Ionics (2010) 16:481486 DOI 10.

1007/s11581-010-0437-y

ORIGINAL PAPER

Electrical properties of cerium fluoride thin films

Arun Kumar Dorai & S. Selvasekarapandian & Nithya Hellar & Sakunthala Ayyasamy & Hema Muthusamy

Received: 7 February 2010 / Revised: 10 March 2010 / Accepted: 19 March 2010 / Published online: 18 April 2010 # Springer-Verlag 2010

Abstract Thin films of ionic conductors have low internal resistance. Hence, it could be used as an electrolyte material in sensors to operate at ambient temperatures. Cerium fluoride, a unipolar fluoride ion conductor, has got a different application in electrochemical sensor. In the present work, cerium fluoride thin films have been prepared by physical vapor deposition method and their electrical properties are studied. X-ray diffraction studies reveal the polycrystalline nature of the prepared thin films and the structure of the material. Scanning electron microscopy (SEM) images show grain-like structures. Conductivity analysis of the thin films has been studied by ac impedance analysis and the maximum conductivity value is found to be 1.04106 S cm1. The impedance spectra emphasize intergranular conduction in the prepared thin films. Keywords Cerium fluoride . Thin film . Oxygen sensor . Conductivity . Electrical properties

Introduction Among the superionic conductors, of special interest are solids with high fluoride ion disordering of lattice and
A. K. Dorai : S. Selvasekarapandian (*) : H. Muthusamy Department of Physics, Bharathiar University, Coimbatore 641046 Tamil Nadu, India e-mail: sekarapandian@yahoo.com A. K. Dorai : N. Hellar : S. Ayyasamy : H. Muthusamy DRDO-BU Center for Life Sciences, Bharathiar University, Coimbatore, Tamil Nadu, India S. Selvasekarapandian Kalasalingam University, Krishnankoil, Srivilliputhur, Tamil Nadu, India

correspondingly high conductivity of fluoride ions in the solid phase. The fluorine-conducting solid electrolytes (FCSE) are non-stoichiometric fluorides with tysonite structure. They are promising material for various devices such as the fluoride-selective electrodes, gas-sensitive sensors, power sources, etc. The efficiency of application of FCSE depends on the peculiarities of their bulk properties, processes at the interfaces with electrode materials, and reactivity with the interfaces [1]. The two major advantages that fluoride ion electrolytes offer over other ionic conductors are lower electronic conductivity and higher ionic conductivity at ambient temperatures. Among the rare earth fluorides, LaF3 and CeF3 show high F conductivity at ambient temperature. Fluoride ionconducting materials such as LaF3 [2], PbF2 [3], CeF2, and PbSnF4 [4] are found to be suitable for oxygen sensor at ambient temperatures. Miura et al. has reported a potentiometric oxygen sensor using LaF3 single crystal to work at room temperature [5???]. Tan et al. reported an oxygen sensor based on lanthanum fluoride thin films to work at room temperature [6]. The electrical properties of lanthanum fluoride single crystals have been studied extensively by Schoonman et al. [7], and the transport properties of lanthanum fluoride have been studied using impedance spectroscopy by Sinitsyn et al. [8]. The dielectric properties of lanthanum fluoride thin films have been studied by Mahalingam et al. [9]. The ionic thermoconductivity and capacitance properties of LaF3 thin films were studied by Tiller et al. [10]. The ion conduction properties of LaF3 thin films have been studied by Vijayakumar et al. and Selvasekarapandian et al. [11, 12]. Cerium fluoride has not found wide use yet, though the transport properties of CeF3 characterize it as a unipolar fluoride ion conductor, which can operate at room temperature. However, the poor mechanical strength of this

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(110) (300)

material restricted its usage in bulk form, and it can be overcome by the use of this material in the thin film form. The use of thin film electrolytes reduces the impedance of the material and thus improves the response time and reduces the operating temperature of the sensor. Lancaster et al. studied the conductance and capacitance properties of cerous fluoride thin films [13]. Kalra et al. has studied the influence of thickness and temperature on the conductance properties of thin film cerium fluoride capacitors [14]. To our knowledge, there are no reports on the impedance and conductivity analysis of cerium fluoride thin films. Hence, cerium fluoride thin films have been prepared by physical vapor deposition method and its electrical properties (impedance and conductivity) have been studied using ac impedance spectroscopy.

CF

500

Intensity (arb unit)

400

200
(141)

(111)

300

100

0 10 20 30 40 50 60 70 80

2 (deg)

Fig. 1 XRD pattern of cerium fluoride thin films

Experimental methods The highly pure cerium fluoride purchased from Sigma Aldrich (99.9%) has been used as a starting material. Tungsten helical source has been used for thermal evaporation, and glass slides have been used as substrate material. The films were coated under the vacuum pressure of around 106 Torr (2.66 Pa), using HINDHIVAC 12 A4D coating unit. The structure and crystalline phase of the film has been studied by X-ray diffraction analysis using a PANalytical Xpert pro X-ray diffractometer using CuK radiation. Silver has been coated as electrodes to form the capacitive structure for impedance measurements. PC-based HIOKI 3532 LCZ meter (frequency range of 42 Hz4 MHz) has been used for the impedance analysis in the temperature range of 473573 K.

