Applied Surface Science 418 (2017) 264–269

Contents lists available at ScienceDirect

Applied Surface Science

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

Full length article

Flexible diode of polyaniline/ITO heterojunction on PET substrate

A. Bera a , K. Deb a , V. Kathirvel b , T. Bera c , R. Thapa d , B. Saha a,∗
a
Department of Physics, National Institute of Technology Agartala, Jirania 799 046, India
b
Department of Physics and Nanotechnology, SRM University, Kattankulathur 603 203 Tamil Nadu, India
c
Research and Development Centre, Indian Oil Corporation Limited, Sector-13, Faridabad 121007, India
d
SRM Research Institute, SRM University, Kattankulathur, Tamil Nadu 603 203, India

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

Article history: Hybrid organic-inorganic heterojunction between polyaniline and ITO film coated on flexible polyethy-
Received 25 September 2016 lene terephthalate (PET) substrate has been prepared through vapor phase polymerization process.
Received in revised form Polaron and bipolaron like defect states induced hole transport and exceptional mobility makes polyani-
28 November 2016
line a noble hole transport layer. Thus a p-n junction has been obtained between the hole transport layer
Accepted 1 December 2016
of polyaniline and highly conductive n-type layer of ITO film. The synthesis process was carried out using
Available online 7 December 2016
FeCl3 as polymerizing agent in the oxidative chemical polymerization process. The prepared polyani-
line has been found to be crystalline on characterization through X-ray diffraction measurement. X-ray
Keywords:
Electronic material
photoelectron spectroscopic measurements were done for compositional analysis of the prepared film.
Hole transport The UV–vis-NIR absorbance spectra obtained for polyaniline shows the characteristics absorbance as
Polymer observed for highly conductive polyaniline and confirms the occurrence of partially oxidized emeraldine
Heterojunction form of polyaniline. The energy band gap of the polyaniline has been obtained as 2.52 eV, by analyzing
the optical transmittance spectra. A rectifying behavior has been observed in the electrical J-V plot, which
is of great significance in designing polymer based flexible electronic devices.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Occurrence of conjugating ␲-electron in different polymers
and its role in electronic transport has made them of great
scientific worth. Polaron and bipolaron [1,2] assisted charge trans-
port, and polaron bipolaron energy bands formation in polymers
attracted the physicists to consider those in electronic and opto-
electronic device applications. Therefore polymer based flexible
semiconductors [3] are being studied for exploring their out-
standing properties. Different polymers such as polyacetylene
[4–8], polypyrrole [9–12], polyaniline [13–15], poly(p phenylene-
vinylene) (PPV) [16], poly(3,4-ethylene dioxythiophene) (PEDOT)
[17–20], are therefore investigated extensively.
The inherent and superior physico-chemical properties of
polyaniline (PANI) have received a great deal of attention, making it
a promising material in the frontline research areas of semiconduc-
tor physics and devices [21]. Particularly the p-type conductivity of
polyaniline has made it very important, since the p-type conduc-
∗ Corresponding author.
E-mail addresses: biswajit.physics@gmail.com, biswajit juphy@yahoo.co.in
(B. Saha).
tion in metal oxides and other semiconductors are not up to the
mark.
Thus conductive organic materials [22–25] are of technological
importance for their applications in photovoltaic devices [26–28],
optoelectronics [29–31], and in displays devices [32]. Substan-
tial works have already been done on inorganic heterojunctions
[33–35], while heterojunction of organic-inorganic [36] hybrid
structure is the main focus of this work. Such an inorganic-organic
hybrid structure comprising of polyaniline: ITO has been reported
here. The polyaniline and ITO (PANI/ITO) heterojunction was pre-
pared through vapor phase oxidation of aniline. The PANI film has
been grown on flexible ITO coated PET substrate. There are various
techniques to prepare PANI film such as seeding polymerization
[37,38], electrochemical polymerization [39–42], photo-induced
polymerization [43,] solution polymerization [44,45], vapor phase
self-assembling polymerization [46,47], interfacial polymerization
[48–50], plasma polymerization [51,52], and sonochemical synthe-
sis process [53], The vapor phase polymerization process has been
chosen, because of its advantages in preparing a uniform film to
device the heterostructure with ITO coated PET substrate. Moreover
the vapor phase polymerization process offers number of advan-
tages like low process temperature (∼60◦ C), providing crystalline
form of PANI and options for easy control of the conductivity level
and thus electronic transport properties during junction fabrica-

http://dx.doi.org/10.1016/j.apsusc.2016.12.003
0169-4332/© 2016 Elsevier B.V. All rights reserved.
 A. Bera et al. / Applied Surface Science 418 (2017) 264–269 265

tion process just by controlling the concentration of polymerizing

agent and reaction time. In this heterojunction PANI acts as a ‘p’
layer, while ITO acts as an ‘n’ layer. The prepared heterojunction was
then studied in detail with its structural, compositional, optical and
electrical properties. Formation of a crystalline and flexible hetero-
junction has been confirmed from the characterization results. An
organic-inorganic interface of polyaniline: ITO has been formed in
this work and used for the detailed studies regarding its electrical
properties. A rectifying behavior in its current density vs. voltage
(J-V) characteristics has been observed and reported in this article.
Thus an organic-inorganic heterojunction with promising physical
properties have been obtained through low cost and technically
advantageous process of vapor phase polymerization.

