15 Text

Eng. & Tech. Journal,Vol.27, No.
6, 2009
Correlation between Thickness, Grain Size and

Optical Band Gap of CdI2 Film
Modaffer A. Mohammed*
Received on:18/3/2008
Accepted on:22/1/2009
Abstract
Structural and optical property was studied as a function of film thickness for
thermally evaporated CdI2 films. Stoichiometric films (up to 250 nm thickness) showing
hexagonal structure, and good c-axis alignment normal to glass substrate plane. The
optical absorption data indicate an allowed direct inter band transition near the
absorption edge with optical energy gap varies continuously from 2.9 eV to 3.6 eV.Part
of the optical data was fitted to an indirect type transition to determine the indirect optical
energy gap which also varies continuously from 2.2 eV to 3.1 eV . Both energy gaps
show thickness dependences, which can be explained qualitatively by a thickness
dependence of the grain size through the decreasing of the grain boundary barrier height
with grain size.
Keywords: CdI2 thin films, Optical Band-Gap

( 250nm ) .
.( c-axis)
.(2.9eV to 3.6eV)

, .(2.2eV to 3.1eV)

.
1- Introduction
CdI2 is an important compound having a layered structure with a hexagonal
unit cell held with neighbring layers by
Van derWaals forces, in which each
hexagonal sheet of Cd atoms sandwich
between two similar sheets of I atoms, the
Cd atoms being octahedrally coordinated
[1]. As many as 200 polytypes of CdI2
material are recorded [2]. Recent studies
have revived interest in cadmium iodide
films [3-5].The optical absorption data fit
best to direct band to band transition
indicating a direct band gap, a smaller
indirect band gap can also be near the
absorption edge. The optical absorption
measurement carried out on CdI2 single
crystal samples were fitted to an indirect
energy gap of 3.2 eV while the

reflectivity spectra reveal a direct
transition at 3.8 eV.The band structure
calculation show the presence of both
direct and indirect band gaps, the
difference between the two is only about
0.3-0.6 eV [6-11].
Material modification such as grain size, morphology etc, can be achieved by
bombarding CdI2 single crystals and
thin films with laser radiation or highly
kinetic ions (plasma), where CdI2
crystals showed a linear variation of
energy gap with intensity of laser
radiation (0 to 125 mW) and decreasing
in the energy gap value from (3.28 to
3.11 eV). The effect of plasma irra-
* Applied Sciences Department, University of Technology / Baghdad
1174
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Eng.& Tech. Journal ,Vol. 27, No.6, 2009
diation on poly type (002) oriented CdI2

stoichiometric film was found to change
the orientation to (110), decre- ase in
grain size and residual stress. The iodine iodine distance in the unit cell could be
responsible for the change in Eg with
stress [12, 13]. The report on the structure
of CdI2 films show that thinner films
(<100 nm) are amorphous and thicker
films tend to crystallize[2-5], it is also
known that CdI2 films grown at substrate
temperature less than 300 k are
amorphous and these either grown or
annealed above 300 k polycrystalline[14].
In this paper we tried to correlate the
variation in the band gap of evaporated
films with different thickness with the
optical properties.
2- Experimental:
The CdI2 films were grown on glass
substrates at room temperature by thermal evaporation at a pressure better than
10-6 Torr (BALZERS BAE 080) using a
molybdenum boat .The start- ing material
was analar grade powder 99.999% pure
stoichiometric material, which was
pelletized for evaporation. Film thickness
was measured after evaporation by optical
interfero- meter method, using He-Ne
Laser = 0.632 m and the thickness were
determined using the formula:
....(1)
d =
2
Where: x is fringe width, x is the
distance between two fringes and is the
wavelength of the laser light. Films up to
100 nm were completely transparent and
become translucent for higher thicknesses
.The films of thickness below 50 nm were
nonuniform, and above 600 nm peel off
from the substrate. To determine the
nature of the growth and the structural
characteristics of CdI2 film, x-ray
diffraction measurement has been done
and compared with the ASTM cards,
using
(Philips
PW-1840
X-ray
diffractometer of = 1.54 from Cu-K).
Optical transmission measured using a
double beam spectrophotometer (Cecile
CE 7200 spectrophotometer, by Aquarius
Company).
Correlation between Thickness, Grain

Size and Optical Band Gap of CdI2 Film
3 Results and discussion

3-1 Structural Investigation:
The structural properties of the CdI2
films were studied using XRD
irrespective of the films thickness. The
XRD result shows that the films are
polycrystalline. Figure (1) shows
diffraction spectrum scan over a rang of
10 2 50,from which it is clear that
our X-ray diffraction data is in agreement with ASTM No.(12-574).Table
(1) summarize the calculated parameters for XRD. The total absence of (001),
(101),or(111) reflection, the high degree of orientation with the basal plane
parallel to substrate and c-axis normal to
the substrate plan can be seen as
indication of a good agreement with
earlier study[15].However, another less
intensity reflection plane(110) have been
observed with 250 nm thick films.
This indicates a slight misalignment
among the grains .We have determined
the average grain size from the full
width at half maximum (FWHM) of
the most intense peak using the Scherre
formula [16]:
A
.... (2)
GS =
cos
Where is the full width at half maximum (FWHM) of XRD peak appearing at the diffraction angle , A the
shape factor depends on the crystalline
shape, and generally it is 1. Fig. (2)
shows the average grain size as a
function of films thickness, from this
curve we could conclude the following
points:
a- For thickness less than 250 nm the
thickness have no influence on grain
size.
b- For thickness greater than 250 nm
the grain size increased with a ratio of
0.13.
By comparing this result with these of
Fig. (1) if is clear that such variation
with grain size is due to the prwdominated orientations. At thickness<250 nm
both planes (002),(004) are in compotation and by increasing deposition time
(increasing thickness) the plane (002)

