Nuclear Instruments and Methods in Physics Research B 269 (2011) 27982806

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Nuclear Instruments and Methods in Physics Research B

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

Swift heavy ion irradiation induced modications in the optical band gap
and Urbachs tail in polyaniline nanobers
Somik Banerjee, A. Kumar
Materials Research Laboratory, Department of Physics, Tezpur University, Tezpur 784028, Assam, India

a r t i c l e

i n f o

Article history:
Received 17 June 2011
Received in revised form 1 September 2011
Available online 10 September 2011
Keywords:
Polyaniline nanobers
Swift heavy ions
Optical band gap
Urbachs tail
Quantum connement

a b s t r a c t
Optical band gap and Urbach tail width of HCl and CSA doped polyaniline (PAni) nanobers and the ion
beam induced modications in the band gap and Urbachs tail of the samples have been studied employing UVVis absorption spectroscopy. All the major bands appearing in the FTIR spectra exhibit a decrease
in intensity and broadening in their band widths upon interaction with the highly energetic ion beams.
This suggests that SHI irradiation induces chain-scissioning events in the PAni nanobers. An interesting
result that comes out from the FTIR analysis is a transition from the benzenoid to quinoid states in the
PAni chains, which reveals that there is a decrease in the degree of conjugation in the polymer upon irradiation. Optical absorption studies indicate three direct allowed transitions at 2.64, 3.61 and 4.08 eV for
HCl doped PAni nanobers and at 2.62, 3.49 and 4.02 eV for the CSA doped PAni nanobers. The optical
band gap is found to increase with increasing ion uence which may be attributed to the reduction in the
ber diameters upon irradiation, which is corroborated by TEM analysis. Increase in the optical band gap
also points out to a decrease in the conjugation length due to the larger torsion angles between the adjacent phenyl rings of the polymer with respect to the plane of the nitrogen atoms, which is also supported
by FTIR results. The Urbach tail width decreases with increasing ion uence indicating that structural disorders are annealed out of the PAni nanobers which is also observed from the plots of (ahm)2 against
photon energy (hm) for HCl doped PAni nanobers. The quantum connement effect is conrmed by fact
that a band gap exhibits a linear dependence on the inverse of the square of the radius of the PAni nanofibers. Infact, the increase in the optical band gap may be a combined effect of the decrease in the Urbach
band width and the quantum connement effect.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Research in the eld of conducting polymers in recent years have
been focussed on the development of conducting polymer nanostructures, which combine the advantages of organic conductors
with low dimensionality and also show better processibility. Several types of conducting polymer nanostructures such as nanobers, nanotubes, nanoparticles, nanowires and nanoribbons have
been synthesized by several techniques including microemulsion,
soft and hard template methods, interfacial polymerization,
electrospinning, etc. [17]. These nanostructures have applications
in sensors, memory devices, microelectronics, etc. [810] and in
majority of the cases show better efciency than their bulk counterpart. Among the family of p-conjugated polymers, polyaniline
(PAni) has attracted much attention because of its properties such
as special doping mechanism, good thermal and environmental stability and high conductivity. Conductivity of PAni can be modied

Corresponding author.
E-mail address: [email protected] (A. Kumar).
0168-583X/$ - see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2011.09.004

through the variation of either the number of protons, the number

of electrons or both [11]. Among the PAni nanostructures, PAni
nanobers have attracted a lot of attention because of their easy
synthesis, high processibility, their unique applications in mesoscopic physics and fabrication of nanoscale devices. 1D nanostructures are believed to be the ideal systems for investigation of the
dependence of electrical, thermal, optical and mechanical properties on quantum connement and dimensionality [12].
Ion irradiation of polymers can be used to induce irreversible
modications of their macromolecular structure, in a controlled
way, leading to remarkable changes in their chemical, optical, electrical, mechanical, morphological and thermal properties [13,14].
Modern technologies demand polymers with specic properties
that can be achieved by using ion beams. The effects of ionpolymer
interactions are more pronounced and quite different when they
are subjected to swift heavy ions (SHI) irradiation. Irradiation of
polymers with swift heavy ions leads to the change of initial structure by cross-linking, chain-scission and emission of atoms, molecules and molecule fragments [15,16]. The effect of high energy
heavy ion irradiation on the chemical and optical properties of
polymers has been investigated by several groups [1720]. The