2. Experimental procedure
Fig. 1. XRD pattern of the polyaniline hole transport layer deposited on ITO coated
PET, and XRD spectrum of polyaniline on glass (inset).
2.1. Synthesis of polyaniline

The synthesis of the hole transport layer of polyaniline (PANI)

has been carried out on indium tin oxide (ITO) coated flexible
polyethylene terephthalate (PET) substrates (Sigma-Aldrich) with
surface resistivity of 60 /sq. Aniline was polymerized upon the
ITO film by transforming the aniline into its vapor phase. Prior
to the synthesis the aniline (C6 H5 NH2 , Merck ≥ 99%) was purified
through double distillation process. FeCl3 was employed as poly-
merizing agent. In a beaker 50 ml of purified aniline was taken and
in another beaker 50 ml of 3.0 M iron (III) chloride anhydrous (FeCl3 ,
Merck ≥ 96%) in methanol (Merck ≥99.8%) was prepared. Ethylene
glycol (HOCH2 CH2 OH, Merck ≥99%) was added dropwise to ferric
chloride solution to make the solution viscous by using variable vol-
ume pipette. The entire process of polymerization was carried out
in a closed reactor chamber, where the aniline was heated at a tem-
perature of 60◦ C to obtain its vapor. The ITO coated PET was then
dipped gently in the FeCl3 solution and placed inside the reactor
chamber. Aniline vapor was come in contact with the polymeriz-
ing agent of FeCl3 loaded on the surface of ITO film. During reaction
time of 10 min a green colored layer of polyaniline was deposited on Fig. 2. FESEM image of polyaniline deposited on ITO coated PET.
the surface of ITO layer. The film was then taken outside chamber
and washed in methanol and deionized water to remove unre-
3. Results and discussions
acted FeCl3 and other byproduct if any. Thus a heterojunction of
polyaniline with ITO has been obtained.
3.1. Structural characterization

