Organic Electronics 11 (2010) 1489–1499

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Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

Fabrication of device quality films of high loaded PPy/MWCNT

nanocomposites using pulsed laser deposition
S.K. Swathi a, T. Jeevananda b, Praveen C. Ramamurthy a,*
a
Department of Materials Engineering, Indian Institute of Science, Bangalore 560012, India
b
Department of Chemistry, RNS Institute of Technology, Bangalore 560061, India

a r t i c l e i n f o a b s t r a c t

Article history: Polypyrrole (PPy) – multiwalled carbonnanotubes (MWCNT) nanocomposites with various
Received 2 March 2010 MWCNT loading were prepared by in situ inversion emulsion polymerization technique.
Received in revised form 5 May 2010 High loading of the nano filler were evaluated because of available inherent high interface
Accepted 20 June 2010
area for charge separation in the nanocomposites. Solution processing of these conducting
Available online 30 June 2010
polymer nanocomposites is difficult because, most of them are insoluble in organic
solvents.
Keywords:
Device quality films of these composites were prepared by using pulsed laser deposition
Conducting polymers
Nanotubes
techniques (PLD). Comparative study of X-ray photoelectron spectroscopy (XPS) of bulk
Nanocomposites and film show that there is no chemical modification of polymer on ablation with laser.
Structure property relationships TEM images indicate PPy layer on MWCNT surface. SEM micrographs indicate that the
MWCNT’s are distributed throughout the film. It was observed that MWCNT in the com-
posite held together by polymer matrix. Further more MWCNT diameter does not change
from bulk to film indicating that the polymer layer remains intact during ablation. Even for
very high loadings (80 wt.% of MWCNT’s) of nanocomposites device quality films were fab-
ricated, indicating laser ablation is a suitable technique for fabrication of device quality
films. Conductivity of both bulk and films were measured using collinear four point probe
setup. It was found that overall conductivity increases with increase in MWCNT loading.
Comparative study of thickness with conductivity indicates that maximum conductivity
was observed around 0.2 lm.
Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction and fullerenes will increase the available interface area

Device quality films of many conducting polymers
with excellent electrical properties cannot be fabricated,
because neither they are soluble in most organic solvents
nor it can be melt processable [1,2]. Furthermore, when
nanocomposites of these polymers were prepared with
addition of fillers to enhance the electronic properties,
fabricating device quality films becomes much more diffi-
cult [3,4]. In case of bulk heterojunction polymer solar
cells, charge separation takes place at the donor and
acceptor interface. Nanomaterials like carbon nanotubes
* Corresponding author. Tel.: +91 80 2293 2627; fax: +91 80 2360 0472.
E-mail address: praveen@materials.iisc.ernet.in (P.C. Ramamurthy).
between donor and acceptor materials in the composites.
In addition it helps in mixing donor and acceptor materi-
als at molecular scale. Consequently, efficiency of charge
separation will increase. Furthermore, certain applications
demand higher loading of nanomaterials to tailor the
electronic properties.
There is a lot of interest in laser ablation of polymers in
recent years because of its application in the electronics
field where there is a need for fabrication of solvent free
films [5–9]. Various groups have evaluated ablation of
polymer using laser sources like Nd-YAG, excimer and
CO2 [10–12]. Hanson et al. studied laser ablation of various
polymers like polyethyleneterethalate (PET), polymethyl-
methacrylate (PMMA), and polycarbonates using pulsed

1566-1199/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.orgel.2010.06.013
1490 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499

UV laser. It was found that the highly absorbed wavelength

PPy 3440
produces a good film and poorly absorbed will result in a 20
PPy(80%)-MWCNT(20%)
powdery film. It was also found that, even though molecu-
PPy(20%)-MWCNT(80%)
lar weight is reduced there is no change in chemical com- 16 c-MWCNT
position of the molecules during ablation [13]. Satoru
1184 1310
Nishio et al. studied the structural difference in the polyac- 12
rylonitrile (PAN) films with various laser wavelengths. 1546

