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Effect of Annealing and Time of Crystallization On Structural and Optical Properties of PVDF Thin Film Using Acetone As Solvent
Effect of Annealing and Time of Crystallization On Structural and Optical Properties of PVDF Thin Film Using Acetone As Solvent
Effect of Annealing and Time of Crystallization On Structural and Optical Properties of PVDF Thin Film Using Acetone As Solvent
1
0
7
3
8
8
6
5
1
1
8
4
0
d
c
b
a
T
r
a
n
s
m
i
t
t
a
n
c
e
(
a
.
u
.
)
wavenumber cm
-1
Fig.1.2 XRD pattern of PVDF set1 films (a) as
cast film, (b), (c) and (d) are films annealed at 70,
90 and 110 C respectively
Fig.1.2 FTIR spectra of PVDF set-1 films (a) as
cast film, (b), (c) and (d) are films annealed at 70,
90 and 110 C respectively.
Optical spectra for set 1 PVDF films
Effect of Annealing and Time of Crystallization on Structural and Optical Properties of PVDF Thin
www.iosrjournals.org 45 | Page
200 300 400 500 600 700 800
2.0
2.5
3.0
3.5
4.0
(a)
234 nm
opaque as deposit pvdf film
a
b
s
o
r
p
t
i
o
n
(
a
.
u
.
)
wavelength (nm)
200 300 400 500 600 700 800
1.5
2.0
2.5
3.0
3.5
4.0
(b)
318 nm
opaque pvdf film annealed at 70
0
C
a
b
s
o
r
p
t
i
o
n
(
a
.
u
.
)
wavelength(nm)
200 300 400 500 600 700 800
2.5
3.0
(c)
326 nm
opaque pvdf film annealed at 90
0
C
a
b
s
o
r
p
t
i
o
n
(
a
.
u
.
)
wavelength(nm)
200 400 600 800
2.0
2.5
3.0
(d)
358 nm
opaque pvdf film annealed at 110
0
C
a
b
s
o
r
p
t
i
o
n
(
a
.
u
.
)
wavelength(nm)
Figure 1.3 Absorption plot of PVDF set-1 films (a) as grown film, (b), (c),and (d) for samples annealed at 70,
90 and 110 C respectively.
Tauss Plot:
2 3 4 5 6
0
5
10
15
20
(a)
5.20eV
energy (eV)
(
*
h
v
)
2
2 3 4 5 6
0
5
10
15
20
(b)
4.77 eV
(
*
h
v
)
2
energy(eV)
2 3 4 5 6
0
5
10
15
20
25
(c)
4.62 eV
(
*
h
v
)
2
energy(eV)
2 3 4 5 6
0
5
10
15
20
25
4.05 eV
energy(eV)
(d)
(
a
*
h
v
)
2
Figure1.4 Square of alpha*energy Vs energy plots of set-1 films (a) As cast film. (b), (c) and (d) are films
annealed at 70, 90 and 110 C.
10 20 30 40 50
500
1000
1500
2000
2500
3000
10 20 30 40 50
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
10 20 30 40 50
200
400
600
800
1000
1200
1400
1600
1800
2000
10 20 30 40 50
0
200
400
600
800
1000
1200
1400
1600
1800
2000
(a)
as deposit
i n
t
e
n
s
i t
y
i n
t
e
n
s
i t
y
i n
t
e
n
s
i t
y
2
(b)
annealed at 70
0
C
(c)
2
2
i n
t
e
n
s
i t
y
annealed at 90
C
(d)
2
annealed at110
0
C
400 600 800 1000 1200
d
c
b
a
T
r
a
n
s
m
i
t
t
a
n
c
e
(
a
.
u
.
)
wavenumber(cm
-1
)
6
1
6
c
m
-
1
7
7
3
c
m
-
1
Figure 2.1 XRD patterns for set 2 films, (a) as
cast film, (b) films annealed at 70 C, (c) films
annealed at 90 C and (d) films annealed at 110 C.
Figure 2.2 FTIR patterns for set 2 films, (a) as
cast film, (b) films annealed at 70 C, (c) films
annealed at 90 C and (d) films annealed at 110
200 300 400 500 600 700 800
2.0
2.5
3.0
3.5
4.0
(a)
234 nm
opaque as deposit pvdf film
a
b
s
o
r
p
t
i
o
n
(
a
.
u
.
)
wavelength (nm)
200 300 400 500 600 700 800
1.5
2.0
2.5
3.0
3.5
4.0
(b)
318 nm
opaque pvdf film annealed at 70
0
C
a
b
s
o
r
p
t
i
o
n
(
a
.
u
.
)
wavelength(nm)
200 300 400 500 600 700 800
2.5
3.0
(c)
326 nm
opaque pvdf film annealed at 90
0
C
a
b
s
o
r
p
t
i
o
n
(
a
.
u
.
)
wavelength(nm)
200 400 600 800
2.0
2.5
3.0
(d)
358 nm
opaque pvdf film annealed at 110
0
C
a
b
s
o
r
p
t
i
o
n
(
a
.
u
.
)
wavelength(nm)
Effect of Annealing and Time of Crystallization on Structural and Optical Properties of PVDF Thin
www.iosrjournals.org 46 | Page
Figure 2.3 Absorption plot of PVDF set 2 film (a) As cast film. (b), (c) and (d) are films annealed at 70, 90
and 110C.