The crystalline structure of polyaniline is of much scientific con-

2.2. Characterization of polyaniline/ITO heterojunction
The prepared heterojunction was studied for its structural
properties, surface morphology, optical properties and electrical
junction characteristics. The structural properties were studied
from the X-ray diffraction (XRD) pattern obtained using X-ray
diffractometer (Bruker D-8 advance). The morphological charac-
terizations were done using scanning electron microscopic (SEM)
measurements as well as atomic force microscopic (AFM) mea-
surements. The FESEM measurements were carried out using
JEOL (JSM-6610 LV Model) and AFM measurement using Bruker,
MultiMode-8 through taping mode with phosphorous doped sil-
icon tip. The compositional analysis was performed using X-ray
photo electron spectroscopic (XPS) measurements by Physical
Electronics PHI Versa Probe 5000 spectrometer. For Optical charac-
terization the optical transmittance and absorbance spectra were
measured using UV–vis-NIR spectrophotometer (Perkin-Elmer
Lambda 950 spectrophotometer). Current density was measured at
different applied voltages for studying the p-n heterojunction prop-
erties using the Agilent (B2912A, USA) precision source/measure
unit.
cern, because the crystalline phase of such conductive polymer
offer superior hole mobility. The X-ray diffraction pattern has been
illustrated in Fig. 1, which shows that the polyaniline film has been
in its crystalline phase of its emeraldine salt form. The X-ray diffrac-
tion was carried out using the X-ray source of Cu K␣ radiation
of wavelength 1.54 A◦ . The XRD peak appeared at 2␪ = 15.8◦ and
2␪ = 22.8◦ [54,55] are originated from the Braggs reflection occur-
ring from (011) and (020) Millar Planes respectively. As compared
with the XRD peak intensity of highly crystalline PET, the peaks
of polyaniline are relatively small [56–58]. However for proper
visualization of polyaniline peaks, an XRD spectrum of polyani-
line prepared by the same technique on glass substrate has been
depicted in Fig. 1 (inset).
The microstructure and surface topography of the prepared
polyaniline have been studied through FESEM and AFM measure-
ments. The FESEM measurement reveals the formation of high
density polyaniline deposited on ITO coated PET substrate as
depicted in Fig. 2. The polyaniline chains are uniformly distributed
over the surface. The AFM image with scan area of 500 nm × 500 nm
is shown in Fig. 3. AFM image also indicates uniform distribution of
polyaniline over the surface with distinct grains and grain bound-
266 A. Bera et al. / Applied Surface Science 418 (2017) 264–269
Fig. 3. AFM image of the top surface of polyaniline.
Fig. 4. XPS spectra of the polyaniline hole transport layer.
aries. The average and root mean square (rms) roughness of the
film was found to be as ∼19.5 nm and ∼24.6 nm respectively.
3.2. Compositional analysis
The deposited polyniline film has been analyzed for its com-
positional studies through X-ray photoelectron spectroscopic
measurements. XPS analysis was performed using a Physical Elec-
tronics PHI Versa Probe 5000 spectrometer operating at a pressure
of 10−9 torr. All spectra were recorded using a monochromatic Al K␣
X-ray source in conjunction with an electron ion gun. The source
conditions were 100W and 18 kV and the diameter of the analy-
sis area was 100 ␮m2 . The compositional analyses were done from
the XPS spectrum as shown in Fig. 4, and in order to explore the
conduction mechanism of polyaniline this studies are very much
significant. The peaks occurring at 198 eV and 268 eV in the XPS
spectra are from Cl 2p and Cl 2 s states. The presence of Cl in
polyaniline film indicates the formation of emeradine salt form of
polyaniline, which is high electrically conductive. The peak appear-
ing at 284.6 eV is due to carbon (C 1s), the peak at 400 eV is due to
nitrogen (N 1s) and peak at 532 eV is from O1s. The peak located
at 284.6 eV is associated to the C C bonding of sp2 . The binding
energies of the quinonoid imine [ N ] and the benzonoid imine
[ NH ] bonds are 399.5 eV and 400.33 eV respectively [59].
Fig. 5. Optical transmittance spectra of the PANI/ITO heterojunction and optical
absorbance spectra (inset).
3.3. Optical properties
The optical properties draw significance in determining the
semiconductor properties related to its energy levels. In the par-
tially oxidized states of emeraldine form of polyaniline several
defect levels such as polaronic bands and bipolaronic bands are
created. These are of ample scientific significance in optimizing
the semiconductor properties. The signatures of such polaronic
and bipolaronic energy levels have been investigated from the
optical studies. The optical properties of hybrid organic-inorganic
heterojunction have been studied through optical transmittance
measurement as shown in Fig. 5. Simultaneously the optical absorp-
tion spectra (shown as inset of Fig. 5) were investigated to observe
the different absorption bands occurring in the polyaniline in
its partially oxidized states of emeraldine salt form. At around
340 nm and 400 nm an absorption bands were observed which are
attributed to polaron band transition [60]. The broad absorption
band observed at around 770 nm is due to bipolaron band transi-
tion [61]. The occurrence of the polaronic and bipolaronic bands
confirms the formation of emeraldine oxidation state of polyani-
line. The optical transmittance results were extended to obtain the
band gap of the polyaniline film deposited on flexible ITO coated
PET, using the following relation [62]
1
(˛hv) n = A(hv − Eg ) (1)
where ␣ represents the absorption coefficient, the incident photon
energy is denoted by h, Eg is the band gap and A is a constant. The
index n is related to the distribution of the density of states. The
index n = 1/2 corresponds to the direct allowed transition energy
gap and n = 2 corresponds to the indirect allowed transition energy
gaps. Using equation 1, the energy band gap of the polyaniline
loaded papers have been obtained by extrapolating the linear por-
tion of the (␣h)2 vs. h plot as shown in Fig. 6, and the band gap
has been observed as 2.52 eV, which is suitable for designing opto-
electronic devices. The optical band gap measurement has been
extended also for polyaniline film without ITO to observe any such
effect of ITO. It has been obtained as 2.48 eV for polyaniline itself,
thereby having a difference of 0.04 eV only.
3.4. Electrical properties
The hybrid organic-inorganic nanostructure formed at the
Polyaniline: ITO heterojunction is of generous scientific interest
for their electrical properties. In such cases a coupling is formed
between the two materials at the interface through electronic as
 A. Bera et al. / Applied Surface Science 418 (2017) 264–269 267

Fig. 6. Energy band gap of polyaniline from (˛h)2 vs. h plot.

well as chemical point of view. A chemical bonding of the elec-

trons of ITO is expected to be formed with the quinonoid rings of
polyaniline as shown in Fig. 7. The highlighted section in Fig. 7 Fig. 8. Schematic energy band diagram of PANI/ITO heterojunction.