Films of PAN were deposited for wavelengths 308 nm
(XeCl), 248 nm (KrF) and 193 nm (ArF). It was found that
the original structure of PAN is retained for the films
deposited by ablation at 308 nm and deformation and
elimination of nitrile groups occur for the films prepared
by ablation at 248 nm and 193 nm, respectively. Further-
more, power dependent structural change at 248 nm was
found [14]. Recently a new method of ablation has been
developed called matrix assisted pulsed laser ablation
(MAPLE) [15]. Sellinger et al. produced PMMA films with
up to 2 wt.% carbon nanotube (CNT) in MAPLE technique
using KrF laser [9]. Vrnata et al. deposited thin layers
polypyrole (PPy) by MAPLE technology. Deposition was
carried out by KrF excimer laser with PPy in water and
dimethylsulfoxide matrix [10]. In this paper, we will
discuss about fabrication of device quality films from poly-
pyrrole-multiwalled carbon nanotube (PPy–MWCNT)
nanocomposites with high loadings by pulsed laser abla-
tion. Nanotube loadings up to 80 wt.% were used to evalu-
ate appropriateness of employing laser ablation technique
for fabrication of device quality films of nanocomposites.
2. Experimental section
2.1. Materials
MWCNT’s (diameter 10–20 nm, length 10–50 lm) pro-
duced by catalytic vapor decomposition technique and
with a purity of >95% were purchased from Iljin Nanotech
Co. Ltd., South Korea. Pyrrole monomer (99% purity,
Aldrich) was distilled under reduced pressure and stored
at low temperature prior to use. Benzoyl peroxide (BPO),
sodium dodecyl-sulfate (SDS), nitric acid (60% purity),
hydrochloric acid (37% purity) and all other organic sol-
vents used in this study were of analytical grade and used
without further purification.
Abs(%)
1045
1637
8
1605
4
0
-4
0 1000 2000 3000 4000
Wavenumber(cm-1)
Fig. 1. FTIR of PPy, PPy–MWCNT nanocomposites and c-MWCNT.
2.2. Equipment details
Deposition of PPy and PPy–MWCNT nanocomposites
were carried out by Q-switched Nydonium-doped Yttrium
Aluminium Garnet (Nd-YAG) laser source (Quanta ray
INDI-Newport Corporation). Operating wavelength used
during deposition was 1064 nm. Analysis of nanocompos-
ites and deposited films were carried out by X-ray photo-
electron spectroscopy (XPS, ThermoFisher Scientifitic
Multilab 2000), Fourier transform infrared spectroscopy
(FTIR) was used to characterize the integrity of chemical
composition of the polymer and nanocomposites before
and after ablation. FTIR spectra were recorded on a JASCO
FTIR-300E spectrometer in the wave number range of
4000–400 cm 1 with a resolution of 4 cm 1. Samples were
dispersed in KBr powder and compressed into pellets for
analysis. Thickness and RMS roughness of the films were
measured by optical profilometer (WYKO NT1100), X-ray
powder diffraction patterns were recorded on a Panalytical
Debye–Scherrer powder diffraction camera to study the
bulk and film crystallinity. Scanning electron microscopy
(SEM-Sirion field emission) and transmission electron
microscopy (TEM-Tecnai F-30) were used for morphologi-
cal studies, electrical conductivity was measured by Keith-
ley 2182A (nanovoltmeter), 6221 (current source).

Table 1
Conductivity, thickness and roughness data of PPy, PPy–MWCNT nanocomposites.

Sample no. Conductivity (S/cm) Thickness (lm) RMS roughness (nm)

Bulk Film Bulk Film
P1 P1–2 0.11 ± 0.02 1.80 ± 0.26 0.05 ± 0.0056 26
P1–5 61.35 ± 8 0.23 ± 0.0098 22
P1–10 26.50 ± 3.5 0.52 ± 0.0066 128
P2 P2–2 231.68 ± 15 93.25 ± 10.2 0.23 ± 0.0158 152
P2–5 56.50 ± 11.9 0.66 ± 0.0186 357
P2–10 23.09 ± 0.63 0.85 ± 0.0220 385
P3 P3–2 105.80 ± 2.1 102.07 ± 2.68 0.19 ± 0.0068 115
P3–5 41.07 ± 0.89 0.49 ± 0.0162 334
P3–10 21.11 ± 0.28 0.89 ± 0.0224 325
P4 P4–2 243.90 ± 10.74 256.04 ± 66.45 0.17 ± 0.0114 64
P4–5 64.78 ± 3.79 0.30 ± 0.0200 93
P4–10 30.56 ± 0.74 0.63 ± 0.0104 186
 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499 1491

Table 2
XPS data of nanocomposites.

