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APSUSC 17155 1–3

Applied Surface Science xxx (2008) xxx–xxx

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

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2 Positron beam studies on polyaniline and Ag-coated polyaniline

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3 J.B.M. Krishna a, S. Abhaya b, G. Amarendra b,*, C.S. Sundar b, Abhijit Saha a, B. Ghosh c
4 a
UGC-DAE Consortium for Scientific Research, Kolkata 700 098, India
5 b
Materials Science Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, India
6 c
Jadavpur University, Kolkata 700 032, India

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A R T I C L E I N F O A B S T R A C T

Article history: The effect of doping of the polyaniline emeraldine base (PEB), with Ni as well as Ni over layer coating has
Available online xxx been investigated using variable low energy positron beam. Depth-resolved Doppler S-parameter
measurements have been performed on undoped, Ni-doped polyaniline (PANI), and Ag (40 nm) film
Keywords: deposited PANI samples. Significant variation in S-parameter is observed for undoped and Ni-doped
Polyaniline
Positron annihilation
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PANI. The size of the free volume hole has shifted to lower values upon doping with Ni as compared to
that of undoped PANI, which is consistent with the conductivity measurements. For Ag-coated PANI
systems, the S vs. Ep curves show distinct changes at the surface and interior regions. These results are
discussed in the light of changes in free volume hole size distribution.
ß 2008 Published by Elsevier B.V.
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7
8 1. Introduction aniline hydrochloride in distilled water and another 50 ml solution 32
containing 5.71 g of the oxidant, ammonium peroxydisulphate, in 33
9 Conducting polymers have evoked considerable interest owing distilled water were pre-cooled to about 10 8C. The solution 34
10 to their high conductivity upon doping as well as ease of containing the oxidant was added slowly to the solution containing 35
11 fabrication [1,2]. Considerable attention has been paid to polyani- the monomer and polymerization was allowed to take place 36
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12 line as one of the electrical conducting polymer. Polyaniline (PANI) around 10 8C. Polyaniline was formed in this reaction in its 37
13 is an electrical conducting polymer that has been subjected to conducting state, as a dark green precipitate. The precipitate was 38
14 several investigations due to its reasonably good conductivity and filtered and washed repeatedly by distilled water until the pH was 39
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15 environmental stability [3,4]. Doping in terms of oxidation, 7. The precipitate was also washed with acetone to remove the 40
16 reduction or protonation of the neutral conjugated polymers will oligomers present and was then freeze dried at ’80 8C. For 41
17 create more mobile charge carriers thereby increasing the controlling the doping concentration, the dried polyaniline was 42
18 conductivity. When the insulating form of PANI (polyaniline ground into fine powder and allowed to equilibrate with 1 M 43
19 emeraldine base, PEB) reacts with acid HCl, protons are added to a NH4OH. In this process polyaniline was converted into its non- 44
20 fraction of formerly unprotonated nitrogen sites, thereby convert- conducting form, known as emeraldine base (EB). Doping with Ni 45
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21 ing EB to conducting emeraldine salt (ES). Protonation enhances was carried out by equilibrating EB with 1 M aqueous solution of 46
22 the conductivity by increasing the number of protons but keeping NiNO3 [7]. The doped polymer was dried, ground into fine powder 47
23 the number of electrons on the polymer backbone constant. and pellets of 13 mm diameter and 1 mm thickness were prepared 48
24 Conductivity can be further increased by doping the PANI with by applying a pressure of 250 kg/cm2. The four-point conductivity 49
25 appropriate dopants. Conventional positron lifetime measure- of all the samples was measured by Van-der Pauw method and the 50
26 ments have been reported in pure PANI [5]. In this paper, we report undoped sample had a conductivity of 1010 S/cm and the Ni- 51
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27 the effect of doping of the PEB and the metal deposited PANI using doped sample had a conductivity of 102 S/cm. Silver was vacuum 52
28 variable low energy positron beam. deposited at a pressure of 103 Torr. The thickness of the silver 53
overlayer was 40 nm. Depth-resolved positron annihilation 54
29 2. Experimental details measurements were carried out on undoped, Ni-doped and Ag- 55
deposited PANI samples at room temperature using a compact, 56
30 Polyaniline was synthesized by oxidative polymerization as UHV-compatible and magnetically guided positron beam system 57
31 described elsewhere [6]. A 50-ml solution containing 2.59 g of by implanting positrons of tunable energy (0–20 keV) into the 58
sample [8]. The Doppler spectrum is measured at each energy 59
using a 25% efficient intrinsic germanium detector having an 60
* Corresponding author. energy resolution of 1.4 keV at 662 keV. From the Doppler 61
E-mail address: amar@igcar.gov.in (G. Amarendra). spectrum, a defect-sensitive lineshape S-parameter, is deduced 62