Taucs plot:
2 3 4 5 6
0
5
10
15
20
(a)
5.20eV
energy (eV)
(
*
h
v
)
2
2 3 4 5 6
0
5
10
15
20
(b)
4.77 eV
(
*
h
v
)
2
energy(eV)
2 3 4 5 6
0
5
10
15
20
25
(c)
4.62 eV
(
*
h
v
)
2
energy(eV)
2 3 4 5 6
0
5
10
15
20
25
30
energy(eV)
(
*
h
v
)
2
4.05 eV
(d)
Figure 2.4 Square of alpha*energy Vs energy for PVDF set 2 films (a) As cast film. (b), (c) and (d) are films
annealed at 70, 90 and 110 C.
0 20 40 60 80 100 120
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
6.0
(b)
(a)
B
a
n
d
g
a
g
(
e
V
)
Annealing Temperature(
o
C)
Figure 3.1 Band gap against annealing temperature
(a) and (b) for samples prepared under set 1 and
set 2 conditions respectively
TABLES
Set 1 Set 2
Sample 2 Assignment 2 Assignment
As grown film 20.6 phase 18.46 phase
22.6 phase 20.45 phase
42.7 phase 26.80 phase
39.20 phase
Annealed at 70 C 18.4 phase 18.46 phase
20.2 phase 20.42 phase
26.7 phase 26.80 phase
39.6 phase 39.30 phase
Annealed at 90 C 18.2 phase 18.59 phase
20.1 phase 20.40 phase
38.4 phase 26.80 phase
39.30 phase
Annealed at 110 C 18.6 phase 18.30 phase
20.1 phase 20.40 phase
21.0 phase 26.80 phase
39.30 phase
Table1 Peaks feature in XRD patterns of samples under study.
Band gap and absorption edge of PVDF samples:
S.
no.
Samples Set 1 PVDF thin films Set 2 PVDF films
Absorption Edge (nm) Band gap (eV) Absorption Edge (nm) Band gap (eV)
1. As deposit 227 5.20 238.8 5.86
2. Annealed at 70 C. 320 4.77 233.3 5.65
3. Annealed at 90 C. 326 4.62 240.6 5.56
4. Annealed at 110 C. 358 4.05 296 5.11
Effect of Annealing and Time of Crystallization on Structural and Optical Properties of PVDF Thin
www.iosrjournals.org 47 | Page
Table-2 Experimental values of band gap and absorption edge for under study samples.
V. CONCLUSION
In this report it is observed that the same solvent can yield all the three phases of PVDF. By changing
the time of crystallization different phases of PVDF can be obtained using less polar acetone solvent. The time
of crystallization and annealing conditions decide the presence of different phases and conversion of one phase
to other phase of PVDF. The -phase which is important for ferroelectric application is obtained using less polar
solvent and by suitable annealing. Maximum -phase exists in the rapidly dried PVDF films when are annealed
at 90C for 5 h. for. The enhanced -phase at different annealing condition has been confirmed from XRD and
FTIR of PVDF film. Thus dominant -phase films can be prepared under rapid drying of solution and annealing
at 90C for 5 hour. Films produced by slow crystallization are rich in stable -phase and remain unaltered after
annealing. UV-VIS study shows presence of absorption edge in each case. The position of absorption edge shifts
to longer wavelength with annealing temperature. Energy band gap is calculated using tauc plot and it is found
that annealing effect band gap. The decrease in energy band gap for each film is observed. Thus films with
wholly -phase can be produced by less polar solvents.
REFERENCES
[1] Lovinger, A. J. Ferroelectric polymers. Science 220, 1115_1121 (1983).
[2] Nalwa, H. S. Ferroelectric Polymers (Dekker, 1995).
[3] S. Eleshmawi, Spectroscopic, Thermal, and Electrical Investigations of PVDF Films Filled with BiCl3. Journal of Applied Polymer
Science, Vol. 102, 21252131 (2006)
[4] A. Tawansi, FeCl3CoCl2 mixed fillers effects on the structural, electrical and magnetic properties of PVDF films. Journal of
Magnetism and Magnetic Materials 262 (2003) 203211
[5] S. Satapathy Effect of annealing on phase transition in poly(vinylidene fluoride) films prepared using polar solvent. Bull. Mater.
Sci., Vol. 34, No. 4, July 2011, pp. 727733.
[6] A. Tawansi Structural and electrical properties of MgCl2-filled PVDF Films. Polymer Testing 18 (1999) 569579.
[7] Vipin Kumar , Sachin Kr. Sharma , T.P. Sharma and V. Singh, Band gap determination in thick from repentance measurements.
Elsevir Optical Materials 12 (1999) 115-119.
[8] Ali Akbar Yousefi, Influence of Polymer Blending on Crystalline Structure of Polyvinylidene Fluoride. Iranian Polymer Journal, 20
(2), 2011, 109-121
[9] B. Jaleh P. Fakhri M. Noroozi N. Muensit, Influence of Copper Nanoparticles Concentration on the Properties of Poly(vinylidene
fluoride)/Cu Nanoparticles Nanocomposite Films J Inorg Organomet PolymDOI 10.1007/s10904-012-9660-5
[10] A. Rawat, H. K. Mahavri, S Chauhan, A.Tanwar & P. J. Singh, optical band gap of polyvinylpyrrolidone/polyacrilamide blend thin
films. Indian Journal of Pure & Applied Physics, Vol. 50, February 2012, pp. 100-104