Vacuum 169 (2019) 108939

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Vacuum
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Short communication

100 MeV Silicon9+ swift heavy ion irradiation - Strategic defect annealing T
approach to enhance the electrical conductivity of few-layered MoS2 sheets -
PVA nanocomposite film
Amar Ratana, Suhasini Kunchakaraa, Meenakshi Dutta, Ambuj Tripathib, Vaishali Singha,∗
a
Mesoporous Systems and Nanocomposites Research Laboratory, University School Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, Sector 16-C
Dwarka, New Delhi, 110078, India
b
Materials Science Group, Inter-University Accelerator Centre, New Delhi, 110067, India

ARTICLE INFO ABSTRACT

Keywords: In this study, we report a strategic route to enhance the electrical conductivity of solvent exfoliated MoS2 na-
MoS2-PVA nanocomposites nosheets dispersed in Poly-vinyl alcohol (PVA) matrix as a free-standing thin film. 100 MeV Silicon9+ swift ion
Swift heavy ion irradiation beam is used to anneal the defects and decrease the degree of disorderness of MoS2 while in the polymer matrix.
Annealing effect Homogeneous dispersion and strong interfacial interaction between the nano-sheets and PVA matrix increases
Raman disorderness
the charge carrier mobility, which in turn results in a dynamic increase of conductivity by 2 orders of magnitude
Electrical conductivity
i.e. from 2.5 x 10−5 S/cm (pristine) to 2.9 x 10−3 S/cm (irradiated) at a fluence of 1 x 1011 ions/cm2.

1. Introduction enhance its electrical conductivity via defect-annealing effect at low

Nano-dimensional molybdenum disulphide (MoS2), a layered tran-
sition metal dichalcogenides possesses a direct band gap of 1.9 eV (for
monolayer), excellent ON/OFF current ratio 105-107 and high carrier
mobility up to 200 cm2/(V.s) at room temperature [1,2]. Polymer na-
nocomposites consisting of layered nano-fillers have gained a lot of
interest in the past two decades due to their markedly enhanced me-
chanical properties, thermal stability, fire resistance and gas perme-
ability etc [1]. Poly (vinyl alcohol) (PVA) is a water-soluble polymer
which is biocompatible and biodegradable [3].
Swift heavy ion (SHI) irradiation have high projected range in the
orders of few μm, by virtue of which the target atoms are excited and
the corresponding energy is deposited per unit length which is ex-
pressed in the term of electronic stopping power Se = dE/dx. The
physio-chemical processes is well explained by Thermal spike model,
i.e. electron-phonon coupling in the atomic lattice due to the local
heating induced by energy deposition along the ion beam trajectory
having nanometric dimensions which results to a transient thermal
spike, having lifetime of few picoseconds [4,5]. SHI irradiation effect is
expected to enhance the intrinsic property of MoS2-PVA nanocomposite
free standing film.
In this work, solvent assisted exfoliated MoS2 -PVA nanocomposite
free-standing film was irradiated with 100 MeV Si9+ ion beam to
fluence and dispersion of filler material in the polymer matrix.
2. Materials and methods
In a typical organic- solvent assisted exfoliation procedure [6],1 mg
of MoS2 bulk powder was ground with 10.5 ml of N-Methyl-2-Pyrroli-
done (NMP), which resulted in the formation of gel-like mixtures, and
vacuum dried at 60 °C for 6 h. The dried powder was then dispersed in
10 ml of NMP in a centrifuge tube and was ultra-sonicated for 7 h at
100 Hz, followed by centrifugation at 4000 rpm for 40 min. The pale
yellowish MoS2 supernatant, was used to prepare MoS2-PVA nano-
composite free-standing films via solution casting technique. 0.5 gm of
PVA was dissolved slowly in 10 ml double distilled water under con-
tinuous stirring at 60 °C, followed by dispersion of 20 μl of MoS2 col-
loidal solution at RT. The solution was then poured in poly-propylene
petridish and vacuum dried until the free-standing transparent thin film
was cast after solvent removal. These films were subsequently cut in the
dimensions of 1 X 1 cm2. These films irradiated with 100 MeV Silicon
ion beam using the 15UD Pelletron facility at IUAC, New Delhi, India.
The focussed ion beam scanned an area of 1 × 1 cm2 with stable cur-
rent of 0.5 pnA for each sample. The vaccum inside the chamber was
maintained at 5.6 x 10−6 mbar. The energy of the ion beam was esti-
mated using Stopping and Range of Ions in Matter (SRIM) [7]

∗
Corresponding author. Mesoporous Systems and Nanocomposites Research Laboratory, University School of Basic & Applied Sciences, Guru Gobind Singh
Indraprastha University (Govt. of NCT of Delhi), Sector-16 (C), Dwarka, New Delhi, 110078, India.,
E-mail addresses: dr_vaishali_singh@yahoo.co.in, vaishalisingh@ipu.ac.in (V. Singh).