0169-4332/$ – see front matter ß 2008 Published by Elsevier B.V.

doi:10.1016/j.apsusc.2008.05.189

Please cite this article in press as: J.B.M. Krishna et al., Positron beam studies on polyaniline and Ag-coated polyaniline, Appl. Surf. Sci.
(2008), doi:10.1016/j.apsusc.2008.05.189
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2 J.B.M. Krishna et al. / Applied Surface Science xxx (2008) xxx–xxx

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Fig. 1. Variation of S-parameter with positron beam energy (Ep) for undoped and Ni-
Fig. 3. S vs. Ep curves for Ni-doped and Ag-deposited Ni-doped PANI and VEPFIT
doped PANI.
fitted curves shown as solid lines. The mean implantation depth is shown on the top
axis. The vertical dashed line at 4.4 keV shows the Ag/Ni-doped PANI interface.
63 which is defined as the ratio of the counts in the central region
64 (511  1 keV) to the total counts under the peak (511  10 keV).
65 Since, the S-parameter is very sensitive to open-volume defects, the decrease and saturation in S-parameter beyond 5 keV can be 80
66
67
presence of the vacancy-defects results in increase in the S-parameter
value [9,10]. VEPFIT analysis [11] was carried out on these
ED attributed to uniform size distribution of smaller holes. Upon
doping with Ni, it is found that at low implantation energies, the S-
81
82
68 experimental curves and the S-parameter corresponding to over parameter values are lower when compared to the S-parameter 83
69 layer and substrate, positron diffusion lengths in these layers and the values between 0 and 5 keV for undoped sample because the 84
70 thickness of the over layer was also deduced. increase in conductivity due to Ni doping has slowed down the 85
propensity for positronium formation. As the positron beam 86
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71 3. Results and discussions energy is increased, the S-parameter gradually decreases and 87
saturates. This suggests that there is shifting of sizes of free 88
72 Fig. 1 shows the variation of S-parameter as a function of volume holes to lower values due to Ni doping. This observation is 89
73 positron beam energy for undoped and Ni-doped PANI. For consistent with the conductivity measurements which show an 90
74 undoped PANI, at low implantation energies between 0 and 5 keV, increase in conductivity for Ni-doped PANI as compared to 91
75 the S-parameter stays constant at some value and beyond 5 keV, undoped PANI. Gomaa [12] has studied free volume changes in 92
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76 the S-parameter decreases and saturates. It is an established fact polyacrylic acid using positron lifetime and Doppler broadening 93
77 that S-parameter is a measure of free volume/defect property and and showed that there is a strong correlation between the 94
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78 therefore an increase in S-parameter value at the surface will conductivity and the positron annihilation parameters, viz., 95
79 correspond to larger free volume hole size in polymers. And the positron lifetime and S-parameter. The addition of dopants 96
polyacrylic acid raises the electrical conductivity due to the filling 97
up of the holes by the dopants making the free volume hole size 98
smaller. Similar investigations in polyurethane [13] have also 99
shown a strong correlation between S-parameter and the free 100
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volume hole size. Figs. 2 and 3 show the S vs. Ep curves for Ag 101
deposited undoped PANI and Ni-doped PANI. As seen in the 102
figures, the S-parameter is high at low implantation energies ( 103
1 keV) and is attributed to positron annihilation in structural 104
defects present in the Ag over layer. As the positron beam energy is 105
increased, the S-parameter decreases and reaches a minimum at 106
2 keV. This minimum value is attributed to the annihilation of 107
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positrons in the Ag over layer. The S-parameter increases and 108

saturates for further increase in positron beam energy. The 109
saturation value is attributed to annihilation events in PANI. This 110
behavior in the S vs. Ep curve is similar to that obtained for a metal/ 111
semiconductor system [14]. From VEPFIT program, the thick- 112
nesses of the over layers were deduced to 35  5 nm, which is 113
consistent with quartz crystal monitor values during film deposition. 114
For both the thin film structures, the interface lies at 4.4 keV. It may 115
be noted that for undoped PANI (Fig. 2) (a) the deposition of Ag has 116
not disturbed the polyaniline structure much because the S- 117
Fig. 2. S vs. Ep curves for undoped and Ag-deposited undoped PANI. The mean
implantation depth is shown on the top axis. The vertical dashed line at 4.4 keV
parameter for undoped as well as for Ag/undoped PANI matches 118
shows the Ag/undoped PANI interface. The solid line through the data points is a well beyond 10 keV and (b) there is slight diffusion of Ag into the 119
result of VEPFIT analysis. PANI matrix making the free volume hole size small (in the range 120