represents the distorted part of polymeric chain, which causes

the formation of polaron. Generally benzene ring contains three
double bonds and three single bonds occurring alternatively. The
ring of the highlighted section (Fig. 7) is not similar with ben-
zene ring as it has only two double bonds. Since one of the double
bond breaks in the ring during polymerization an extra electron
is obtained. Thus a distortion appears in the ring due to which
the C N (single bond) changes to C N (double bond) outside the
distorted ring. However it requires two extra electrons to form
double bonds with two nitrogen atoms, whereas the distorted ring
supplies only one extra electron thereby lacking for another one.
This induces partial positive charge nature on both the nitrogen
atoms leading towards formation of polaron. Secondly the elec-
tronic energy levels are well aligned and thus attract interesting
electrical behavior. The electron affinity of polyaniline is assumed
to be 4.7 eV [63]. The positions of the lowest unoccupied molec-
ular orbital (LUMO), highest occupied molecular orbital (HOMO)
in polyaniline, the conduction band and valence band in ITO, and
the fermi levels [64] with respect to the vacuum level have been Fig. 9. Current density vs. applied voltage plot of PANI/ITO heterojunction, and effect
of bending on J-V characteristics (inset).
shown schematically in the energy band diagram in Fig. 8. The
electrical properties of polyaniline itself is of significant scientific
interest as it show p-type conductivity, and further its conductiv- layer. The coupling of the polaron and the electron of ITO at the
ity can be tuned easily during synthesis process. Three different polyaniline: ITO (organic-inorganic) interface, plays the key role
possible form of polyaniline are leucoemeraldine (fully reduced) in the electronic behavior of the heterojunction. The heterostruc-
emeraldine (partially oxidized form) and pernigraniline, (fully oxi- ture electrical behavior of the organic-inorganic interface formed
dized). Among these the emeraldine form has attracted attention at PANI/ITO junction has been studied in this work and a rectify-
because of the possibility of formation of defect energy levels and ing behavior has been observed in the J-V plot as shown in Fig. 9.
thus being a candidate for electronic material. Formation of polaron In reverse biased condition the polyaniline side is provided neg-
and bipolaron are feasible in polyaniline due to the presence of ative potential and ITO side is provided with a positive potential,
quinonoid and benzonoid groups in the polymer chain of polyani- which cause a temporary perturbation in the polymeric state of
line. Polaron are the delocalized charge carriers in the polyaniline chain at the junction region. During this perturbation the non ben-

Fig. 7. Quinonoid rings formed in the polyaniline chain.