https://doi.org/10.1016/j.vacuum.2019.108939
Received 2 September 2019; Received in revised form 10 September 2019; Accepted 10 September 2019
Available online 11 September 2019
0042-207X/ © 2019 Elsevier Ltd. All rights reserved.
A. Ratan, et al.
Fig. 1. Characterization of solvent assisted exfoliated MoS2 nanosheets (a) XRD peaks at (002), (110), (103) and (110) at 13.96°,33.58°,40.89°, and 59.36°, well
matched with JCPDS card no. 37–1492 b Raman spectra showing characteristic shifts at 383.2 and 408.52 cm-1 corresponding to A1g and E21g Raman mode re-
spectively (c) FE-SEM micrographs (d)TEM image showing the formation of sheet-like structures of MoS2.
programme. Diffraction patterns were obtained using Bruker D-8 X-Ray
diffractometer. Raman spectra were recorded using Renishaw Invia
microscopy with Ar laser (λ = 514.5 nm, 5 mW laser power). MIRA II
LMH (TESCAN) field emission scanning electron microscope (FE-SEM),
Tecnai, G 20 (FEI) for TEM imaging and Verter 70V Bruker Optik High-
resolution Fourier transform infra-red (HR-FTIR) spectrophotometer
was used to analyse different functional groups. Motic BA310 polar-
izing microscope was used to study the morphology of polymer films.
I–V characteristic measurements were done using Keithley 2400 source
meter using silver paste as contacts.
3. Results and discussion
X-Ray diffraction pattern (Fig. 1a.) of the solvent-assisted exfoliated
MoS2 nanosheets shows the planes (002), (110), (103) and (110) at
13.96°,33.58°,40.89°, and 59.36°, well matched with JCPDS card no.
37–1492. The conformational Raman spectra (Fig. 1b.) of the exfoliated
MoS2 nanosheets show the characteristic E21g mode (in-plane vibration
of Mo and S atoms) at 383.2 cm−1 and 408.52 cm−1 A1g mode (out of
the plane vibrational mode of Sulphur atoms) [8,9]. The morphology of
the MoS2 nanosheets (Fig. 1c.) shows the formation of a sheet-like
structure having flake length of around 2 μm.
Upon irradiation, a shift in the XRD peak position of (002) plane
from 13.95° to 14.26° was observed indicating a decrease in the inter-
planar spacing (Fig. 2b). This decrease is attributed to the annealing
effects observed at lower fluences due to the energy deposited in the
target material [10]. Defect annealing effect is observed in the Raman
spectra as a decrease in the degree of disorderness parameter, defined
as a ratio of intensities of A1g and E21g , at low fluences of 1 x 1011 ions/
cm2, which further increases at higher fluence of 3 x 1011 ions/cm2. HR-
2
Vacuum 169 (2019) 108939
FTIR spectra showed different vibrational peaks, the characteristic
peaks mainly at 3328, 2930,1728,1649,1252 and 1084 cm−1 corre-
sponding to O–H stretching of PVA and water hydroxyl groups, C–H
stretching, C]O carbonyl group, water bonding at MoS2, C–H bending
and C–O stretching respectively [3]. The transmittance in the spectra
shows the decrease in the intensity of the bonds present in the pristine
films owing to the loss of functional groups and the formation of various
active sites and defect sites [11]. Optical micrographs at 40kX of the
pristine film (Fig. 2f) showed the dense distribution of MoS2 structures
along with the transparent polymer matrix while at a fluence of 1 x 1011
ions/cm2 (Fig. 2g) better dispersion is observed. Schematic re-
presentation of swift energetic ion- target interaction results in two
processes i.e. (i) Interaction between MoS2 nanosheets and polymer
chain and (ii) Removal of –OH groups from PVA chains facilitating
cross-linking is shown (Fig 3a).
The observed defect annealing effect and damage due to ion beam is
explained by Thermal spike model [5]. Deposition of large amount of
energy within a few nm area, creates a cylindrical molten zone with
radius r of the order of few nm, the centre as core region having high
temperature and the peripherical area having comparatively low tem-
perature, termed as halo region. This halo region is responsible for
defect annealing while the high-temperature core region induces the
damage in the target material. According to a physical approach de-
veloped by Toulemonde and co-workers [10,12], space and tempera-
ture evolution in a cylindrical track formed by the ion beam is ex-
plained using the Non-Linear differential coupled heat diffusion/
transport equations as given below.
Equation A- Local energy density deposited by the collision of swift
heavy ion along the ion trajectory raises the temperature of the elec-
tronic subsystem
A. Ratan, et al. Vacuum 169 (2019) 108939

Fig. 2. Characterization of pristine and irradiated MoS2 nanocomposite films (a) X-Ray diffraction pattern for fluence range 1 x 1010-3 x 1011 ions/cm2 (b) increase in
the 2Ɵ values of (002) plane showing the decrease in interplanar spacing with increase in fluence due to loss of water molecules. (c) Raman spectra for fluence range
1 x 1010 - 3 x 1011 ions/cm2 ions/cm2 d) decrease in disorderness parameter up to fluence of 1 x 1011 ions/cm2 due to SHI induced defect annealing effect and further
increase at 3 x 1011 ions/cm2 due to damage (e) Decrease in the transmittance in FT-IR bands attributing to the loss of chemical groups with increasing fluence.
Optical micrographs at 40kx of (f) pristine and (g) at 1 x 1011 ions/cm2 showing dispersion of MoS2 due to irradiation.

