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The Subject

No. of

The 28 Days Compressive

Strength of Portland Cement
in Iraqi And International
Optical properties of Mn203
Thin Films Using Chemical
Spray Pyrolysis Technique
Mohammed Baqir Twaij
Convenient Synthesis or 3,5
diamino Substituted 1,2,4
Najat J.AI-Obaydia
Mahmoud N.AI-Jibouri Thiadiazoles by oxidative
Mohammad G.Abid
Dimerization of Thioureas
Amer M.AL-Mahdawi
Suhad M.AL-Taee




AL-fath Journal, No.l5,2003

lsmhi, F.A
Habucation, N.F

Optical properties of Mn20 3 Thin Films Using

Chemical Spray Pyrolysis Technique
F.A. Ismhil

N.F. Habubi

Department of Physics- College of Education I

AL-Mustansiriya University

Thin film of Mn203 have been prepared using spray pyrolysis
technique . The effect on optical properties were studied , these
includes the absorbency optical energy gap for direct allowed
and forbidden band to band transition , our study on Mn 20 3 lead
us to know that Mn20 3 is a direct semiconductor;-

Recently there has been considerable inferable interest in
the development of new types of low cost solar absorption coatings

pyrolysis technique , this method has been proved to

interest in many applications , selective
be of great
surfaces for solar energy conversion , anti reflecting coatings and
electro luminescent devices can take advantage from this simple ,
cheap and convenient technique , This method is greatly used
nowadays for


AL-fath Journal , No.15,2003

Ismhi, F.A
Habucation , N.F

the preparation of many oxides and sulfides of metal and

semiconductors [ 1-5]
The oxides of the transition elements belong to special glass
of materials is that the (D) shell is incomplete . The optical
transmission of single oxides In the paramagnetic and anti
ferromagnetic states is reported by pratt [6] , the optical allowed
transition of Mn20 3 coatings is reported by Ahmed et .Al.[7].
The most relevant applications of manganese oxide coating is
to reduce the admission of solar heat through the glazin during
summer time and therefore reduce the air-conditioning cost .
We report in this paper the preparation of thin
polycrystalline Mn 20 3 film for the first time , detailed analysis of
optical data were carried out to gain new information .

Mn 20 3 films have been deposited using _spray pyrolysis
technique .The experimental arrangements is similar to that.
described previously [8,9] . A solution of 0.1 molarity Mn(N03)2,
in redistilled water is prepared , this solution was sprayed on
preheated borosilicate glass plate , it has been found that the
optimum conditions to obtain high quality film , transparent
,adherent ,strongly to glass and uniform thickness were :
i. Substrate temperature 350"C .
ii. Spraying rate 10 cm3/min.
iii. Distance between sprayer and substrate 30 1 em.
iv. Solution contains 7.17627 gin 250cm3 H 20.

lasted about 10 s followed by 5min wait to avoid

excessive cooling of hot substrate due to spraying , thin film
prepared with 'llifferent thickness calculated by using weighing
method and were in the range ( 0.33851-0.56418), and their
color was dark brown.
X-ray diffraction were used to distinguish the film structure
as show in fig (1), the interplanar spacing and intensity ratio were


found to be in good agreement with those of ASTM card for

polycrystalline y-Mn203.
The absorption and transmission spectra of these films were
recorded using Pye-Uincom SP/8800 in the range of (300-900) nm
and all measurements were carried at room temperature , the
measurements were repeated using a large number of films and
reproducible results were obtained , a simple computer program
were used to calculate the optical parameters .
Results and Discusssion
The absorption coefficient is calculated from the relation

........... (1)


is the difference in the absorption at each
wavelength of two thin. films of different thickness . The
phonon energy dependence of the optical absorption coefficient of
Mn203 is shown in fig(2) , it can be seen that the-absorption edge
is not so sharp , this may be related to the polycrystalline
structure of the coatings . _
As expected direct transition occur in the region of high
absorption a.> 103 cm- 1 , and indirect transition occur in the low
absorption region a.> 103 cm-1 , so Mn20 3 is a direct transition
material, using the assumption that the transition probability
becomes constant near the absorption edge,the variation of the
absorption coefficient with photon energy for direct allowed band
to band transition is of the form [7]:


2 (hf-Eg) = (LnT1-2) 2 ..... (2)

where is aconstant depending on the probabability of

transition . Ln T t-2 is the transmission of the first and the second
film respectively .
The absorption coefficient is calculated from the absorption
andtransmission spectrum and the result are the result are almost
identical , Fig (3) shows a plot of (Ln T 1_2)2 versus hf, the plot



shows straight line when extended to (Ln T 1_2) =0 giving the value
of Eg =2.25 0.05 eV for direct allowed .band to band transition.
The energy gap in the direct forbidden transition (kt=O) is
calculated from the relation [11]:
(aht) 213 .= a 0 (hf-Eg) ........ (3)
A satisfactory fit was obtained from (a ht) 213 as a function of
photon energy as shown in fig (4) extrapolation of the straight line
to (a ht) 213 =0
gives the band gap of the direct forbidden
transition Eg=1.85 0.05 eV. The variation of the absorption
cofficient with photon energy for direct transition is given by

Where n=2 for allowed indirect transition and n=3 for

forbidden indirect transition , E' g is the indirect band gap and Ep
the absorbed (+) or emitted (-) photon
,it can be clearly
seen from fig (5) and (6), the plots of (a ht) and (a ht) versus
hf , does not indicate any straight line portion intercepting the hf
axis suggesting the absence of indirect allowed transition .
Mn203 was prepared for the first time using spray pyrolysis
technique , and for our knowledge there is no publication have
been reported in this matter except for Mn 20 3 films [7]. The value
of the direct transition were calculated and found to be 2.81 eV.
The absorption coefficient is high and is of order 10 5 cm-1 ,
we finally conclude that Mn 20 3 is a direct semiconductor, since

of indirect transition were found .

1. A.K.Abass , Z.A.Ahmed and R.E. Tahir, Phys.Sta.Sol. (a)
97 ,234(1986).
2. N.F.Habubi , M.M.Radi, W.Z.Manookain, J.Math .Phys.
,13,(2) ,(1992) .



NF.Habubi , K.A. Mishjal , A.A. Hesen , J.of Education

College, No. 1, (1994).
A.K.Abass , N.H. Ahmed ,J .Phys. Chern .Solids, 47 ,143
R.H. Misho , W.A. Murad ,G.H. Fattahalla , Thin Solid
Films , 5, 169 (1988) .
G.W. Pratt and Roland Coelhs, Phys .Rev. 16,281 (1951).
Z.A. Ahmed, W.A. Taha, A.J. Buggaly, J.Math .Phys ., 13
,1 (1992).
O.P. Agnihotri , M.I. Mohamed , A.K. Abass and K.I.
Arshak, Solid Sate <:;ommn . 47, 195 (1983) .
A.K. Abass and E. M. Jaboori , Phys .Stat . Sol . (a),
116,k111(1989) .
A.K. Abass ,F.Y. M. Al.Ethan and R.H.Misho. Phys. Stat
.Sol . (a, 89,225 (1985)).
T.S. Moss," Optical properties of semiconductors", Butter
worths Sci . Publ ., Londin , 37 (1985) .


Ismhi, F.A
Habucation , N.F

AL-fath Journal , No.15,2003

Fig(J) XRD (Intensity versus 26).





- ,_

Absorption Coefticient versus Photon Energy .





lsmhi, F.A
_ Habucation , N.F

AL-fath Journal , No.l5,2003

- =







Fig(4) (n

versus Photon Energy.

--,.---,---!.:Fig(5) (a hf)""versus Photon Energy.





- - ; - - - . , . - - - -

Fig(6) (a hf)' J versus Photon Energy.