Sample Binding energy (eV)

Bulk Film O1s
C1s (Gaussian fitting) N1s (Gaussian fitting) O1s C1s (Gaussian fitting) N1s (Gaussian fitting)
Before After Before After Before After Before After
P1 284.7 284.9 399.9 399.8 532 285 284.7 399.9 399.9 531.8
286.4 403.5 286.5 400.9
P2 284.7 284.8 400 400 532.2 285 285 400 399.7 532.5
287.4 402 287.1 404.4
P3 285 284.8 399.6 399.7 532.5 284.9 284.9 399.8 399.6 532.5
286.4 403.5 286.5 400.8
P4 284.8 284.6 399.6 399.4 532.4 284.7 284.8 399.5 399.6 532.6
286.3 402.4 286.4 400.6

32000
Counts (arb. units)

40000 284.9eV
Counts (arb. units)

C1s-Bulk 400eV
28000
N1s-Bulk
20000 287.47eV
24000

402eV
20000

0
280 284 288 292 392 396 400 404 408
Binding energy (eV) Binding Energy (eV)

80000 36000

399.7eV
counts (arb. units)

285eV
counts (arb. units)

34000 50000 532.2eV

60000 C1s-Film
counts (arb. units)

N1s- Film
32000 O1s-Bulk
40000
40000
287.1eV
30000 404.4eV
20000

28000 30000
0
280 284 288 292 296 392 396 400 404 408
Binding Energy (eV) Binding energy (eV)
524 528 532 536 540
Binding Energy (eV)
O1s-Film
60000
532.6eV
counts (arb. units)

C1s
Counts (arb. units)

80000 50000

O1s
40000
40000 N1s
Film
Bulk 524 528 532 536 540
0 Binding Energy (eV)

0 400 800
Binding Energy

Fig. 2. X-ray Photoelectron Spectra of P2.