268 A. Bera et al. / Applied Surface Science 418 (2017) 264–269
Fig. 10. dV/d(ln J) vs. J plot of PANI/ITO heterojunction.
zonoid ring transformed back to the benzonoid ring, and thus extra
carriers (electrons) are generated. Consequently a small change
in the barrier potential takes place, and the extra carrier gener-
ated at the interface contribute to the reverse current. This causes
decrease in the rectification behavior. The electronic parameters
of the heterostructure such as ideality factor and series resistance
were determined from the J–V measurements, and the possible
current transport mechanism was discussed. A built in potential
appeared at the interface of such heterojunction. This creates a bar-
rier at the interface and the thus rectifying behavior is observed in
the J-V characteristics. The measured values of current voltage were
used in the standard diode equation,
 qV
 [4] C.K. Chiang, C.R. Fincher Jr., Y.W. Park, A.J. Heeger, H. Shirakawa, E.J. Louis, S.C.
I = Is exp −1
kT
where q is the electronic charge, V is the applied voltage, k is the
Boltzmann constant, ␩ is the ideality factor, T is the absolute room
temperature in Kelvin and Is is the reverse saturation current. The
shallow donors in ITO, contribute significantly to the conductivity.
The diode ideality factor (␩) and series resistance (Rs ) of the
PANI/ITO coated PET heterojunction, have been obtained employ-
ing Cheung-Cheung’s method [65,66] using the following equation
dV kT
= ARs J +
d (lnJ) q Phys. Lett. 33 (1978) 18.
Fig. 10 shows the dV/d(ln J) vs. J plot of PANI/ITO-PET heterojuc-
tion, which appears as a straight line indicating good agreement
of formation of heterojunction. From the slope of the straight line,
series resistance was estimated as 31.98 M and from the inter-
cept the value of ideality factor was found to be 3.48. The electrical
J-V measurement has also been tested at different bending angle to
observe the bending effect if any. No such significant deviation has
been observed as shown in Fig. 9 (inset).
4. Conclusion
Rectifying heterojunction at the organic and inorganic inter-
face of polyaniline and ITO has been prepared successfully. The
synthesis process has been done through polymerization of ani-
line vapor over ITO coated PET substrate. The oxidative chemical
polymerization was done using FeCl3 as polymerizing agent.
Structural characterization through X-ray diffraction measurement
confirms crystalline phase of polyaniline in its emeraldine salt
form. The appearance of the characteristics peaks correspond-
ing to polaron and bipolaron in the optical absorbance spectra
indicates the formation of polaron and bipolaron bands in polyani-
line. The polyaniline acted as hole transport layer and thus an
organic-inorganic heterostructure has been developed. The hole
transport in polyaniline layer occurs through the polaron and bipo-
laron defect carriers, which are formed in the partially oxidized
state of polyaniline. Diode like rectifying behavior of the organic-
inorganic heterojunction was revealed from its electrical J-V plot
and explained from the schematic energy band diagram of polyani-
line: ITO heterojunction. Thus this report must find its significant
usefulness in the further development of such organic-inorganic
heterojunction and cost-effective easy synthesis of hole transport
layer.
Acknowledgements
One of the authors (B. Saha) acknowledges the Department of
Science and Technology (DST), Government of India for partial
financial support (Grants order No. SERB/F/7430/2013-14) under
Fast Track Young Scientist award scheme. The authors would like to
acknowledge the central research facilities (CRF) of National Insti-
tute of Technology Agartala for providing XRD, UV–vis-NIR and
AFM measurement facilities.
References
[1] S. Stafström, J.L. Brèdas, A.J. Epstein, H.S. Woo, D.B. Tanner, W.S. Huang, A.G.
MacDiarmid, Polaron lattice in conducting polyaniline: theoretical and optical
studies, Phys. Rev. Lett. 59 (1987) 1464–1467.
[2] Y. Ali, K. Sharma, V. Kumar, R.G. Sonkawade, A.S. Dhaliwal, Polypyrrole
microspheroidals decorated with Ag nanostructure: synthesis and their
characterization, Appl. Surf. Sci. 280 (2013) 950–956.
[3] Y. Yao, H. Dong, W. Hu, Charge transport in organic and polymeric
