Journal of Al-Nahrain University Vol.16 (1), March, 2013, pp.

17-20 Science

Study the Optical properties of Poly (vinyl alcohol)

Doped Cupper Chloride
Mustafa Abdallh, Osama Hamood and Emad Yousif
Department of Chemistry, College of Science, Al-Nahrain University,
Baghdad-Iraq.

Abstract
The change in the optical band gap and optical activation energy have been investigated for pure
and doped Poly (vinyl alcohol) films with different cupper chloride concentrations. The optical
properties were measured in the wave length range from (200-800) nm at room temperature. The
optical band gap (Eg) for allowed direct transition decrease with increase the concentration of
cupper chloride. The optical activation energy for allowed direct transition band gap was evaluated
using Urbach- edges method.
Keywords: optical band gap, optical activation energy, PVA.

Introduction Experimental
In recent years, studies on the electrical 1. Films preparation
and optical properties of polymers PVA films doped with Cupper Chloride
have attracted much attention in view of were prepared at room temperature by solution
their applications in optical devices casting method. The PVA was dissolved in
with remarkable reflection, antireflection, distilled water and heated gently in water bath
interference and polarisation properties [1-3]. to prevent thermal decomposition of polymer.
Various composite materials have been The polymer was stirred by magnetic stirrer for
recently synthesized by starting from different completely dissolved. The copper chloride with
polymers and a wide variety of dopants like different ratios (1, 3, 5, 7, 9, and 10%) were
metals, oxides, inorganic salts, and other dissolved in distilled water and added to the
particles [4,5].The incorporation of the polymer solution, heated for a while for
dopants into polar organic polymers can completely dissolved. The solution poured on
induce pronounced changes in various to a glass plate and left to dry for 24 hr to
properties of polymers in order to modify and remove any residual solvent. The thickness of
improve its properties[6-8]. the films were ranging from (55 – 60) µm.
This article discloses the investigation Thickness measurements were made using
of the effect of doping with different micrometer.
concentrations of CuCl2 on the optical The optical absorbance (A) of the samples
properties of poly(vinyl alcohol) films. In were measured as function of wavelength (λ)
general the absorption spectra in UV region at the range from (200-800) nm using
increase with increasing dose. In principle, computerized Shimadzu UV-VIS 160
photon with energy greater than the band gap A-Ultraviolet- spectrophotometer full scale
energy will be absorbed. Electromagnetic absorbance up to (2.5). The light sources are
wave packet interacts with electron in the halogen lamp and socket-deuterium lamp.
Valence Band (VB), which is then raised
across the band gap on the conduction band 2. Optical measurement
(CB) via two possible types of electronic The absorption peak at UV region, were
transition, i.e. direct transition and indirect used to study the shifting in the optical energy
transition. In the direct transition the wave gap for PVA and PVA-CuCl2 films at 25 oC.
vector for the electron remains unchanged, The best definition of the energy gap is the
while in the indirect transition the lattice minimum energy difference between the
vibration or phonons assist the transition so lowest minimum of conduction band and the
that the minimum of the CB lies in the highest maximum of the valance band [10].
different part of k-space from the maximum of The value and shape of the mobility gap in
the VB [9]. PVA depends on the proportion conditions