2.3. Oxidation of MWCNT’s mechanical stirrer and thermometer, which was mounted
in a preheated oil bath. Reaction was carried out at
In the oxidation process, 0.5 g of untreated MWCNT’s 100 °C for 1 h. Obtained carboxy functionalized MWCNT’s
were suspended in 10 ml of concentrated nitric acid (c-MWCNT) were filtered using a 0.1 lm Teflon filter
and refluxed for 30 min in an ultrasonic bath. Subse- paper, washed with copious amount of de-ionized water
quently, oxidation was carried out in a two necked, until the pH value was about 7 and dried at 80 °C for
round-bottomed flask, equipped with a reflux condenser, 24 h [16].
1492 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499
2.4. Synthesis of PPy/c-MWCNT nanocomposites
Nanocomposites of PPy/c-MWCNT’s were synthesized
by inverted emulsion polymerization technique [17,18].
Emulsion was formed using SDS (0.2 M) in 1 M HCl solution
with vigorous stirring. Various weight percentages of
c-MWCNT’s (20, 40, and 80 wt.%) were then dispersed in
an emulsion under sonication for 1 h. For convenience, fol-
lowing nomenclature has been adopted in this paper: P-1
for 100% PPy, P-2 for 80% PPy and 20% MWCNT, P-3 for
60% PPy and 40% MWCNT, P-4 for 20% PPy and 80%
MWCNT. Precooled solution of pyrrole monomer (0.25 M)
was added to the above dispersion with constant stirring.
Finally, BPO solution (0.25 M) in chloroform was added
drop wise over a period of 30 min with constant stirring
to initiate the polymerization. Pyrrole adsorbed on the sur-
face of c-MWCNT’s (core layer) was polymerized to form
outer shell of the nanotubes. Within 30 min of the addition
of BPO suspension turned black, indicating formation of
polypyrrole. Reaction was continued for 5 h at room tem-
perature. Polymerization was quenched by pouring the
reaction mixture into acetone where, PPy/c-MWCNT com-
posites precipitated out and excess BPO was dissolved in
acetone. Precipitated product was then filtered and washed
with copious amount of de-ionized water to remove unre-
acted monomer and excess SDS. Finally resulting mixture
Fig. 3. Optical Profilometer of P1–5, P2–5, P3–5 and P4–5.
was washed with acetone and was dried under vacuum at
60 °C for 24 h.
Most of the electroactive polymers are difficult to dis-
solve, even if it is dissolved, presence of residual solvent
in the film affects the device performance [19,20]. Further-
more, addition of nanoparticles to the polymer matrix
would decrease the processability. Hence alternate meth-
ods of fabricating device quality films were evaluated.
Laser ablation is an interesting technique where polymer
films can be fabricated.
Pellets of nanocomposite were fabricated and used as
target material for laser ablation. Pellets with 15 mm
diameter and 3 mm thickness were fabricated using a
desk top press, with applied pressure of 10 ton. Care
was taken to keep the pellet thickness above 3 mm to
safeguard the integrity of the target during ablation.
Films were deposited for laser energy of 100 mJ and
50 mJ. Target and substrate are rotated at a constant
speed of 60 rpm to achieve uniform ablation. Films of
nanocomposites on all three different substrates i.e. sili-
con, glass and ITO were deposited in a single deposition
to minimize batch to batch process variations that might
occur. For convenience, samples were named according
to deposition time, for example films of P1 is labeled
as P1–2, P1–5 and P1–10 deposited for 2 min, 5 min
and 10 min, respectively (Table 1).
 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499
3. Result and discussion
FTIR spectra of chemically modified MWCNT’s, PPy and
PPy-coated MWCNT’s are shown in Fig. 1. Characteristic
bands due to newly formed polar functional groups were
observed in the FTIR spectra of the MWCNT’s after acid
treatment in HNO3. IR bands at 3440, 1637, and
1182 cm 1 were consistent with the OH stretching, C = O
stretching and C–C–O stretching in modified MWCNT’s,
respectively [21]. In case of PPy, characteristic fundamen-
tal ring vibration appeared at 1546 cm 1, and C–H in-
plane vibration and C–N stretching vibration appeared
at 1310 and 1045 cm 1, and at 1184 cm 1, respectively
[22]. PPy–MWCNT’s nanocomposites showed characteris-
tics peaks for both PPy and MWCNT’s. From the spectra it
is evident that there is a shift in C–O peak from
1637 cm 1 in neat PPy to 1605 cm 1 in the case of PPy–
MWCNT nanocomposites. Presence of carboxylic groups
on the nanotube surface will increase the interaction be-
tween NH groups of the PPy and COOH groups of chemi-
cally modified MWCNT’s. This indicates that PPy has
modified the MWCNT surface.
25.5°
600
(a) Powder
Intensity ( arb. units)
400
200
43°
25
2θ
25°
(b) Film
60
Intensity (arb. units)
40
20
20
2θ
Fig. 4. XRD of PPy-MWCNT nanocomposite (a) powders, (b) films.
1493
Furthermore, according to Tian and Zerbi, the intensity
ratios of the 1560 and 1480 cm 1 bands (I1560/I1480) is
inversely proportional to the extent of delocalization
[23]. Thus, polymer molecules with high concentrations
of defect sites (short conjugation lengths) showed high
values of I1560/I1480, whereas, polymer molecules with
low concentrations of defect sites (long conjugation
lengths) showed low values of I1560/I1480. It was observed
that the I1560/I1480 increases with increasing MWCNT con-
tent (i.e., with decreasing thickness of the PPy layer). This
indicates that the layer of PPy that is deposited directly
on the surfaces of MWCNT’s has a shorter conjugation
length than subsequently deposited layers, probably due
to the p–p interaction between MWCNT’s and pyrrole
monomers. With increase in MWCNT concentration, the
defect on PPy increases because nanotubes act as dopant
and also due to the fact that network structure of
P1
P2
P3
P4
P5
Fig. 5. Scanning electron microscopy image of P4-film.
50
P1
P2
P3
P4
40
Fig. 6. Transmission electron microscopic image of P2.
1494 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499

