinc oxide, a wide band gap intrinsic n-type semiconductor is one among the most
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widely studied materials for gas sensing application [7]. It offers several advantages like high
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electron mobility, nontoxic nature, abundant availability and high chemical stability [810]. It

can be prepared in many forms such as single crystal, powder, pellet, thin film and thick film
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[1113] among which thin films has good sensing response towards reducing and oxidising
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gases [14]. Sensing characteristics of the film greatly depends on surface state and

morphology of semiconducting metal oxide [15] which act as a chemical reaction centre [16

18]. In order to get tailored surface states preferable for sensing application sol gel dip

coating has been chosen as a film deposition technique in this work.

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Dip coating is a simple, cost effective and wet chemical method which is widely used

for ZnO film fabrication [19]. In this technique, uniformity, thickness, porosity and

morphology of the film can be altered by controlling sol concentration, withdraw speed,

dipping and drying time [20] also larger film area can be covered when compared to spin

coating [21]. In our work Dip coating was done by the automated dip coating unit

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(HOLMARC, HO-TH-01). Sol preparation, thin film coating followed by heat treatment are

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the steps followed in sol gel dip coating method [22]. Adhesiveness of the coated film on the

substrate depends upon viscosity of sol. Na-CMC is used in sol-preparation, because of its

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film forming ability due to abundant OH group [23] and its characteristic thickening property.

Na-CMC is an inorganic green polymer which is easily soluble in water[24]. Viscosity

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builder, stabilizer, emulsifier are some of the general utilities of Na-CMC[2527]. Its
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property mainly depends on molecular weight and degree of substitution i.e. number of OH
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groups substituted per an-hydro glucose unit [28,27]. Most widely used CMC has degree of

substitution of 0.7
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Acetone is a highly volatile and reactive compound which is colourless and

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flammable. It is widely used as solvent for plastics and synthetic fibres, extracting reagent,
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biomarker and also find applications in cosmetics, petro chemical industries [29] etc. At its

low concentration it is non-toxic, non-carcinogen and non-neurotoxic. However,

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concentration of acetone above 10,000 ppm in atmosphere causes irritation to eyes and throat
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and also cause nausea [2,30]. Human breath analysis is a rapid and non-invasive method used

as a bio marker for various diseases [31]. Acetone, hydrocarbon, ammonia, carbon monoxide,

nitric oxide are some of the endogenous molecules present in human breath and change in

their concentration is an indication of various diseases [32]. Some of the examples are,

sulphide content in human breath indicates oral malodour [33], ammonia content in breath is

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related to renal failure [34], acetone is found in the breath of diabetic patients [35], evolution

of nitric oxide indicates the presence of asthma [36] etc.

Among the above mentioned diseases most of the humans are affected by diabetes.

For diabetic patients, fat is utilized as energy for cellulose rather than glucose, due to absence

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of insulin. Hence ketoacidosis occurs due to accumulation of ketones during metabolic

activity which leads to odour of acetone in breath [37]. Acetone concentration in the breath

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exceeds 2 ppm when a person has diabetes whereas it is less than 1ppm for a healthy person

[38]. For easy and painless diagnosis of diabetes, there are number of works are going on to

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detect the least concentration of acetone in breath. Hence, we focus our work towards

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fabrication of ZnO thin film which could detect the acetone vapour at room temperature.
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2. Experiment
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The synthesis process starts by mixing two different solutions namely precursor and

thickening agent. A homogeneous solution was obtained by dissolving 4.68gms of zinc

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nitrate hexa hydrate in 100 mL of deionized water, which acts as a precursor solution.
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Further, 1.56gms of Na-CMC is dissolved in 100mL of deionized water, which acts as a

thickening agent. Precursor solution was added slowly to the thickening agent with the flow
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rate of 1mL/min. Colour change was observed when 8mL of precursor solution was added,
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which indicates the formation of ZnO nano particles. During the entire process the solution
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was under constant stirring and the temperature maintained was 75oC (2C) finally white

colour viscous solution was obtained. It was washed repeatedly with deionized water to

remove impurities.

The washed solution was kept for ageing with constant stirring for 24 hours. The aged

solution was used as a sol for dip coating. Dip coating was done on the glass substrate which

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was ultrasonically cleaned with deionized water, acetone and ethanol for 10 minutes each.

Thin films of ZnO were obtained by immersing the substrate into the sol, dip for 3minutes,

with draw vertically with the speed rate of 9000 sec and dried at 120C for 5 minutes. The

above mentioned process was repeated 20 times to get a uniform coating. It was then

annealed at 450C for 3 hours to get crystalline ZnO thin film nano particles. Na-CMC is

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mainly used to get tailored nano particles and to provide adhesion of ZnO nano particles on

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untreated glass substrate.