become faster growth rate and become
longer where as slower growth rate (004)
are conserved.
3-2 Optical Properties
Optical transmition and absorption
spectra of various thickness films were
obtained and analyzed in wavelength from
350-900 nm at room temperature Fig.3
and Fig. 4. The absorption coefficient
was calculated by [17]:
A
.....(3)
= 2 . 303
t
Where A is the absorbance and t the film
thickness. The samples show a high
absorption coefficient ( > 105 cm-1 for <
400 nm, 104 cm-1 for > 400 nm).
The dependence of on h near the band
edge is shown in Fig.5. It is clear that the
value of increases with increasing
photon energy. In a crystalline or
Polycrystalline material both direct or
indirect optical transition is possible
depending on the band structure of the
material.In general absorption coefficient
is related to the photon energy by
following equation [17]:
h = A( h E g ) n
...... (4)
Where A is constant depending on

transition probability Eg is the band gap of
the material and n has different values
depending on the nature of the absorption
process.
The usual method of determining
energy gap is to plot a graph between ( h
) 1/n and h and look for that value of n
which gives best linear curve in the
absorption edge region. Plotting ( h ) 1/ n
versus h for CdI2 films of various
thickness shows that the best fit was
obtained for n =1/2, indicating a direct
type of allowed transition as shown in
Fig.6.The part of the optical absorption
data near the tail of the direct absorption
edge have to be replotted as (h) 1/2 vs h

to determine indirect gap as shown in

Fig.7.Table (2) summarizes the optical
direct and indirect band gap, average
grain size for CdI2 films with different
thickness. Our value of Eg(direct) of 3.6
eV determined for thicknesses 150nm
agrees well with the predicted value of
3.8 eV from band structure calculation
[9]. However, both type of band gaps
showed thickness dependence as shown
in table (2) which gives also the grain
size.
In general, thickness dependence of
band gap can a rise due to one or combined effect of (1) the change in barrier
height due to change in grain size in
polycrystalline films. (2) A large density of dislocation for thickness > 150
nm.
The decreasing of energy gaps with
grain size for CdI2 as shown in Fig.8.
However, both energy gaps show
thickness dependence as shown in Fig.9.
4. Conclusion
1. The optical absorption data indicate
a direct type of inter-band transition near
the absorption edge yielding a direct
optical energy gap varies continuously
from 2.9 eV to 3.6 eV.
2. Part of the optical data was fitted to
an indirect type of transition to
determine the indirect optical energy gap
varies continuously from 2 eV to 3.1 eV.
3. The direct and indirect band gap of
CdI2 films decreasing with film
thickness can be attributed to grain size
dependent grain boundary barrier height,
at least for film thickness > 150 nm.
4. The lattice parameter c of hexagonal
structured CdI2 films shows a wavy
dependence on film thickness in the rang
150 600 nm, the films show c-axis
alignment normal to substrate plan for
film thickness up to about 250 nm.
References
[1]. Hulliger F, Levy F and Reidel D
1976 in structural chemistry of layer
type
phases (Dordrecht, Holland:
Ed. Publishing Company) pp 31 -34 and
275
[2]. G. C. Trigunayat; Solid
State Ion. 48 (1991) 3.
[3]. P. Tyagi, A. G. Vedeshwar,
N. C. Mehra, Physica B 304 (2001)166.
[4]. P.Tyagi, A. G. Vedeshwar;
Bull. Mater. Sci. 24 (2001) 297.
[5]. P. Tyagi, A. G. Vedeshwar; Eur.
Phys. J. AP 19 (2002) 3.
[6]. I. Pollini, J. Thomas, R. Coehoorn,
C. Haas; Phys. Rev. B 33 (1986) 5747.
[7]. J. Bordas, J. Robertson, A.
Jakobsson; J. Phys. C: Solid State Phys.
11 (1978) 2607.
[8]. J. Robertson; J. Phys. C: Solid State
Phys. 12 (1979) 4753.
[9]. J. V. McCanny , R. H. Williams , R.
B. Murray , P. C. Kemeny ; J. Phys. C :
Solid State Phys. 10 (1977) 4255.

[10]. H. Nakagawa, T. Yamada, H.