MWCNT’s. On the other hand, with decrease in PPy thick- presence of C–C bonding and C–N, C–H bonding, respec-
ness some parts of MWCNT will not interact fully with tively. N1s peak was observed at 400 eV. Gaussian fitting
PPy molecules. This results in shorter conjugation length resolves this into two peaks at 399.7 eV and 404.4 eV
of PPy [24]. indicating the presence of N–H bonding and N–C bond-
XPS was employed to determine chemical composi- ing, respectively. O1s peaks are observed at 532.5 eV.
tion of nanocomposite before and after ablation and These results are in good agreement with that of the
results are tabulated in Table 2. XPS spectrum of the tar- target material. These results indicate nanocomposite
get material P2 is as shown in the Fig. 2. C1s peak was does not get degraded during ablation process. XPS stud-
observed at 284.7 eV. Gaussian fitting resolves this into ies for P1 (Fig. 7 supporting information) film which is
two peaks at 284.8 eV and 287.4 eV indicating the pres- pure PPy also shows a good agreement with bulk indi-
ence of C–C bonding and C–N, C–H bonding, respectively. cating even though PLD process may change the molec-
N1s peak was observed at 400 eV. Gaussian fitting re- ular weight it does not change the chemical composition
solves this into two peaks at 400 eV and 402 eV of polymer [13].
indicating the presence of N–H bonding and N–C bond- Surface roughness is very important parameter in poly-
ing, respectively. O1s peaks are observed in the spectra mer thin film devices. Higher the roughness, chances of
at 532.2 eV was believed to be due to adsorbed oxygen, electrically shorting the electrodes due to pin holes
on exposure to environment. Absence of peaks at 390 eV increases. Hence low roughness is desirable. Surface
and 406 eV indicate that there is no bonding with C or roughness and thickness of the films were measured by
N, which indicates that the films are not oxidized [25– 3D optical surface profilometer (Fig. 3 and Table 1). It
27]. XPS of ablated film is shown in Fig. 2. C1s peak was observed that surface roughness increases initially
was observed at 285 eV. Gaussian fitting resolves this with addition of MWCNT’s however on further addition,
into two peaks at 285 eV and 287.1 eV indicating the surface roughness decreases. P1 films were found to be

44000
80000
Counts ( arb. units)

Count (arb.units)

399.85eV
284.9eV
60000 40000
C1s- Film N1s- film

40000 286.41eV 36000

403.5eV
20000
32000
280 284 288 292 392 396 400 404 408
Binding energy (eV) Binding Energy (eV)

100000 80000 531.8eV

Counts ( Arb. Units)

Counts (arb.units)

Counts (arb.units)

80000 284.7eV 50000 399.9eV

N1s-bulk
70000
C1s-bulk
60000
60000 O1s-bulk
40000
40000 286.5eV 400.9eV
50000
20000
30000
0 40000
275 280 285 290 295 300 392 396 400 404 408 524 528 532 536 540
Binding Energy(eV) Binding energy (eV) Binding Energy (eV)

80000
160000 532eV
Counts (arb. units)

70000
O1s-film
120000 C1s
Counts (arb. units)

60000

80000 O1s 50000

N1s Film
40000 40000
524 528 532 536 540
Bulk Binding Energy (eV)
0

0 400 800
Binding Energy (eV)

Fig. 7. (a) X-ray photoelectron spectra of P1. (b) X-ray photoelectron spectra of P3. (c) X-ray photoelectron spectra of P4.
 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499 1495

34000
Counts (arb. units) 80000 284.8eV 399.72eV

Counts (arb.units)
C1s-Film N1s-
N1s- Film
Film
32000

40000 286.4eV
30000 403.55eV

0 28000
280 284 288 292 392 396 400 404 408
Binding energy (eV) Binding Energy (eV)
O1s Bulk

Counts (arb. units)

120000
42000 80000
Counts (arb. units)

284.9eV
Counts (arb. units)
80000 40000 399.6eV
C1s - Bulk 60000
N1s-Bulk

400.8eV
286.5eV 38000 40000
40000
528 532 536 540
Binding Energy (eV)
36000
0
280 284 288 292 80000
392 396 400 404 408

Counts (arb. units)