semiconductors for flexible and stretchable devices, Adv. Mater. 28 (2015)
4513–4523.
Gau, A.G. MacDiarmid, Electrical conductivity in doped polyacetylene, Phys.
(2) Rev. Lett. 39 (1977) 1098.
[5] J.L. Bredas, R. Silbey, D.S. Boudreaux, R.R. Chance, Chain-length dependence of
electronic and electrochemical properties of conjugated systems:
polyacetylene, polyphenylene, polythiophene, and polypyrrole, J. Am. Chem.
Soc. 105 (1983) 6555–6559.
[6] X. Bu, Y. Zhou, M. He, Z. Chen, T. Zhang, Optically active
SiO2 /TiO2 /polyacetylene multilayered nanospheres: preparation,
characterization, and application for low infrared emissivity, Appl. Surf. Sci.
288 (2014) 444–451.
[7] C.K. Chiang, Y.W. Park, A.J. Heeger, H. Shirakawa, E.J. Louis, A.G. MacDiarmid,
Conducting polymers: halogen doped polyacetylene, J. Chem. Phys. 69 (1978)
5098.
[8] C.K. Chiang, S.C. Gau, C.R. Fincher Jr., Y.W. Park, A.G. MacDiarmid, A.J. Heeger,
(3) Polyacetylene, (CH) x : n-type and p-type doping and compensation, Appl.
[9] F. Wu, W. Li, L. Guan, Y. Ye, J. Qian, X. Yang, Y. Xu, R. Chen, A
polypyrrole-supported carbon paper acting as a polysulfide trap for
lithium–sulfur batteries, RSC Adv. 5 (2015) 94479–94485.
[10] L. Zhang, K. Zhao, W. Xu, Y. Dong, R. Xia, F. Liu, L. He, Q. Wei, M. Yan, L. Mai,
Integrated SnO2 nanorod array with polypyrrole coverage for high-rate and
long-life lithium batteries, Phys. Chem. Chem. Phys. 17 (2015) 7619–7623.
[11] J.S. Lee, D.H. Shin, W. Kim, J. Jang, Highly ordered, polypyrrole-coated Co(OH)2
architectures for high-performance asymmetric supercapacitors, J. Mater.
Chem. A 4 (2016) 6603–6609.
[12] B. Alshammary, F.C. Walsh, P. Herrasti, C.P. de Leon, Electrodeposited
conductive polymers for controlled drug release: polypyrrole, J. Sol. Stat.
Electrochem. 20 (2016) 839–859.
[13] P. Lv, Y. Zhao, F. Liu, G. Li, X. Dai, X. Ji, Z. Dong, X. Qiu, Fabrication of
polyaniline/polyimide composite fibers with electrically conductive
properties, Appl. Surf. Sci. 367 (2016) 335–341.
[14] T.M. Kabomo, M.S. Scurrell, The effect of protonation and oxidation state of
polyaniline on the stability of gold nanoparticles, Eur. Polym. J. 82 (2016)
300–306.
[15] J.N. Gavgani, A. Hasani, M. Nouri, M. Mahyari, A. Salehi, Highly sensitive and
flexible ammonia sensor based on S and N co-doped graphene quantum
dots/polyaniline hybrid at room temperature, Sens. Actuators B Chem. 229
(2016) 239–248.
[16] N. Zaquen, L. Lutsen, D. Vanderzande, T. Junkers, Controlled/living
polymerization towards functional poly(p-phenylene vinylene) materials,
Polym. Chem. 7 (2016) 1355–1367.
[17] A.E. Rakhshani, Visible light emission and UV light detection properties of
solution-grown ZnO/polymer heterojunction diodes on stainless steel foil,
Appl. Surf. Sci. 311 (2014) 614–620.
 A. Bera et al. / Applied Surface Science 418 (2017) 264–269
[18] J. Liu, X. Wang, D. Li, N.E. Coates, R.A. Segalman, D.G. Cahill, Thermal
conductivity and elastic constants of PEDOT:PSS with high electrical
conductivity, Macromolecules 48 (2015) 585–591.
[19] M.S. Ramasamy, A. Nikolakapoulou, D. Raptisa, V. Dracopoulos, G. Paterakis, P.
Lianos, Reduced graphene oxide/Polypyrrole/PEDOT composite films as
efficient Pt-free counter electrode for dye-sensitized solar cells, Electrochim.
Acta 173 (2015) 276–281.
[20] J. Liu, S. Pathak, T. Stergiopoulos, T. Leijtens, K. Wojciechowski, S. Schumann,
N.K. Busies, H.J. Snaith, Employing PEDOT as the p-type charge collection
layer in regular organic–inorganic perovskite solar cells, J. Phys. Chem. Lett. 6
(2015) 1666–1673.
[21] G. Li, Z.K. Tan, D. Di, M.L. Lai, L. Jiang, J.H.W. Lim, R.H. Friend, N.C. Greenham,
Efficient light-emitting diodes based on nanocrystalline perovskite in a
dielectric polymer matrix, Nano Lett. 15 (2015) 2640–2644.
[22] O. Bierwagen, Indium oxide—a transparent, wide-band gap semiconductor for
(opto)electronic applications, Semicon. Sci. Technol. 30 (2015) 024001.
[23] Y. Shi, L. Peng, Y. Ding, Y. Zhaoa, G. Yua, Nanostructured conductive polymers
for advanced energy storage, Chem. Soc. Rev. 44 (2015) 6684–6696.
[24] L. Cui, J. Wu, H. Ju, Electrochemical sensing of heavy metal ions with inorganic,
organic and bio-materials, Biosens. Bioelectron. 63 (2015) 276–286.
[25] K. Saranya, Md. Rameez, A. Subramania, Developments in conducting
polymer based counter electrodes for dye-sensitized solar cells − an