Results and discussion Structural analysis Figure 1 shows the XRD pattern of cerium fluoride thin films. The presence of well-defined peaks reveals the polycrystalline nature of the thin films. The 2 values are found to be in good agreement with the JCPDS card no. 70-0002 in hexagonal phase with space group p-3c1. The peaks observed around 24.98, 27.83, 44.01, 52.89, and 71.13 correspond to the (110), (111), (300), (221), and (141) planes, respectively. These are the characteristic peaks for cerium fluoride in hexagonal symmetry and tysonite structure. The particle size of the film is calculated using the Scherrer equation. The dislocation density and

Fig. 2 SEM images of cerium fluoride thin films

(302) (221)

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7000000 6000000 5000000 4000000

483
473 K 498 K 523 K 548 K 573 K
-3.5 -4.0 -4.5

473 K 523 K 573 K

Log (Scm )

Z"

-1

-5.0 -5.5 -6.0 -6.5

3000000 2000000 1000000

-7.0
0 0 1000000 2000000 3000000 4000000 5000000 6000000 7000000

-7.5 2 3 4 5 6 7 8

Z'

Log (Hz)

Fig. 3 Cole Cole plot for cerium fluoride thin films Fig. 4 Conductance plot for cerium fluoride thin films

microstructural strain are calculated from the most intense peaks using the relations [15] D 0:94l b2q cos q 1 D2  " where l 2 is the is the peak is the is the is the wavelength of the X-ray full width at half-maxima of the corresponding dislocation density of the prepared thin film microstrain of the prepared thin film diffraction angle l b D cos q  1 tan q  3 1

The particle size calculated using the Scherrer formula is found to be 25 nm, the dislocation density is found to be 1.4 1015 lin2 m4 and the micro structural strain has been found to be 0.001 lin m4. Similar results have been reported by Vijayakumar et al. for lanthanum fluoride thin films [11]. Figure 2 shows the scanning electron microscope image of cerium fluoride thin films. At lower magnification, the SEM image shows that the grains were evenly distributed on the surface of the film. At higher magnification, the image shows clearly the grain-like structures oriented in different directions along the film. Impedance analysis Figure 3 shows the Cole Cole plot of impedance at different temperatures. The complex impedance diagram shows a

-3.2

Linear Fit

-3.4

Log T (Scm )

-1

-3.6

-3.8

Table 1 Bulk capacitance and conductivity values for the thin films at different temperatures Temperature (K) 473 498 523 548 573 Cb (F) 1.0910 4.421014 8.731014 6.301013 1.091012
14

-4.0

(Scm ) 1.0410 1.83107 2.60107 6.84107 1.04106

7

-4.2

-4.4 1.70 1.75 1.80 1.85 1.90 1.95

-1

2.00

2.05

2.10

2.15

1000/T K

Fig. 5 Arrhenius plot 1,000/T Vs log T

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Z' Z'' 498 K

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Impedance

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0 10 100 1000 10000 100000 1000000 1E7

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100

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1E7

Frequency (Hz)
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Frequency (Hz)
600000

800000

Z' Z'' 548 K

Z' Z"
500000

573 K

400000
600000

Impedance

impedance

300000

400000

200000

200000

100000
0

0
10 100 1000 10000 100000 1000000 1E7

10

100

1000

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Frequency (Hz)

Frequency (Hz)

Fig. 6 Plot between impedance and frequency at a 498 K, b 523 K, c 548 K, and d 573 K

semicircle in the high frequency range which is related to the grain interior resistance in the bulk of the electrolytes. The bulk capacitance values are calculated using the relation wmax RC 1 4

6.0
Linear Fit

5.5

The bulk capacitance values are found to be in the order of Pico farad (pF) which indicates the nature as grain interior resistance [11]. The center of the semicircle falls below the real axis, indicating the non-Debye nature of the material. At low temperature, in the cerium fluoride thin film only very few fluoride ions contribute to the ionic conductivity. As the temperature increases, more and more fluoride ions occupy the high mobility sublattice, resulting in high ionic conductivity. This result can be interpreted by considering the Hoff et al. criterion [16], which describes the tysonite structure of lanthanum fluoride, in which the fluoride ions occupy different positions of the sublattice. Hence, the increase in conductivity suggests that the

5.0

Log p

4.5

4.0

3.5 1.70

1.75

1.80

1.85

1.90

1.95
-1

2.00

2.05

2.10

2.15

1000/T K

Fig. 7 Arrhenius plot 1,000/T Vs log p

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mobility of fluoride ions increases with increase in temperature. The ionic conductivity is calculated using the relation s l RA resistance of the material thickness of the film (m) effective contact area (cm2) 5