3. Characterization

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X-ray diffractometry and Field emission secondary electron micrograph (FESEM)

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characterizations were done to determine crystallinity, crystallographic structure, crystallite
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size and surface morphology of the ZnO thin film annealed at 450C. The XRD pattern was

obtained by X-ray powder diffractometer (PANalytical X-ray diffractometer) equipped with

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Cu K radiation having wavelength of 0.1548nm as a source. The crystallite size was

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calculated using Debye Scherrers formula [39],

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k
D= (1)
cos
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Where k is shape factor (k=0.89), is the wavelength of X-ray source, is full width at half
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maximum (FWHM) and is the diffraction angle. Morphological investigation was done
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using FE-SEM, 6701F, JEOL, Japan. The sample surface was coated with thin layer of gold

in order to avoid charge accumulation during characterisation. Gas sensing behaviour of the

film was studied by chemiresistive method.

4. Results and discussion

4.1 Thin film characterisation

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The crystalline nature of dip coated thin film was characterised by XRD . Fig. 1.

shows the XRD pattern, where the peak positions 31.859 and 34.335 are the characteristic

peaks of ZnO at [100], [002] plane respectively. The presence of hexagonal wruzite structure

was confirmed using [002] plane and Peak broadening concludes the formation of nano

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particles. The average crystallite size of the film was measured using eqn.(1) and it was found

to be 20 nm. However, due to very thin layer of film coated on glass substrate, a strong hump

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was seen on XRD pattern of ZnO thin film below 35. FE-SEM of thin film shows a

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spherical morphology as depicted in Fig. 2. Due to agglomeration, overall morphology

resembles uneven and irregular.

4.2 Gas sensing studies

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Sensing studies were done on basis of chemi resistive method, in which the chemical
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reaction between adsorbed oxygen on the material surface and the target gas results in

variation of resistance. When the thin film is exposed to air, atmospheric oxygen get adsorbed
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on the film surface in any one of the form (O2 , O , O2 ) [40]. These chemisorbed oxygen
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captures electron from the surface of the film, as a consequence of which an electron

deficient region is formed near the film surface. It leads to increase in height of the potential
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barrier and it causes an increase in resistance of the material. The point at which the
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resistance remains almost stable is considered as base resistance [41,42]. When a test gas is
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injected into the test chamber, they readily reacts with the chemisorbed oxygen. As a result of

chemical reaction between chemisorbed oxygen and test gas resistance change occurs in two

possible ways. If the test gas is an oxidising gas, they trap more electrons from the material

surface results in increase of resistance from the base resistance. While for reducing gas,the

trapped electrons are released back to the film surface and hence resistance of the film

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decreases from the base resistance [43,44]. The ratio between change in resistance from the

base resistance is said to be response of the sensing material and is represented below [45].

Ra
For reducing gas S= (2)
Rg

Rg
For oxidizing gas S= (3)

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Ra

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where Ra is the resistance of the film in air and R g is the resistance of the film in the

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presence of test gas.

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In our work, sensor response towards various test gases such as acetone, ethanol and
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acetaldehyde was measured at room temperature using a computer interfaced dynamic gas

sensing setup.The set up used was same as the one reported in [46]. To know the sensing
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characteristics of fabricated ZnO thin film, response of the film towards 50 ppm of acetone,
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ethanol and acetaldehyde was estimated. Response of the film towards test gas was

calculated using eqn. (2). Transient response of the film towards 50 ppm acetone, ethanol and
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acetaldehyde is illustrated in Fig.3 and its corresponding histogram is shown in Fig.4. From
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the result, maximum resistance change was observed for acetone and its corresponding

magnitude of response was 490. Compared with acetone, ethanol has less response and
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almost no reponse was observed for acetaldehyde. These variation in magnitude of response
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arises from the amount of chemisorbed oxygen on the surface of the film and the variation in

interaction strength of the test gas with the surface of the sensing element [47]. The acetone

sensing mechanism involves the following phenomena. After attaining the base resistance, 50

ppm acetone was injected into the closed test chamber. Due to its reducing nature, acetone

tends to release the trapped electrons back onto the ZnO thin film surface. This leads to

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decrease in height of the potential barrier so the conduction increases. This causes resistance

to fall from its base resistance. The possible chemical reaction mechanism for acetone is as

follows [48]

CH 3COCH 2 ( gas ) + O CH 3+ CO + CH 3O + e (4)

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CH 3+ CO CH 3 + + CO (5)

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CO + O CO2 + e (6)

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Selectivity of the film was estimated based on the general eqn.(7), where Si is the

S
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response of the gas for which the selectivity is to be estimated and
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response of the test gases used [49]. From the obtained response value the selectivity of the

dip coated ZnO thin film among acetone, ethanol and acetaldehyde was calculated using eqn.
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(8). Where Sethanol , S acetone , S acetaldehyde denotes the response of the film towards 50 ppm of
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acetone, ethanol and acetaldehyde at room temperature.