S. Banerjee, A. Kumar / Nuclear Instruments and Methods in Physics Research B 269 (2011) 27982806

electrical properties of irradiated polymer lms have also been

studied extensively. It has been observed by Hussain et al. [21,22]
that conducting polymers thin lms show improvement in
conductivity and increase in the degree of crystallinity upon
160 MeV Ni12+ ion irradiations of uences between 5  1010 and
3  1012 ions cm2. The increase in dc conductivity has been attributed to the creation of defects, which produce new charge carriers
(polaron) whereas the enhanced degree of crystallinity is due to
production of close packed regions with aligned chains by chain
folding or cross-linking. Enhancement in electrochemical stability
of the polymers has also been observed. However, the crystallinity
of most polymers decreases upon irradiation. A decrease in crystallinity of PAni upon irradiation with 70 MeV carbon ions of uence
as high as 4.5  1013 ions cm2 has also been reported [23,24].
Ramola et al. have reported that above deposition energy in the
range 5070 keV/lm, the crystallinity of the polymer lms increases whereas at deposition energy higher than 200 KeV/lm,
the polymer gets destructed and as such the degree of crystallinity
decreases [25,26]. A change in the crystallinity of polyethylene terephthalate and polyvinylidene uoride (PVDF) polymers upon irradiation by 180 MeV Ag14+ ions in the uence range 1  1010
6.6  1012 ions cm2 have also been reported [27,28] and has been
correlated to the crystallinity changes to the secondary radiationinduced crystallization process. This process has also been observed in c-rays irradiated polypropylene by Mateev and Karageorgiev [29].
Recently the authors have investigated the SHI irradiation effects on PAni nanobers. It has been observed that upon SHI
irradiation PAni nanobers are fragmented and amorphized
[30]. Transmission electron microscopy reveals that the average
diameter decreases from 29.35 to 9.45 nm for the HCl doped
PAni nanobers and from 50 to 11.38 nm for the CSA doped PAni
nanobers upon SHI irradiation [30]. The typical average lengths
of the HCl and CSA doped PAni nanobers varies from about
800 nm in the pristine form to about 100 nm upon irradiation
with 90 MeV O7+ ions at uence of 1  1012 ions cm2. Micro-Raman studies of the irradiated PAni nanobers indicate a benzenoid to quinoid transformation upon exposure to SHI
irradiation [31]. In this paper, we investigate the optical properties of the PAni nanobers and the uence dependent variations
in the optical band-gap and the Urbach energy upon irradiation
by 90 MeV O7+ ions with uence varying from 3  1010 to
1  1012 ions cm2.
2. Experimental details
Aniline (p.a Merck) was distilled under reduced pressure prior
to use. All other chemicals were analytical grade reagents. Polyaniline nanobers doped with 1 M hydrochloric acid (HCl) and 1 M
camphor sulfonic acid (CSA) synthesized using interfacial polymerization technique [6] were puried by washing with HPLC grade
methanol, ltered several times and dispersed uniformly in a 2%
PVA solution for casting thin lms (50 lm) on 1 cm2 glass slides
for irradiation purpose. The samples were designated as sample S1
and S2, respectively.
90 MeV O7+ ions with mean projected range much larger than
the thickness of the lms were used to irradiate the PAni nanobers
at normal beam incidence at different uences of 3  1010, 3  1011
and 1  1012 ions cm2 using the 15UD Pelletron accelerator at the
Inter University Accelerator Centre (IUAC), New Delhi under very
high vacuum (106 Torr). The uence was controlled by controlling the time up to which the samples were irradiated. The beam
current was xed at 0.5 particle nano ampere (pnA). FTIR spectra
of the samples were acquired using a Perkin Elmer spectrum 100
FTIR spectrophotometer. UVVisible spectroscopy was recorded
employing a Shimadzu 2450 UVVisible spectrophotometer by