Matsumoto, T. Hayashi; J. of the Phys.
Soc. of Jap. 56 (1987) 1185.
[11]. S. Kondo, H. Matsumoto; J. of the
Phys. Soc. of Jap. 50 (1981) 3047.
[12]. A. Nayak , G. L. Bahlla , B.
Kumar , G. C. Trignnyat ; Phys. Stat.
Sol. (b) 213 (1999) 487 .
[13]. K. Sreelatha, C. Venugopal, S. K.
Chaudhary, N. V. Unnikrishnan; Cryst
Res. Technol. 34(1999) 897.
[14]. S. Konda, T. Suzuki, T. Saito; J.
Phys. D 31(1998) 2733.
[15]. R. D. Bringans, W. Y. Liang; J.
Phys. C 14(1981) 1065.
[16]. B .D. Cullity and S. R. Stock,"
Elements of X-ray Diffraction",Third
edition Prentice-Hall in the United
States of America, 2001.
[17]. N. F. Mott, E. A. Davis 1979
Electronic Processes in Noncrystalline
materials (Oxford:Clarendon
Press) P. 27.

Table (1) analysis of the XRD study of CdI2 films
(hkl)
Thickness
d()
d ()
2
(nm)
Observed ASTM degree
150
250
450
600
6.77
3.46
2.30
6.75
3.475
2.30
6.828
3.42
3.233
2.284
2.119
2.024
6.828
3.42
3.233
2.284
2.119
6.84
3.42
2.28
6.84
3.42
2.28
6.84
3.42
3.24
2.28
2.122
2.024
6.84
3.42
3.24
2.28
2.122
13
25.7
39.2
13.1
25.6
39.1
12.95
25.97
27.55
39.4
42.6
44.7
12.95
25.97
27.55
39.4
24.6
Average
G.S.(nm)
(002)
(004)
(006)
(002)
(004)
(006)
(002)
(004)
(102)
(006)
(110)
(112)
(002)
(004)
(102)
(006)
(110)
110
113
144
180
Table (2) direct and indirect optical band gap, average grain
size of CdI2 films of different thickness
Thickness Eg(eV) Eg(eV) Average

(nm)
direct indirect G.S.(nm)
150
3.6
3.1
110
250
3.3
2.93
113
450
3.18
2.7
144
600
2.9
2.2
180

Figure 1: X-ray diffraction patterns and Miller indices of CdI2

films prepared with different thickness.
190
Average G.S. (nm)
180
170
160
150
140
130
120
110
100
0
100
200
300
400
500
600
Thickness (nm)
Figure 2: Variation of grain size with thickness of CdI2 films.
700

Figure 3: The optical transmission spectra for different thicknesses of CdI2 films.
Figure 4: The optical absorption spectra of CdI2 films of different thickness.

Figure 5: The absorption coefficient as a function of h for CdI2

films with different thickness.
Figure 6: Photon energy dependences of the absorption coefficient squared for CdI2
films with different thickness to determination of Eg (direct).

Figure 7: Shows ( h ) 1/2 versus h plot for the determination of Eg (indirect)

4.0
direct Eg
indirec Eg
Eg (eV)
3.5
3.0
2.5
2.0
1.5
100
120
140
160
180
Average G.S. (nm)

Figure 8: The grain size dependence of Eg for CdI2 films.
200

4.0
direct Eg
indirec Eg
Eg (eV)
3.5
3.0
2.5
2.0
1.5
100
200
300
400
500
600
Thickness (nm)
Figure 9: Thickness dependence of Eg for CdI2 films.
700

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Eng. & Tech. Journal,Vol.27, No.

Correlation between Thickness, Grain Size and

energy gap of 3.2 eV while the

* Applied Sciences Department, University of Technology / Baghdad

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Eng.& Tech. Journal ,Vol. 27, No.6, 2009

diation on poly type (002) oriented CdI2

Correlation between Thickness, Grain

3 Results and discussion

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Eng.& Tech. Journal ,Vol. 27, No.6, 2009

(increasing thickness) the plane (002)

Where A is constant depending on

Correlation between Thickness, Grain

to determine indirect gap as shown in

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Eng.& Tech. Journal ,Vol. 27, No.6, 2009

Correlation between Thickness, Grain

[10]. H. Nakagawa, T. Yamada, H.

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Eng.& Tech. Journal ,Vol. 27, No.6, 2009

Correlation between Thickness, Grain

Table (1) analysis of the XRD study of CdI2 films

Thickness Eg(eV) Eg(eV) Average

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Eng.& Tech. Journal ,Vol. 27, No.6, 2009

Correlation between Thickness, Grain

Figure 1: X-ray diffraction patterns and Miller indices of CdI2

Average G.S. (nm)

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Eng.& Tech. Journal ,Vol. 27, No.6, 2009

Correlation between Thickness, Grain

Figure 4: The optical absorption spectra of CdI2 films of different thickness.

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Eng.& Tech. Journal ,Vol. 27, No.6, 2009

Correlation between Thickness, Grain

Figure 5: The absorption coefficient as a function of h for CdI2

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Eng.& Tech. Journal ,Vol. 27, No.6, 2009

Correlation between Thickness, Grain

Figure 7: Shows ( h ) 1/2 versus h plot for the determination of Eg (indirect)

Average G.S. (nm)

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Eng.& Tech. Journal ,Vol. 27, No.6, 2009

Correlation between Thickness, Grain

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