532.5eV
Binding Energy (eV)
Binding energy (eV) 70000
O1s- Film
60000

50000

40000

160000 524 528 532 536 540

Binding Energy (eV)
C1s
Counts (arb. units)

120000

80000
O1s

40000
N1s
Film
0 Bulk

0 200 400 600 800 1000

Binding Energy(eV)

Fig. 7 (continued)

smoother than P2, P3 and P4 because it is not a mixture, XRD analysis of pure PPy and nanocomposite powders
but single homogeneous material system. On the contrary, are as shown in Fig. 4a. A broad peak at 25.5° was observed
P4, mixture of different materials viz, nanotubes and poly- for pure PP, indicating amorphous nature of PPy. In case of
mer, was found to be smoother than P2 and P3. Because at nanocomposite powders, in addition to peak at 25.5°
such high loadings, major component in the composite will another peak at 43°, which is attributed to (1 0 0) reflection
be nanotubes and polymer would get filled in intricacy of from MWCNT, was observed [28]. It was also observed that
MWCNT’s mat structure upon film fabrication. Conse- as MWCNT loading increases in nanocomposite, intensity
quently, roughness decreases by filling up of crests and of the peak at 43° increases and peaks become sharper.
troughs formed by the nanotube matrix. In case of P2 Since XRD of MWCNT show peaks at same 2h values,
and P3 MWCNT mat will have bigger voids because of increase in intensity can be attributed to increase of
lesser nanotube wt.% than P4. Hence, films of P2 and P3 MWCNT loading in nanocomposites. XRD patterns of the
show higher values of roughness indicating insufficient fill- films also show that the films are amorphous (Fig. 4b).
ing of voids in the matrix by the polymer. Hence intermix- Distribution of MWCNT in the matrix is analyzed by
ing of PPy-MWCNT at such loadings will result in rough scanning electron microscopy of both film and the powder
surface. Films deposited for 100 mJ were rougher (RMS (Fig. 5). Film morphology of P1 which is pure PPy, is
320 nm) than the films deposited for 50 mJ (RMS smooth with a RMS roughness of 22 nm. Film images of
152 nm) moreover at 100 mJ deposition rate is too high P2, P3and P4 which are MWCNT loaded in various wt.%
to control the thickness. Hence, all the films fabricated in shows presence of MWCNT’s and also images, which has
this study are at 50 mJ. MWCNT wt.% of 20, 40 and 80, respectively, shows that
1496 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499

120000 40000
284.6eV N1s- Film

Counts (arb. units)

Counts (arb. units)

C1s - Film
399.4eV
80000
38000

286.3ev
40000 402.4eV
36000

0
280 284 288 292 392 396 400 404 408
Binding energy (eV) Binding Energy (eV)

O1s- Film

284.8eV 532.4eV

Counts (arb. units)

Counts (arb. units)

Counts (arb. unit)

N1s-Bulk
N1s- Bulk
C1s- Bulk 48000 399.6eV 80000
80000

286.4eV 400.6eV 60000

40000 46000

0 44000 40000
280 284 288 292 392 396 400 404 408 524 528 532 536 540
Binding energy (eV) Binding Energy (eV) Binding Energy (eV)
100000
532.6eV

Counts (arb. units)

O1s-Bulk
160000 80000
C1s
Counts (arb. units)

120000
60000
80000 O1s

40000 524 528 532 536 540

N1s Film Binding Energy (eV)
Bulk
0

0 400 800
Binding Energy (eV)

Fig. 7 (continued)