2799

dispersing equal amount of the samples in milli-Q water at room

temperature.
3. Results and discussion
3.1. FTIR spectroscopy
Fig. 1(a and b) shows the FTIR spectra of the pristine and irradiated PAni nanobers doped with HCl and CSA, respectively. The
vibrational bands at 1670 and 3300 cm1 occur due to the NH
stretching vibration of the benzenoid units of the emeraldine form
of PAni. The peaks at 1400 and 1460 cm1 are assigned to the C@C
stretching vibrations of the benzenoid and quinoid units of PAni,
respectively. The band at 1199 cm1 is ascribed to the CN bending
vibration mode. The band at 1122 cm1 has been ascribed to the CH
in plane deformation while the peaks at 600 and 660 cm1 are assigned to the CH out of plane deformations.
The variations in the band widths and band shifts have been
studied quantitatively by deconvoluting the FTIR spectra of the
pristine and 90 MeV O7+ ion beam irradiated PAni nanobers using
Lorentzian oscillation curves corresponding to the IR-active modes
of PAni nanobers, in the range of 5004000 cm1. Each FTIR spectra for the pristine and irradiated samples have been normalized
with respect to the maximum value prior to deconvolution using
Lorentzian oscillation curves. The detailed position, intensity and
band widths of the deconvoluted peaks are listed in Table 1.
Although there is a negligible change in the peak positions, the
intensity and band widths show remarkable variations with the increase in the irradiation uence. Fig. 2(ad) shows the deconvolution of the sub-peaks representing C@C stretching of the
benzenoid and the quinoid resonant structures for the pristine
and irradiated samples in the FTIR spectra in the range 1360
1520 cm1 using Lorentzian oscillation curves. A comparison of
the deconvoluted sub-peaks representing the C@C stretching of
the benzenoid and the quinoid ring for the pristine and irradiated
samples has been shown in Fig. 3. The intensity of the peak at
1400 cm1 due to the C@C stretching of the benzenoid ring for
the HCl doped PAni nanobers (S1) irradiated at the uence of
1  1012 ions cm2 decreases as compared to that for the pristine,
while in case of the CSA doped PAni nanobers (S2) the intensity
of the peak decreases almost to three times than that of the pristine.
The FWHMs for the HCl doped and CSA doped PAni nanobers increases by 2.69 and 1.85 cm1, respectively with increasing ion uence. On the other hand, the peak at 1460 cm1 due to the C@C
stretching of the quinoid ring intensies for both the HCl and CSA
doped PAni nanobers upon SHI irradiation as observed from the
Table 1. This suggests that there is a partial transformation from
the benzenoid to the quinoid structure in the PAni chains upon
SHI irradiation. The fact that there is a partial transition from the
benzenoid to the quinoid structure in the PAni chains is further corroborated by the decrease in the intensity of the peaks corresponding to the NH stretching at 1670 and 3300 cm1 as can be observed
from the Table 1. The intensity of the NH stretching peak at
1670 cm1 decreases from 23.9 to 9.3 for the HCl doped PAni nanober (sample S1) whereas from 23.8 to 6.0 for the CSA doped PAni
nanobers (S2). A similar decrement in the intensity is also observed for the NH stretching peak centered at 3300 cm1. The
band is also found to broaden with increasing ion uence and the
band width increases by 214.83 cm1 for the HCl doped PAni nanofibers and by 175.95 cm1 for the CSA doped PAni nanobers.
The authors have already conducted a detailed study of the effect
of 90 MeV O7+ ion irradiation on the crystalline nature of PAni nanofibers using X-ray diffraction and lR spectroscopy, which also show a
decrease in the overall degree of crystallinity and the local range of
order (domain length) of PAni nanober upon SHI irradiation. The
decrease in the degree of crystallinity is also accompanied by the

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S. Banerjee, A. Kumar / Nuclear Instruments and Methods in Physics Research B 269 (2011) 27982806

Fig. 1. FTIR spectra of pristine and irradiated (a) HCl doped and (b) CSA doped PAni nanobers.