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Si
SEL i = x100% (7)
Si
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SELi = Si / ( Sethanol + Sacetone + Sacetaldehyde ) 100% (8)

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The selectivity for acetone, ethanol and acetaldehyde was calculated to be 71.32%,
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28.67% and 0.01% respectively and it was shown in Fig. 5.

Since very few concentration of acetone is evolved in the breath of diabetic patients,

sensor should be designed in such a way that it could detect low concentration as possible

inorder to work as a efficient breath analyser. Hence to test the lowest detection limit of ZnO

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thin film various concentration of acetone was used for testing. Transient resistance response

of the acetone gas sensor towards various concentration of acetone is illustrated in Fig. 6. The

corresponding histogram was shown in Fig. 7. From Fig. 6. the observed trend tells that the

lowest detection limit of annealed ZnO thin film was 2ppm and its response was found to be

S = 1.08. Very low response at 2 ppm was due to very few acetone molecules available for

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interaction with chemisorbed oxygen molecules. Further the response of the film increases

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gradually with increase in acetone concentration from 5 to 50 ppm. Reason behind this

proportionality between the acetone concentration and response was due to catalytic effect of

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ZnO nano sphere and participation of more acetone molecules with adsorbed oxygen

molecules [50]. However the reason for drastic increase in response when the concentration

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of acetone increased from 25 to 50 ppm was not clear. Above 50 ppm there was no much
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variation in response and it remains almost stable till 100ppm, which agreed with the results
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reported in [46].

Response and recovery time for various concentration of actone was shown in Fig. 8.
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In general, the response time of the sensor towards test gas decreases with increase in test gas
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concentration [44,51]. In our work that was observed above 50 ppm, below which an unusual
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trend was observed with increase in concentration. However, in recovery time both the

trends were observed for various concentration. Table 1 represents the response and recovery
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time for various concentrations of acetone, from the results obtained the dip coated thin film
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has the lowest detection limit of 2 ppm with the response time of 10 seconds at room

temperature, but it lacks high response (S = 1.08). The selective sensing mechanism of ZnO-

based materials to acetone is still not explained or understood. At the same time, high

sensitivity of ZnO to acetone was attributed to the powerful interaction force between the

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spontaneous electric dipole moment of ZnO and the largest dipole moment of acetone

compared to the other test gases used.

5. Conclusion

ZnO thin films have been fabricated by sol gel dip coating technique and its gas

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sensing characterisitcs were studied. Crystallinity and the existence of most stable hexagonal

wurtzite structure was confirmed with XRD. The sensing test was carried out in a closed

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chamber using chemiresistive method at room temperature. The test result showed that the

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fabricated ZnO thinfilm can act as a acetone sensor, since it shows high response towards

acetone among the test gases and also it exhibit higher selectivity for acetone with the value

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of 71.32%. Response and recovery time for various concentration of acetone is in the order
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of seconds. The lowest detection limit of room temperature ZnO thin film was observed to be

2 ppm of acetone with the response of 1.08. Hence, it could act as a breath analyser for
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diagnosing diabetes.
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Table caption:
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Table 1. Response and recovery time for various concentration of acetone ranging from 2 to

100 ppm.

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Figure caption:

Fig.1. XRD pattern of annealed ZnO thin film.

Fig.2. FE- Scanning Electron Micrograph of annealed ZnO thin film

Fig.3. Transient resistance response of ZnO thin film towards 50 ppm of acetone, ethanol,

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acetaldehyde at room temperature.

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Fig.4. Histogram showing room temperature response of ZnO thin film for acetone, ethanol,

acetaldehyde of 50 ppm conc.

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Fig.5. Selectivity of ZnO thin film at room temperature

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Fig.6. Variation in transient resistance response for different concentration of acetone
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Fig.7. Response of the annealed ZnO thin film towards various concentration of acetone
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Fig.8. Response and recovery time for various concentration of acetone ranging from 2 to 100
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ppm.
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Tables

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Conc. of Temp. Response Response time Recovery time

acetone (ppm) Ra (sec) (sec)
S=
Rg

2 1.08 10 4

5 1.20 12 7

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10 2.70 19 6

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15 11 20 18

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25 50 43 11

50 490 60 28

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75 564 48 45

100 760 34 40
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Highlights

*ZnO has successfully synthesized using cheap and ease method.

*Detail characterization have carried out and explained

* Sensing behavior has been studied.

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* Acetone sensor has been fabricated.

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