along with polymer MWCNT’s are also ablated. Moreover, intact further supporting the evidence of the integrity
MWCNT’s are distributed through out the matrix. Diameter of the polymer coating that was observed in SEM analy-
of the MWCNT’s for both film and the bulk were measured sis. Measured polymer thickness of P2, P3 and P4 varies
and indicated on the images. For both bulk and film, diam- from 3–15 nm, 5–12 nm and 2–3 nm, respectively. Poly-
eter of MWCNT coated with PPy varies from 24 nm to mer layer thickness decreases with decrease in PPy
66 nm. This indicates that polymer layer wrapped on nano- wt.% as indicated by SEM analysis. It is evident from
tube remains intact during ablation. Many drop like fea- TEM micrographs that MWCNT web is held together by
tures were observed in the nanocomposite films, which the polymer matrix indicating better intermixing of PPy
are attributed to the pure PPy molecular cluster (Fig. 8 and MWCNT (Fig. 9 supporting information). Even
supporting information). though PPy coating on MWCNT is not uniform low mag-
High resolution TEM image of the MWCNT in nano- nification TEM image of both bulk and film shows poly-
composite (Fig. 6) shows presence of PPy coating on mer wrapping on MWCNT’s.
MWCNT wall. It was observed that polymer layer thick- Conductivity of both bulk and films were measured
ness is not uniform throughout the film. In this particu- and compared using four point probe setup. Conductivity
lar example we found it varies from 2 to 8 nm. This of both bulk and films are shown in Table 1. Ablation
supports FTIR analysis that reason for short conjugation targets were used for bulk conductivity measurement.
length as the nonuniform thickness of PPy on MWCNT It was observed that conductivity increases by addition
walls. Polymer layer thickness was measured for all the of (20 wt.%) MWCNT from 0.11 S/cm to 231 S/cm. Electri-
three nanocomposites using TEM and thickness values cal percolation threshold for carbon nanotubes in a poly-
are indicated on Fig. 9 (supporting information). Even mer matrix are about 5–8% [29]. Increase in MWCNT
though coating is not uniform it was observed that poly- loading here does not further enhance the conductivity
mer layer thickness does not vary much from bulk to indicating percolation threshold has already been
film indicating during ablation nanocomposite remains reached. Furthermore these results also indicate that
 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499 1497

Fig. 8. Scanning electron microscopy images of P1, P2, P3 and P4.

conductivity measurements on a bulk material in pellet
form is not appropriate method as conductivity varies
with packing density of the pellet, pressure applied by
the four point probe etc. Even slight variation of these
parameters will change the conductivity values. Hence
conductivity measurements of a polymer material in a
thin film are appropriate compared to bulk measure-
ments. Increase in conductivity with increase in MWCNT
loading was observed in films. It was also observed that
in films, conductivity decreases with increase in film
thickness for all compositions except in the case of
P1–2 made from neat PPy. This is because P1–2 is not
continuous film (at 50 nm thickness) as indicated by
SEM (Fig. 10 supporting information). Optical profilometer
1498 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499

Fig. 9. Transmission electron microscopic image of nanocomposites.

indicates that the film roughness increases with increase
in film thickness (Table 1). Furthermore, with increase in
film thickness, impurities, structural defect density will
increase, hence conductivity decreases with increasing
film thickness [30]. Comparison of film conductivity with
film thickness indicates that maximum conductivity was
observed about 0.2 lm.
4. Conclusions
Device quality films of highly loaded nanocomposites
were fabricated by pulsed laser deposition. Comparative
study of X-ray photoelectron spectroscopy (XPS) of bulk
and film show that polymer does not degrade during abla-
tion. Both SEM and TEM micrographs indicate that the
MWCNT’s are distributed in the ablated films. Further
more, MWCNT diameter does not change from bulk to film
indicating that the polymer layer wrapped on MWCNT
remains intact during ablation. Conductivity of both bulk
and film were measured using collinear four point probe
setup. It was found that conductivity of films increases
with addition of MWCNT and decrease with increasing
thickness. Comparative study of thickness with conductiv-
ity indicates that maximum conductivity was observed
around 0.2 lm. Even for very high loading (80 wt.%) device
 S.K. Swathi et al. / Organic Electronics 11 (2010) 1489–1499
Fig. 10. SEM image of P1–2.
quality films were able to fabricate using PLD technique,
indicating laser ablation is an appropriate technique for
fabrication of device quality films for organic electronic
applications.
Acknowledgements
This work is partially supported by Korea Research
Council of Fundamental Science and Technology (KRCF)
and Korea Institute of Science and Technology (KIST) for
National Agenda Project (NAP) program. In addition
authors gratefully acknowledge the financial support from
DST No. SR/S3/ME/025/2008 and Technical Support from
IISc advanced characterization center. One of the authors
(Dr. T. Jeevananda) would like to thank management of
RNSIT for their support.
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