fragmentation of PAni nanobers which increases with increasing

irradiation uence. The authors propose that PAni nanobers are
amorphized and fragmented within the core of the tracks. As the
ion uence increases, the tracks overlap and fragmentation increases leading to a reduction in the size of the PAni nanobers
which has been clearly observed from TEM experiments performed
by the same authors and is reported elsewhere [30]. The decrease in
the intensity of almost all the prominent peaks in the FTIR spectra
indicates that the interaction of the highly energetic ion beams with
the PAni nanobers induces chain scissions that increases with
increasing ion uence leading to a reduction in the crystalline nature
and induces fragmentation of the PAni nanobers upon ion beam
treatment. The chain scissioning events lead to the emission of
hydrogen atoms and molecular fragments from the aromatic rings
of the polyaniline nanobers backbone resulting in the transformation of benzenoid into the quinoid structure. At lower irradiation uence the transformation is partial and increases with the increase in
uence and beyond a critical uence complete transformation from
the benzenoid to the quinoid structure is expected. However, PAni
nanobers being highly radiation sensitive burn out before complete transformation of the benzenoid to quinoid structure if the uence is increased above 1012 ions cm2 .

on k = 800 nm. The peak at 440 nm is ascribed to the transitions

between the p and polaron bands, and the second peak centered
at 800 nm is due to the polaronp band transitions. It is observed
that with the increase in irradiation uence, the peak at 290 nm is
blue-shifted, which indicates that the size of the PAni nanobers
decreases with the increase in irradiation uence. The authors have
earlier reported that irradiation of PAni nanobers with 90 MeV
O7+ ions leads to the fragmentation of the nanobers clearly observed from TEM experiments [30].
The optical absorption coefcient (a) has been determined from
the absorption spectra using Eq. (1). After correction for reection,
the absorption coefcient (a) has been calculated from the absorbance (A), using the relation:

3.2. Optical band gap

where A is the absorbance and d is the thickness of the quartz cuvette used for the UVVis experiments.
The optical band gap may be evaluated for the values of the
absorption coefcient using the following relation:

Fig. 4 (a and b) shows the absorption spectra of the unirradiated

and irradiated PAni nanobers doped with HCl and CSA, respectively plotted in the wavelength range 200900 nm. The unirradiated sample shows three prominent peaks which are the signature
of PAni in the emeraldine salt form. In case of conducting polymers,
there are always two distinct defect bands within the band gap,
arising from a destabilization of the highest occupied band
(HOMO), which leads to the lower defect band and a stabilization
of the lowest unoccupied band (LUMO) leading to the highest defect band [32]. Stafstrm et al. have suggested that unlike other
conducting polymers, in case of PAni the doubly charged spinless
bipolarons become unstable on a polyemeraldine chain resulting
in the formation of two polarons, which separates to yield a polaron lattice. The fact that the Pauli susceptibility increases linearly
with the degree of protonation in PAni conrms the existence of
a polaron lattice in PAni. Thus, in PAni, instead of two bands, a single broad polaron band appears deep in the gap, which is also supported by band structure calculations [33].
The absorption peak occurring at k = 290 nm can be attributed
to the pp band transition. There are two visible region bands,
one at around k = 440 nm and the other, a broad peak centered

I I0 expax

The Eq. (1) may be written as

  

2:303
I
2:303

log
A;
x
I0
x

where x is the thickness of the sample;

a 2:303

 
A
d

ai

X Ai hm  Egi mi
;
hm
i

where the value of Egi and mi correspond to the energy and the nature of the particular optical transition with absorption coefcient ai.
For allowed direct, allowed indirect, forbidden direct and forbidden
indirect transitions, the value of mi corresponds to 1/2, 2, 3/2 and 3,
respectively [34]. In an allowed direct transition the electron is simply transferred vertically from the top of the valence band to the
bottom of the conduction band, without a change in momentum
(wave vector). On the other hand, in materials having an indirect
band gap, the bottom of the conduction band does not correspond
to zero crystal momentum and a transition from the valence to
the conduction band must always be associated with a phonon of
the right magnitude of crystal momentum. In the present work,
since we are dealing with nanostructures viz., PAni nanobers, we
have attempted to determine the value of mi without pre-assuming
the nature of the optical transition in the PAni nanobers.