17
 Mustafa Abdallh

such as substrate temperature, degree of The effect of CuCl2 addition on the values
impurity and defect of the material. Any of photon energies are shown in Table (1). Eg
variation in such parameters leads to a shift in decreases in the trend pure PVA, PVA+1%
the absorption edge towards higher or lower CuCl2, PVA+3% CuCl2, PVA+5% CuCl2,
energy. The absorption coefficient which can PVA+7% CuCl2, PVA+9% CuCl2 and
be determined from the normal incidence PVA+10% CuCl2.
transmission through plane-parallel plate of The shift in the energy gap could be
thickness (d) interference and multiple attributed to the formation of polorans in the
reflections are neglected. The reflectance (R) doped film [9].
and transmittance (T) are related by the The polymer-salt composites may be
equation (1) characterized by interaction of the salt with the
........................................(1) polar group of the polymer, which gives rise to
Where B is a constant. This equation can be complex formation. The complex formation
rewritten as follows: may be mainly dominated by the cations
..................(2) (Cu 2+) with the OH groups in the polymer. The
cations bound to several OH groups in a
A is the optical absorbance, ( ).
polymer chain may induce a stiffening of the
So the absorption coefficient α (ω) in term of chain (intrachain effect) and bounding with
absorbance become:- other chains may act as temporary cross-links
..................................(3) (interchain effect). PVA-(Cl2)– also shows a
For direct band-to-band transition, the energy similar effect. The evidence of poloran
dependence of absorption coefficient is of the formation made the reaction in band - to- band
form: transition due to shifting of band density of
..............................(4) state toward the energy gap.
Where ( ) is the photon energy and (Eg)
is the energy gap, r is a constant depending on Table (1)
the type of the electronic transitions. It takes The energy band gap according to the direct
the value (1/2) for allowed direct transition and allowed transition for PVA and PVA doped
(3/2) for forbidden direct transition and the with CuCl2 at room temperature.
absorption coefficient (α ≥104 cm-1). The
Films type E g (eV)
energy dependence absorption coefficient is of
the from: Pure PVA 5.9
.........................(5)
PVA+ 1% 5.86
Where (Eg) is the minimum energy gap, (Ep)
is the phonon, (+) absorbed (-) emitted, (r) PVA+3% 5.81
takes the value (2) for allowed indirect
PVA+5% 5.79
transition and (3) for forbidden indirect
transition and the absorption coefficient PVA+7% 5.76
(α <104 cm-1). By plotting (αhν)1/r versus (hν)
for fixed (r)value, the extrapolation of the liner PVA+9% 5.74
part could be used to define Eg [11]. PVA+10% 5.7

Result and Discussion

The relationships between (αhυ)2 versus
photon energy for the polyvinyl alcohol
samples are shown in Fig.(1 to 7) for allowed
transition. It can be evaluated from
extrapolating of linear region of the curve to a
point of (αhυ)2 versus h for pure and doped
PVA with cupper chloride at different
concentrations at room temperature (25)°C.

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Journal of Al-Nahrain University Vol.16 (1), March, 2013, pp.17-20 Science

Fig.(1) The direct transition (αhυ)2 Vs. Fig.(4) The direct transition (αhυ)2 Vs.
energy for pure PVA at room temperature. energy for PVA+5%( CuCl2) at room
temperature.

Fig.(2) The direct transition (αhυ)2 Vs. Fig.(5) The direct transition (αhυ)2 Vs.
energy for PVA+1% ( CuCl2) at room energy for PVA+7% ( CuCl2) at room
temperature. temperature.

Fig.(3) The direct transition (αhυ)2 Vs. Fig.(6) The direct transition (αhυ)2 Vs.
energy for PVA+3% ( CuCl2) at room energy for PVA+9% ( CuCl2) at room
temperature. temperature.

19
 Mustafa Abdallh

[7] Ghani, A., Young, H. Conductive polymer

based on polyaniline-eggshell powder
(PANI-ESP) composites. J. Phys. Sci. 21,
81–97, 2010.
[8] Mohammed, R., Gadou, A., AC-
conductivity and dielectric properties of Y-
irradiated PVA films doped with Mn+2 ions.
Egypt J. Sol. 23, 277–286, 2000..
[9] Elias, S., Susila, W., Doyan, A., Zainal
Abidin, S., Azmi, Z., Zulkfli, A., Mohd
Fig.(7) The direct transition (αhυ)2 Vs. Zaki, AR., Dahlan, K.Z.H., Karni, T.
energy for PVA+10% ( CuCl2) at room Changes the Optical Band Gap and
temperature. Apsorption Edes of Gamma – Irradiated
Polymer Blends, Journal of Applied
Conclusion
The optical absorption in the UV-visible Science.5(10):1825-1829, 2005.
region for pure and doped filmes were studied. [10] Mohammed, A. Studying The
it is found that the Eg for allowed direct Conductivity of Poly(Vinyl Chloride ) using
transtion decreases with increasing the 2-(sub.)-5-[3-(5-nitro-fur-2-yl)-propen-
concentration of CuCl2. 2yldiene]amino-1,3,4thiadizole as Additives
by Measuring Forbidden Energy Gap,
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