overview, Eur. Polym. J. 66 (2015) 207–227.
[26] Y. Zhao, C. Liang, H. Zhang, D. Li, D. Tian, G. Li, X. Jing, W. Zhang, W. Xiao, Q.
Liu, F. Zhang, Anomalously large interface charge in polarity-switchable
photovoltaic devices: an indication of mobile ions in organic–inorganic halide
perovskites, Energy Environ. Sci. 8 (2015) 1256–1260.
[27] A. Sharma, J.B. Franklin, B. Singh, G.G. Andersson, D.A. Lewis, Electronic and
chemical properties of ZnO in inverted organic photovoltaic devices, Org.
Eletron. 24 (2015) 131–136.
[28] J. Wang, V. Ibarra, D. Barrera, L. Xu, Y.J. Lee, J.W.P. Hsu, Solution synthesized
p-Type copper gallium oxide nanoplates as hole transport layer for organic
photovoltaic devices, J. Phys. Chem. Lett. 6 (2015) 1071–1075.
[29] S. Jang, E. Hwang, Y. Lee, S. Lee, J.H. Cho, Multifunctional graphene
optoelectronic devices capable of detecting and storing photonic signals,
Nano Lett. 15 (2015) 2542–2547.
[30] S.J. Ko, H. Choi, W. Lee, T. Kim, B.R. Lee, J.W. Jung, J.R. Jeong, M.H. Song, J.C. Lee,
H.Y. Woo, J.Y. Kim, Highly efficient plasmonic organic optoelectronic devices
based on a conducting polymer electrode incorporated with silver
nanoparticles, Energy Environ. Sci. 6 (2013) 1949–1955.
[31] W.C.H. Choy, W.K. Chan, Y. Yuan, Recent advances in transition metal
complexes and light-Management engineering in organic optoelectronic
devices, Adv. Mater. 26 (2014) 5368–5399.
[32] K. Kudo, D.X. Wang, M. Iizuka, S. Kuniyoshi, K. Tanaka, Organic static induction
transistor for display devices, Synthetic Met. 111–112 (2000) 11–14.
[33] Y. Jung, X. Li, N.K. Rajan, A.D. Taylor, M.A. Reed, Record high efficiency
single-walled carbon Nanotube/Silicon p–n junction solar cells, Nano Lett. 13
(2013) 95–99.
[34] A. Bera, R. Thapa, K.K. Chattopadhyay, B. Saha, In plane conducting channel at
the interface of CdO–ZnO isotype thin film heterostructure, J. Alloy. Compd.
632 (2015) 343–347.
[35] A. Vomieroa, M. Ferronia, M.M. Natilec, T. Fischere, R. Fize, S. Mathure, G.
Sberveglieria, Sequential physical vapor deposition and chemical vapor
deposition for the growth of In2 O3 –SnO2 radial and longitudinal
heterojunctions, Appl. Surf. Sci. 323 (2014) 59–64.
[36] S. Pathak, A. Sepe, A. Sadhanala, F. Deschler, A. Haghighirad, N. Sakai, K.C.
Goedel, S.D. Stranks, N. Noel, M. Price, S. Hüttner, N.A. Hawkins, R.H. Friend, U.
Steiner, H.J. Snaith, Atmospheric influence upon crystallization and electronic
disorder and its impact on the photophysical properties of organic–inorganic
perovskite solar cells, ACS Nano 9 (2015) 2311–2320.
[37] F. Ito, G. Ma, M. Nagai, S. Omi, Study of particle growth by seeded emulsion
polymerization accompanied by electrostatic coagulation, Colloid. Surf. A 201
(2002) 131–142.
[38] S. Jiang, D. Sudol, V.L. Dimonie, M.S. El-Aasser, Kinetics and mechanism of
seeded dispersion polymerization, J. Appl. Polym. Sci. 109 (2008) 2979–2987.
[39] B. Wang, J.G. Tang, F. Wang, Electrochemical polymerization of aniline, Synth.
Met. 18 (1987) 323–328.
[40] D. Li, Y. Li, Y. Feng, W. Hua, W. Feng, Hierarchical graphene oxide/polyaniline
nanocomposites prepared by interfacial electrochemical polymerization for
flexible solid-state supercapacitors, J. Mater. Chem. A 3 (2015) 2135–2143.
[41] A. Watanabe, K. Mori, Y. Iwasaki, Y. Nakamura, S. Niizuma, Electrochromism
of polyaniline film prepared by electrochemical polymerization,
Macromolecules 20 (1987) 1793–1796.
[42] S.P. Mali, S.A. Gosavi, A.S. Inamdar, U.M. Chougale, V.J. Fulari, Synthesis and
characterizations of chemically and electrochemically polymerized
polyaniline thin films for energy storage, Adv. Sci. Letts. 21 (2015) 2534–2538.
269
[43] Q. Wei, M. Mukaida, K. Kirihara, Y. Naitoh, T. Ishida, Photoinduced dedoping
of conducting polymers: an approach to precise control of the carrier
concentration and understanding transport properties, ACS Appl. Mater.
Interfaces 8 (2016) 2054–2060.
[44] M.A. Shehzad, A.A. Qaiser, A. Javaid, F. Saeed, In situ solution-phase
polymerization and chemical vapor deposition of polyanilne on microporous
cellulose ester membranes: AFM and electrical conductivity studies, Synth.
Met. 200 (2015) 164–171.
[45] A.M. Kumar, Z.M. Gasem, In situ electrochemical synthesis of
polyaniline/f-MWCNT nanocomposite coatings on mild steel for corrosion