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S. Banerjee, A. Kumar / Nuclear Instruments and Methods in Physics Research B 269 (2011) 27982806
Table 1
Position, intensity and FWHMs of the prominent FTIR peaks of pristine and 90 MeV O7+ ion beam irradiated PAni nanobers doped with HCl and CSA.
Peak
(cm1)

600

1122
1400

1460

1670
3350
a
b

Designation
of the peaks

CH out of
plane
deformation
CH in plane
deformation
C@C stretching
vibration of
benzenoid ring
C@C stretching
vibration of
quinoid ring
Due to NH
stretching
vibration of
polyaniline

Samples

Lorentzian deconvolution of the FTIR peaks for pristine and irradiated samples at different uences
Position

Intensity

FWHM

Pristine

3  1010

3  1011

3  1012

Pristine

3  1010

3e1011

1  1012

Pristine

3  1010

3  1011

1  1012

S1
S2b

603.37
603.13

602.93
605.77

603.43
603.05

602.93
601.79

23.8
16.7

13.5
15.0

12.7
12.0

10.2
5.0

30.22
27.13

33.93
30.04

34.54
31.75

36.71
40.68

S1
S2
S1
S2

1122.41
1121.61
1401.03
1400.73

1121.00
1119.20
1401.08
1400.93

1119.80
1118.62
1401.39
1400.95

1122.41
1119.68
1401.93
1401.35

49.4
34.5
19.2
13.1

31.5
31.5
12.1
12.3

29.9
27.5
10.1
9.3

26.3
12.9
9.7
4.2

99.57
89.80
24.51
24.37

102.39
98.72
24.95
24.52

106.59
105.87
25.51
25.40

109.29
108.11
27.20
26.22

S1
S2

1459.90
1459.30

1459.28
1458.83

1460.61
1458.21

1458.92
1457.94

3.9
1.7

4.9
5.2

7.2
5.4

7.8
7.8

67.87
101.13

48.44
64.40

45.03
54.80

44.97
44.42

S1
S2
S1
S2

1669.00
1669.17
3277.90
3287.32

1666.96
1669.00
3296.43
3286.34

1669.60
1668.40
3286.42
3271.83

1668.43
1669.70
3279.89
3273.51

23.9
23.8
55.1
35.1

18.4
15.4
36.7
25.3

15.1
14.9
25.1
24.6

9.3
6.0
22.3
9.0

27.95
24.9
731.15
703.74

28.66
27.2
911.17
714.07

34.93
28.4
940.92
718.21

40.25
29.7
945.98
879.69

S1 stands for the HCl doped PAni nanobers.

S2 stands for the CSA doped PAni nanobers.

Fig. 2. Lorentzian deconvolution of the FTIR spectra within 13601520 cm1 for (a) pristine HCl doped PAni nanobers and those irradiated at a uence of (b) 3  1010,
(c) 3  1011 and (d) 1  1012 ions/cm2.

Now, the Eq. (4) can be written as

dln ahm
m

dhm
hm  E

for a particular value of mi and Egi (say mi = m and Egi = E). The plot
of d[ln (ahm)]/d(hm) vs. hm will show a discontinuity at a particular
value hm = E where a possible optical transition might have occured
corresponding to a particular band-gap E = Eg1. Fig. 5 shows the plot

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S. Banerjee, A. Kumar / Nuclear Instruments and Methods in Physics Research B 269 (2011) 27982806

Fig. 3. Comparision of the deconvoluted sub peaks representing the C@C stretching
vibration of the benzenoid and quinoid rings of PAni nanobers.

of d[ln (ahm)]/d(hm) vs. hm for the pristine HCl and CSA doped PAni
nanobers.
It is observed that there are three discontinuities corresponding
to three possible optical transitions (at E = Eg1, E = Eg2 and E = Eg3)
in both the pristine HCl and CSA doped PAni nanobers. In order
to get the m values corresponding to the three optical transitions
at 2.64, 3.61 and 4.08 eV for HCl doped PAni nanobers and 2.62,
3.49 and 4.02 eV for the CSA doped PAni nanobers, we plot ln
(ahm) as a function of ln (hm  E), where E = Eg1, Eg2 and Eg3 for
the three types of optical transitions as shown in Fig. 6(ac). The
slopes of the plots have been determined by performing a linear
tting of the experimental data. It has been observed that for all
the three types of optical transitions at E = Eg1, E = Eg2 and E = Eg3
for the HCl and CSA doped PAni nanobers the slope is quite near
to 0.5. This conrms that the three types of optical transitions in
both the HCl and CSA doped PAni nanobers are of allowed direct
nature.
The direct optical band gap of the pristine HCl and CSA doped
PAni nanober samples have also been determined by plotting
(ahm)2 against the photon energy (hm). The relation between the
optical absorption coefcient (a) for a direct transition and the
photon energy (hm) was given by Fahrenbruch and Bube [35]:

ahm Ahm  Eg 1=2

Fig. 5. Plots of d[ln (ahm)]/d(hm) vs. hm for the pristine HCl and CSA doped PAni
nanobers.

where A is a constant, h is Plancks constant, m is the frequency of

the radiation and Eg is the optical energy gap for direct transition.
Fig. 7 shows the plot of (ahm)2 vs. photon energy (hm) for the
pristine HCl and CSA doped PAni nanobers. The value of the optical energy gap Eg is determined from the intersection of the extrapolated line with the photon energy axis (at a = 0). The direct optical
band gap of the pristine sample is found to be 4.23 and 4.00 eV for
the PAni nanobers doped with HCl and CSA, respectively, which is
similar to the values (Eg3) obtained from the d[ln (ahm)]/d(hm) vs. hm
plots for the same samples. Extrapolating two straight line portions
of the plots to a = 0, one can get two more activation energies viz.,
2.31 and 2.98 eV for the PAni nanobers doped with HCl and 2.41
and 3.31 eV, corresponding to the doping induced polaron defect
levels present within the band gap in the samples, which also correspond to the energies (Eg1 and Eg2) of the other two discontinuities observed in Fig. 5.
The direct optical band gap for the irradiated samples have been
determined directly from the plot of (ahm)2 vs. photon energy (hm),
since the optical transitions in PAni nanobers have been found to
be of the allowed direct nature. Fig. 8 (a and b) shows (ahm)2 vs. hm
plots for the HCl and CSA doped PAni nanobers, respectively, irradiated at a uence of 3  1010, 3  1011 and 1  1012 ions cm2.
The optical band gaps (Eg) determined from these plots have been
tabulated in Table 2. It is observed that the optical band gap in-

Fig. 4. UVVisible spectra of pristine and irradiated PAni nanobers doped with (a) HCl and (b) CSA.

S. Banerjee, A. Kumar / Nuclear Instruments and Methods in Physics Research B 269 (2011) 27982806

2803

Fig. 6. (a) Linear t of ln (ahm) vs. ln (hm  E) where E = Eg1, (b) Linear t of ln (ahm) vs. ln (hm  E) where E = Eg2 and (c) Linear t of ln (ahm) vs. ln (hm-E) where E = Eg3 for both
the HCl and CSA doped PAni nanobers.

Fig. 7. (ahv)2 vs. hm plots for the pristine PAni nanobers doped with HCl and CSA.

creases with increasing irradiation uence. This increase in the direct optical band gap values can be attributed to two factors: (a)
the fragmentation of the PAni nanobers upon SHI irradiation
[30], and (b) a decrease in the extent of conjugation which suggests
that the adjacent phenyl rings of the polymer have larger torsion
angles with respect to the plane of the nitrogen atoms [36]. This result is corroborated by the FTIR results, which show that there is a
benzenoid to quinoid transition in the PAni nanobers upon SHI