Please cite this article in press as: J.B.M. Krishna et al., Positron beam studies on polyaniline and Ag-coated polyaniline, Appl. Surf. Sci.
(2008), doi:10.1016/j.apsusc.2008.05.189
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J.B.M. Krishna et al. / Applied Surface Science xxx (2008) xxx–xxx 3

121 between 4.5 and 10 keV). For Ni-doped PANI (Fig. 3), there is an indicates an increased diffusion of Ag in Ni-doped PANI, which 142
122 increased diffusion of Ag into the PANI matrix till about 18 keV. This results in smaller size of free volume holes. 143
123 is obvious because the S-parameter for Ag/Ni-doped PANI is lower
124 than that of Ni-doped PANI till about 18 keV implying the decrease in References 144
125 size of the free volume hole due to Ag diffusion into Ni-doped PANI.
[1] M. Onoda, K. Tada, Curr. Appl. Phys. 3 (2003) 141. 145
126 The present experimental results are consistent with the results of [2] H. Sirringhaus, P.J. Brown, R.H. Friend, M.M. Nielsen, K. Bechgaard, B.M.W. 146
127 Mackova et al. [15] who have reported diffusion of Ag and Cu into the Langeveld-Voss, A.J.H. Spiering, R.A.J. Janssen, E.W. Meijer, Synth. Met. 111– 147
128 polymer matrix at room temperature itself and the effect of 112 (2000) 129. 148
[3] J.C. Chiang, A.G. MacDiarmid, Synth. Met. 13 (1986) 193. 149
129 deposition methods on the diffusion of these metals into the [4] F. Zuo, M. Angelopoulos, A.G. MacDiarmid, A.J. Epstein, Solid State Commun. 63 150

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130 polymer matrix. (1987) 97. 151
[5] C.M. Huang, J. Liu, T.C. Sandreczki, Y.C. Jean, Mater. Res. Soc. 413 (1996) 653. 152
131 [6] J. Stejskal, R.G. Gilbert, Pure Appl. Chem. 74 (2002) 857. 153
4. Summary

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[7] R.A. Nafdey, D.S. Kelkar, Thin Solid Films 477 (2005) 95. 154
[8] G. Amarendra, B. Viswanathan, G. Venugopal Rao, J. Parimala, B. Purniah, Curr. Sci. 155
132 Depth-resolved Doppler S-parameter measurements have 73 (1997) 409. 156
133 [9] R. Krause-Rehberg, H.S. Leipner, Positron Annihilation in Semiconductors, 157
been carried out on PANI in undoped, doped and Ag-coated Springer-Verlag, Berlin, 1999. 158
134 conditions. In undoped PANI, there seems to be uniform size [10] P.J. Schultz, K.G. Lynn, Rev. Mod. Phys. 60 (1988) 701. 159
135 distribution of large free volume holes up to about 5 keV beyond [11] A. Van Veen, H. Schut, J. de Vries, R.A. Hakvoort, M.R. Ijpma, AIP Conf. Proc. 218 160
136 which the size of the free volume holes have decreased and (1990) 171. 161
[12] E. Gomaa, Physica B 390 (2007) 203. 162

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137 remained uniform. But in Ni-doped PANI, there is not much [13] H. Cao, R. Zhang, J.-P. Yuan, C.-M. Huang, Y.C. Jean, R. Suzuki, T. Ohdaira, B. Nielsen, 163
138 variation in the size of the free volume holes. Variation of S- J. Phys.: Condens. Matter 10 (1998) 10429. 164
139 parameter as a function of positron beam energy for Ag/undoped [14] S. Abhaya, G. Amarendra, G.L.N. Reddy, R. Rajaraman, G. Venugopal Rao, K.L. 165
Narayanan, J. Phys.: Condens. Matter 15 (2003) L713–L719. 166
140 PANI and Ag/Ni-doped PANI are silimlar to that of a metal/ [15] A. Mackova, V. Perinaa, V. Vorckb, J. Zemekc, Nucl. Instr. Methods B 240 (2005) 167
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142 169
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Please cite this article in press as: J.B.M. Krishna et al., Positron beam studies on polyaniline and Ag-coated polyaniline, Appl. Surf. Sci.
(2008), doi:10.1016/j.apsusc.2008.05.189