3
A. Ratan, et al. Vacuum 169 (2019) 108939

Fig. 3. (a) Schematic representation of the interaction of ion beam with MoS2-PVA nanocomposite film due to energy transfer resulting in physio-chemical processes
(b) Conductivity as a function of increasing ion beam fluence showing a good agreement with the Raman disorderness parameters, inferring the defect annealing
effect at low fluence.

Te 1 T groups. At high fluence, molecules of different gases like CO and CO2 are
Ce (Te) = rK e (Te) e g (Te Ta) + A (r , t )
t r r t removed hence, resulting in structural defects which decreases the con-
ductivity as the degree of disorderness also increases [13]. Since, the
Equation B - Electronic temperature is transferred to lattice via electrical conductivity is directly proportional to the charge carrier den-
electron - phonon coupling sity, charge carrier mobility, and the electric field; the electrical con-
Ta 1 T ductivity is affected the most with the increase in number of defects
Ca (Ta ) = rK a (Ta) a + g (Te Ta ) which are responsible for decreasing the mobility of electrons. The only
t r r t
two factors on which conductivity depends is the charge carrier mobility
where C, T, and K are the specific heat, temperature, and thermal and density,since bias voltage is constant. The formation of sp2 carbon
conductivity values for the electronic (denoted by e) and atomic (de- chain due to the graphitization of polymer chains and enhanced inter-
noted by a) subsystems. g is the electron-phonon (e−ph) coupling facial interaction between the filler and polymer matrix results in increase
constant and A (r, t) is the initial energy density function. Electronic of charge carrier mobility. However, at higher fluences, defects increase
specific heat, Ce can be considered as constant. The initial energy resulting in decreasing the charge carrier mobility [13,14]. Hence, SHI
density function depends on the energy of the ion beam and electronic irradiation is a proven technique for defect-annealing of MoS2 within the
energy loss (Se). PVA matrix at lower fluence.

3.1. SHI irradiation effect on conductivity 4. Conclusions

With an increase in the ion fluence to 1 x 1010 ions/cm2, the electrical
conductivity drastically increases to 7.7 x 10−4 S/cm as compared to
pristine having a value of 2.6 x 10−5 S/cm due to the removal of hydroxyl
groups, which is also termed as the introduction of annealing effect at low
ion fluence Table 1 [13]. The hydroxyl groups present in the MoS2 surface
and the PVA chains can be easily removed without the introduction of
defects as shown in Fig. 3a. Now, as the fluence increases, at 1 x 1011
ions/cm2, the further decrease in resistance is attributed to the removal of
oxygen-containing groups such as carbonyl and epoxy groups as sup-
ported by FTIR studies. The shift in the 2Ɵ values as depicted in XRD
results supports the fact of removal of inter-planar oxygen-containing
Exfoliated MoS2 nanosheets/PVA nanocomposites irradiated with
100 MeV Silicon9+ ion at different fluences (1 x 1010 - 3 x 1011 ions/
cm2). Upon irradiation, at lower fluences up to 1 x 1010 ions/cm2, de-
fect-annealing effect and loss of interfacial hydroxyl bonds was ob-
served. With further irradiation at 1 x 1011 ions/cm2 exhibited 2-orders
of increase in electrical conductivity of 2.97 x 10−3 S/cm as compared
to pristine films having a conductivity of 2.58 x 10−5S/cm. Hence, SHI
is a strategic technique for defect annealing and enhancing the dis-
persion in MoS2-PVA nanocomposite system via. filler-matrix interac-
tion for attaining remarkable electrical conductivity, hence placing it in
the class of high-performance polymers.

Table 1
Ion beam parameters, various structural modifications induced like XRD (002) plane shift, Raman disorderness parameter, and electrical conductivity values.
Ion beam characteristics Sn (Nuclear Energy Se (Electronic Energy Fluence in Position of 2Ɵ corresponding to Raman disorderness Conductivity in S/cm
loss) eV/Å loss) eV/Å ions/cm2 (002) plane (XRD) in degrees parameter

100 MeV Silicon 5 x 10-2 61.39 Pristine 13.95 0.58 2.58 x 10−5
Charge state- 9+ 1 x 1010 14.12 0.55 7.69 x 10−4
Current - 0.5 pnA 1 x 1011 14.13 0.52 2.97 x 10−3
Projected Range- 135 μm 3 x 1011 14.26 0.63 5.17 x 10−5

4
A. Ratan, et al.
Acknowledgments
Vaishali Singh acknowledge the financial support from GGSIPU [7]
under FRGS scheme (GGSIPU/DRC/FRGS/2019/1553/10) and UGC-
IUAC (IUAC/XIII.3A/65316), New Delhi. Amar Ratan acknowledge the
fellowship support under UGC -IUAC project as J.R.F. Authors ac- [8]
knowledge the facilities of IUAC, New Delhi, SAIF-AIIMS, New Delhi
and CIF, Jamia Milia Islamia, New Delhi, India.
[9]
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