irradiation that is an evidence of the decrease in the conjugation

length of PAni nanobers.
It has also been observed from the (ahm)2 vs. (hm) plots of the
irradiated PAni nanobers doped with HCl (Fig. 8a), that the defect level observed at 2.31 eV for the pristine material cannot be
detected for the irradiated samples. This suggests that the defect
must have annealed out upon SHI irradiation. SHI irradiation
can anneal out defects as well as create defects within the forbidden energy gap of materials depending upon the nature of
the material irradiated and the ion beam parameters such as
uence, energy and charge state of the ion. The defect level at
2.98 eV observed in the (ahm)2 vs. (hm) plot for the pristine PAni
nanober is found to shift to about 3.38 eV and remains almost
similar for the samples irradiated at different uences. However,
both the defect levels in the CSA doped PAni nanober samples
still continue to exist at almost the same positions (2.41 and
3.31 eV) even after irradiation. In fact, the defect levels in CSA
doped PAni nanobers become more prominent upon SHI irradiation, which is an indication of an increase in the density of
states in the defect levels. The reason as to why the defect
level at 2.41 eV still persists after SHI irradiation in the CSA
doped PAni nanobers is not clear. One might assume that
the parameters of the ion beam being exactly same for both
the samples, the observed phenomenon as discussed above has
to do with the property of the dopant CSA, which is quite
different from HCl since CSA has a long side chain and is much
bulkier than HCl.

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S. Banerjee, A. Kumar / Nuclear Instruments and Methods in Physics Research B 269 (2011) 27982806

Fig. 8. (ahv)2 vs. hm plots for the irradiated PAni nanobers (a) doped with HCl and (b) doped with CSA.

Table 2
Optical band gap (Eopt/Eg3), defect levels (Eg1 and Eg2) and Urbach tail width (eV) of PAni nanobers.
Fluence

Radius of the PAni nanobers (nm)

a

Pristine
3  1010
3  1011
1  1012
a
b
#

Eg2 (eV)#

Eopt (Eg3) (eV)

a

S1

S2

S1

14.7 0.2
9.9 0.1
6.0 0.3
4.7 0.2

25.0 0.1
20.6 0.1
10.0 0.2
5.7 0.3

4.2 0.2
4.5 0.3
5.3 0.2
5.6 0.2

Eg1 (eV)#

Urbach energy (eV)

S1a

S2b

S1a

S2b

2.3

2.4
2.4
2.5
2.4

3.0 0.2
2.0 0.1
1.8 0.1
1.0 0.1

2.2 0.1
1.8 0.1
1.3 0.1
0.7 0.2

S2

S1

S2

3.8 0.2
4.4 0.2
4.5 0.1
4.8 0.3

3.0
3.4
3.4
3.4

3.3
3.5
3.3
3.3

S1 stands for PAni nanobers doped with HCl.

S2 stands for PAni nanobers doped with CSA.
The values of Eg2 and Eg1 may have errors up to 5%.

Fig. 9. Plot of ln a vs. hm for the pristine and irradiated PAni nanobers (a) doped with HCl and (b) doped with CSA.

S. Banerjee, A. Kumar / Nuclear Instruments and Methods in Physics Research B 269 (2011) 27982806

2805

3.3. Urbachs tail

In case of non-crystalline materials there can be dense localized
energy states, near the valence (HOMO) and conduction (LUMO)
band edges, known as Urbach energy bands. The absorption coefcient below the fundamental absorption edge for the non-crystalline materials show an exponential dependence on the photon
energy (hv) which follows the Urbach formula [37]:

am a0 exp

 
hm
Eu

where a0 is a constant, Eu is an energy which is interpreted as the

width of the tail of localized states in the forbidden band gap, m is
the frequency of radiation and h is Plancks constant. This region
is attributed to the electronic transition between a localized band
tail and an extended band. The origin of Eu is considered as thermal
vibrations in the lattice [38]. The above relation has been rst proposed by Urbach [37] to describe the absorption edge in alkali halide crystals. This relation has also been found to be applicable for
amorphous materials.
Fig. 9(a and b) shows the logarithm of the absorption coefcient
a plotted as a function of the photon energy (hm) for the pristine
and irradiated HCl and CSA doped PAni nanobers. The values of
the Urbach energies (Eu) for the pristine and irradiated PAni nanofibers doped with HCl and CSA have been calculated by taking the
reciprocal of the slopes of the linear portion of these curves and
are listed in Table 2.
According to Codys model the Urbach tail width (e) can be
written as:

eT; X



KBh KBh
1
K B hX

2r0
2r0
r0 exph=T  1

where KB is the Boltzmann constant, X is a dimensionless parameter

called structural disorder parameter and h is related to the Debye
temperature (hD) by hD  4h/3. The second term in the Eq. (8) represents the contribution of electronphonon and excitonphonon
interactions and the third term originates due to the mean square
deviation of the atoms from a perfectly ordered lattice due to structural disorder. In the present work, since all the optical absorption
spectra have been recorded at room temperature, the decrease in
the Urbach tail width in PAni nanobers upon SHI irradiation is supposed to be only due to the decrease in structural disorder.
The optical band gap calculated using UVVis spectroscopy is
actually less than the actual band gap of the material. It is due to
the band tailing that we are only able to measure the apparent
band gap and not the actual one. It is observed that the Urbachs
tail width decreases with increasing ion uence, which indicates
that the localized states due to disorder are annealed out upon
SHI irradiation. This leads to the further separation of the valence
and the conduction band edges and hence the band gap of the
material increases. Similar type of annealing out of disorders and
subsequent increase in the band gap has been reported earlier
[39]. However, the increase in band gap may be a combined effect
of the decrease in the Urbach tail width and the quantum connement effect, which has been discussed in the following section.
3.4. Quantum connement effect
Another probable reason for the increase in the band gap upon
SHI irradiation is the reduction in the ber diameter upon SHI irradiation, which reveals the existence of quantum connement effect. Table 2 shows that the absorption edge energy increases as
the diameter of the nanober decreases, which proves the quantum size effect. According to the theoretical treatment for this
small ber size, the electron and hole wave functions are individ-

Fig. 10. Bandgap vs. the inverse of the square of the radius of the pristine and
irradiated nanobers illustrating the quantum connement effect in PAni
nanobers.

ually conned. The gap energy, E, is inversely proportional to the

square of the particle radius, R, as follows [40]:

E Eg

hp
2lR2

where Eg is the bulk band gap of PAni nanobers, 

h h=2p, h is
Plancks constant, and l is the reduced mass of electrons and holes
(0.08 m0). Though the Eq. (9) is valid for spherical particles, the
equation has also been used for one dimensional nanostructures
such as Si nanowires [41,42] and Ge/Si core/shell nanowire heterostructures [43] using a cylindrical connement potential and effective mass approximation.
Fig. 10 shows the absorption edge energy as a function of the inverse of the square of the average radii of the PAni nanobers. A
linear relationship conrms the quantum size effect in PAni nanofibers leading to the enhancement of the optical band gap upon SHI
irradiation. The corresponding bulk band-gap energy obtained by
interpolating the straight line at 1/R2 = 0 is found to be 3.89 eV
for the HCl doped PAni nanobers whereas for the CSA doped is
3.96 eV.
4. Conclusions
We have studied the optical band gap and the Urbach tail width
of HCl and CSA doped PAni nanobers and also investigated the effect of SHI irradiation on the band gap and Urbachs tail. It has been
observed that PAni nanobers exhibit three allowed direct transitions at 2.64, 3.61 and 4.08 eV for HCl doped and at 2.62, 3.49
and 4.02 eV for the CSA doped PAni nanobers. The slight variations in the energies of the allowed optical transitions has been
attributed to different ber diameters in case of the two types of
PAni nanobers (HCl doped  30 nm and CSA doped  50 nm).
The optical band gap determined from the (ahm)2 against photon
energy (hm) is consistent with the energy discontinuities observed
in the plot of d[ln (ahm)]/d(hm) vs. hm, where the possible optical
transition might take place. Upon irradiation an increase in the
optical band gap is observed which has been attributed to the fragmentation of the PAni nanobers upon SHI irradiation and also a
decrease in the extent of conjugation which suggests that the adjacent phenyl rings of the polymer have larger torsion angles with
respect to the plane of the nitrogen atoms, which is also corroborated by the FTIR results which indicate a benzenoid to quinoid
transition and is an indication of reduction in p-conjugation. The
structural disorders have been found to anneal out as a result of

2806

S. Banerjee, A. Kumar / Nuclear Instruments and Methods in Physics Research B 269 (2011) 27982806

SHI irradiation as conrmed by the decreasing value of Urbach tail

width with increasing ion uence, which enhances the band gap.
Acknowledgment
The authors would like to acknowledge Dr. D.K. Avasthi for his
valuable suggestions during the experiments. The pelletron staff of
Inter University Accelerator Centre (IUAC), New Delhi is highly
acknowledged.
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