Frequency dependence of impedance Figure 6 shows the variation of Z with log frequency. It is evident from Fig. 6ad that Z intersects Z at a particular frequency, indicating the existence of relaxation phenomena which show that the impedance relaxation is associated with the frequency relaxation. As the temperature increases, the intersection frequency of Z with Z shifts towards the high frequency side, revealing the shift in relaxation frequency [18]. The relaxation frequency increases with an increase in temperature. This relaxation is clearly seen in the Cole Cole plot (Fig. 3) where a semicircle is observed which is correlated to a parallel combination of resistor with a capacitor. It has been reported that in polycrystalline electrolytes a semicircle in the Cole Cole plot suggests that ZR, which emphasizes the intergranular conduction processes in the material [19]. The relaxation frequency was plotted as a function of inverse temperature, and Arrhenius behavior was found and is shown in Fig. 7. A linear fit to the plot gives the activation energy of the impedance relaxation and is found to be 0.40 eV. This allows us to confirm that the impedance relaxation observed is believed to reflect the process of ionic conduction in the bulk [20]. The values of Ea and Em implies that the carrier concentration is independent of temperature i.e., the enthalpy of charge carrier formation is negligible.

R l A

The ionic conductivity values for the prepared thin films were tabul in Table 1. The maximum conductivity value is found to be 1.04106 S cm1 at 573 K. Conductance analysis Figure 4 shows the conductance spectra for CeF3 thin films at different temperatures. The conductance spectra shows two distinct regions: the low frequency plateau which indicates the dc conductivity of the material and the high frequency dispersion region which obeys the power law feature () n. The material is found to obey the Jonshers Universal Power Law [17] given by s w s dc Awn 6

The conductance spectra were fitted using Jonshers Power Law and the value of n was extracted and it is found to be less than 1, which indicates the translational motion of the fluorine ions in the material. From the plot, it is clear that as the temperature is increased the DC plateau region shifts towards the high frequency region, indicating an increase in mobile charge carriers. Temperature-dependent conductivity The temperature-dependent ionic conductivity measurements are carried out to analyze the mechanism of ionic conduction in the material. Figure 5 shows the variation of conductivity with respect to the reciprocal of temperature for cerium fluoride thin films. The linear variation of log T Vs 1,000/T plot suggests an Arrhenius-type thermally activated process. The conductivity is expressed as: sT s 0 expEa =kT where 0 Ea pre-exponential factor activation energy 7

Conclusion Cerium fluoride thin films have been prepared by physical vapor deposition method. The XRD analysis confirms the tysonite structure of cerium fluoride in hexagonal phase. The SEM images show grain-like structures in the thin films. The complex impedance analysis shows that the bulk resistance decreases with an increase in temperature. The ionic conductivity is found to be 1.04106 S cm1. The conductivity study shows the temperature-independent behavior of charge carrier concentration.

References
1. Urchukova MM, Turaeva MS (2009) Russ J Electrochem 45 (4):393398 2. JP Lukaszewicz, N Miura, Noboru Yamazoe (1992) Sens Act B 9:5558 3. Couturier G, Danto Y, Gibaud R, Salardenne J (1981) Solid State Ionics 5:621624 4. Siebert E, Fouletier J, Kleitz M (1987) J Electrochem Soc 134:15731578 5. S Kuwata, N Miura, N Yamazoe, T Seiyama (1984) Chem Lett 13 (6):981982

The activation energy value is calculated from the slope of the plot and is found to be 0.35 eV.

486 6. Tan GL, Wu XJ, Wang LR, Chen YQ (1996) Sens Act B 34:417421 7. Schoonman J, Oversluizen G, Wapenaar KED (1980) Solid State Ionics 1:211221 8. Sinitsyn VV, Lips O, Privalov AF, Fujara F, Murin IV (2003) J Phys Chem Solids 64:12011205 9. Mahalingam T, Radhakrishnan M, Balasubramanian C (1979) Thin Solid Films 59:221229 10. Tiller CO, Lilly AC, LaRoy BC (1973) Phys Rev B 8(10):4787 4794 11. Vijayakumar M, Selvasekarapandian S, Gnanasekaran T, Fujihara S, Koji S (2004) J Fluorine Chem 125:11191125 12. Selvasekarapandian S, Vijayakumar M, Gnanasekaran T, Fujihara S, Koji S (2003) Physica B 337:5257

Ionics (2010) 16:481486 13. Lancaster MC (1972) J Phys, D:Appl Phys 5:11331144 14. Kalra AD, Simmons JG, Nadkarni GS (1975) J Appl Phys 46 (12):50765079 15. Cullity BD (1978) Elements of X-ray diffraction. AddisonWesley, Reading 16. Hoff C, Wiemhfer HD, Glumov O, Murin IV (1997) Solid State Ionics 101:445449 17. Jonscher AK (1977) Nature 267:673678 18. Hornebecq V, Reau JM, Ravez J (2000) Solid State Ionics 127:231240 19. Hodge JM, Ingram MD, West AR (1976) J Electroanal Chem 74:125 20. Hairentidnov EF, Uvarov Nikolai F (1994) Phys Rev B 50:13259