protection in 3.5% NaCl solution, Prog. Org. Coat. 78 (2015) 387–394.
[46] Y. Yang, L. Zhang, S. Li, Z. Wang, J. Xu, W. Yang, Y. Jiang, Vapor phase
polymerization deposition conducting polymer nanocomposites on porous
dielectric surface as high performance electrode materials, Nano-Micro Lett. 5
(2013) 40–46.
[47] K.L. Bhowmik, K. Deb, A. Bera, R.K. Nath, B. Saha, Charge transport through
polyaniline incorporated electrically conducting functional paper, J. Phys.
Chem. C 120 (2016) 5855–5860.
[48] T. Lia, Z. Qina, B. Lianga, F. Tianb, J. Zhaob, N. Liub, M. Zhua,
Morphology-dependent capacitive properties of three nanostructured
polyanilines through interfacial polymerization in various acidic media,
Electrochim. Acta 177 (2015) 343–351.
[49] Q. Yang, Z. Hou, T. Huang, Self-assembled polypyrrole film by interfacial
polymerization for supercapacitor applications, J. Appl. Polym. Sci. 132 (2015)
41615.
[50] F. Zenga, Z. Qin, B. Liang, T. Lib, N. Liu, M. Zhu, Polyaniline nanostructures
tuning with oxidants in interfacial polymerization system, Prog. Nat. Sci. 25
(2015) 512–519.
[51] S. Elmas, W. Beelders, J. Nash, T.J. Macdonald, M. Jasieniak, H.J. Griesser, T.
Nann, Photo-doping of plasma-deposited polyaniline (PANI), RSC Adv. 6
(2016) 70691–70699.
[52] H. Puliyalil, P. Slobodian, M. Sedlacik, R. Benlikaya, P. Riha, K.K. Ostrikov,
Plasma-enabled sensing of urea and related amides on polyaniline, Front.
Chem. Sci. Eng. 10 (2016) 265–272.
[53] A.K. Das, S.K. Karan, B.B. Khatua, High energy density ternary composite
electrode material based on polyaniline (PANI), molybdenum trioxide (MoO3 )
and graphene nanoplatelets (GNP) prepared by sono-Chemical method and
their synergistic contributions in superior supercapacitive performance,
Electrochim. Acta 180 (2015) 1–15.
[54] M. Khairya, M.E. Gouda, Electrical and optical properties of nickel
ferrite/polyaniline nanocomposite, J. Adv. Res. 6 (2015) 555–562.
[55] K.N. Pandiyaraj, V. Selvarajan, R.R. Deshmukh, M. Bousmina, The effect of
glow discharge plasma on the surface properties of Poly (ethylene
terephthalate) (PET) film, Surf. Coat. Technol. 202 (2008) 4218–4226.
[56] X. Liu, N. Wen, X. Wang, Y. Zheng, A high-Performance hierarchical
graphene@ polyaniline@ graphene sandwich containing hollow structures for
supercapacitor electrodes, ACS Sustain. Chem. Eng. 3 (2015) 475–482.
[57] H.R. Tantawy, D.E. Aston, J.R. Smith, J.L. Young, Comparison of
electromagnetic shielding with polyaniline nanopowders produced in
solvent-limited conditions, ACS Appl. Mater. Interfaces 5 (2013) 4648–4658.
[58] L. Zhang, M. Wan, Self-Assembly of Polyaniline–From nanotubes to hollow
microspheres, Adv. Funct. Mater. 13 (2003) 815–820.
[59] S.S. Patil, K.V. Harpale, S.P. Koiry, K.R. Patil, D.K. Aswal, M.A. More,
Multifunctional polyaniline–tin oxide (PANI–SnO2 ) nanocomposite:
synthesis, electrochemical, and field emission investigations, J. Appl. Polym.
Sci. 132 (2014) 41401.
[60] D.A. Khan, A. Akhtar, S.A. Nabi, Investigation of the electrical conductivity and
optical property of polyaniline-based nanocomposite and its application as an
ethanol vapor sensor, New J. Chem. 39 (2015) 3728–3735.
[61] S. Shreepathi, R. Holze, Spectroelectrochemistry and preresonance raman
spectroscopy of polyaniline-Dodecylbenzenesulfonic acid colloidal
dispersions, Langmuir 22 (2006) 5196–5204.
[62] A. Bera, K. Deb, K.K. Chattopadhyay, R. Thapa, B. Saha, Mixed phase delafossite
structured p-type CuFeO2 /CuO thin film on FTO coated glass and its Schottky
diode characteristics, Microelectron. Eng. 162 (2016) 23–26.
[63] M. Liess, D. Chinn, D. Petelenz, J. Janata, Properties of insulated gate
field-effect transistors with a polyaniline gate electrode, Thin Solid Films 286
(1996) 252–255.
[64] T. Barman, A.A. Hussain, B. Sharma, A.R. Pal, Plasmonic hot hole generation by
interband transition in gold-polyaniline, Sci. Rep. 5 (2015) 1–5.
[65] S.K. Cheung, N.W. Cheung, Extraction of Schottky diode parameters from
forward current-voltage characteristics, Appl. Phys. Lett. 49 (1986) 85–87.
[66] J. Semple, S. Rossbauer, T.D. Anthopoulos, Analysis of Schottky contact
formation in coplanar Au/ZnO/Al nano-gap Radio Frequency diodes processed
from solution at low temperature, ACS Appl. Mater. Interfaces 8 (2016)
23167–23174.