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DOI: 10.1515/msp-2015-0091
1 Department of Physics and Astronomy, King Saud University, Riyadh, Saudi Arabia
2 Mechanical Engineering Department, College of Engineering, King Saud University, Riyadh, Saudi Arabia
3 National Centre for Nanotechnology, Department of Metallurgy and Materials Engineering, Pakistan Institute of Engineering
and Applied Sciences (PIEAS), Islamabad 45650, Pakistan
4 Department of Physics, College of Science, Az Zulfi, Majmaah University, Saudi Arabia
We have investigated the influence of Ag doping on zinc oxide thin films. Pure and Ag doped, preferentially oriented
transparent zinc oxide thin films were prepared by sol gel technique on a glass substrate using diethyl amine as a stabilizer.
The X-ray diffraction analysis revealed that the films with hexagonal wurtzite type structure were polycrystalline in nature with
a preferred grain orientation in the h101i direction. The crystallite sizes decreased from 34 nm to 27 nm after silver doping.
Both photoluminescence and optical transmission measurements showed that the band gap increased after the Ag doping. The
structure and optical characterization studies clearly indicated the incorporation of Ag in ZnO. Hence, the observed increase in
the optical band gap and decrease in crystallite size can be directly attributed to the effect of Ag ion incorporation into the ZnO
lattice.
Keywords: Ag doped ZnO; sol gel; structure properties; optical band gap; defects study
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602 S YED M ANSOOR A LI et al.
growth of the thin films was controlled by the tem- substrates are shown in Fig. 1. All the peaks of
perature and heat treatment conditions [17, 18]. the ZnO thin films correspond to the peaks of stan-
Silver is the most interesting among the met- dard ZnO (JCPDS Card No. S6-314). For both the
als because of its remarkable chemical reactivity in samples, (100), (002) and (101) diffraction peaks
solution [21]. Therefore, it is very interesting to un- are observed. In the XRD pattern, the growth of
derstand the role of silver in a transparent conduct- ZnO crystallites along (101) direction shows a pref-
ing oxide ZnO matrix during sol-gel synthesis. In erential c-axis orientation. The doped films have
this paper we report the effect of silver doping on higher and sharper diffraction peaks indicating an
the crystallization behavior, microstructure proper- improvement in intensity with an increase in full
ties and optical properties of ZnO thin films pre- width at half maximum (FWHM) of all the peaks
pared by a sol-gel process. as compared to pure ZnO film. The spectra show
that the film has a polycrystalline structure, which
is typical of a hexagonal wurtzite [19, 20].
2. Experimental
The procedure for preparing pure and Ag-
doped ZnO thin films was as follows. First,
a 0.25 M solution of zinc acetate dehydrate
(Zn(CH3 COO)2 ·2H2 O, Baker, 99.9 %) was dis-
solved in ethanol under magnetic stirring. After
stirring the solution for about 20 min, 10 drops of
diethyl amine was added as a stabilizing agent and
the mixture was further stirred for an hour at 60 °C.
For Ag doping, the silver nitrate (AgNO3 , Aldrich,
99.8 %) was chosen as a doping source. The films
were deposited on a clean glass substrate by spin-
coating method. The spin coating speed and the de-
position time were 3000 rpm and 1 min, respec-
tively. After the spin coating process, the samples Fig. 1. XRD pattern of pure and Ag doped ZnO thin
were dried at 100 °C for 5 min to evaporate the films on glass substrate.
solvent and organic residuals. The process of spin
coating and subsequent pre-heating treatment was In order to obtain detailed information about the
repeated 10 times to obtain a desired thickness. At structure, the crystallite size D along the c-axis was
last, all the samples were annealed at 300 °C for an calculated according to the Scherrer equation [22]:
hour in air.
Crystallinity of the nanostructures was ana- 0.9λ
D= (1)
lyzed with a Bruker diffractometer (XRD) using β cos θ
the CuKα radiation (λ = 1.5406 Å). Optical trans- where D is the crystallite size, λ is the X-ray wave-
mission and reflectance of the thin films were length (λ = 1.5406 Å), β is the full width at half-
studied with a JASCO (V-670) spectrophotome- maximum (FWHM), and θ is the Bragg angle of
ter. The photoluminescence was recorded at room (002) peak. The dislocation density (δ), defined as
temperature. the length of dislocation lines per unit volume, is
estimated using the equation [23]:
3. Results and discussions δ= 1
D2
(2)
The XRD patterns of pure and Ag doped ZnO The lattice constants for the hexagonal structure of
thin film fabricated by sol-gel method on glass pure and doped thin films on glass substrates were
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Structural and optical properties of pure and Ag doped ZnO thin films. . . 603
4 h2 + hk + k2
1 1
= + 2 (3)
d2 3 a2 c
where a, c are the lattice constants and h, k, l are the
Miller indices of the planes, and d is the interplanar
spacing. The Zn–O bond length L is calculated by
the following equation [25]:
s 2
a2
1
L= + − u c2 (4)
3 2
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604 S YED M ANSOOR A LI et al.
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Structural and optical properties of pure and Ag doped ZnO thin films. . . 605
Table 1. Structural and optical parameters of pure and Ag doped ZnO thin films.
Crystallite Lattice constant (Å) Dislocation Bond length Strain Band gap Max. Refractive
Sample 14 2
size D (Å) a c δ × 10 (lines/m ) L (Å) ε (%) (eV) transmission (%) index n
ZnO 345 3.256 5.221 8.40 1.948 0.1150 3.217 88 1.40
Ag doped ZnO 280 3.259 5.228 12.75 1.951 0.2492 3.245 90 1.46
new broad peak at 385 nm developed in the pho- [14] F IDDES A.J.C., D UROSE K., B RINKMAN A.W., J.
toluminescence spectrum. These peaks in pure and Cryst. Growth, 159 (1996), 210.
[15] K AVAK H., T UZEMEN E.S., O ZBAYRAKTAR L.N.,
Ag doped ZnO films might be attributed to intrinsic
E SEN R., Vacuum, 83 (2009), 540.
defects, such as oxygen and zinc interstitials. [16] O HYAMA M., KOZUKA H., YOKO T., Thin Solid Films,
306 (1997), 78.
Acknowledgements [17] BAO D., G U H., K UANG A., Thin Solid Films, 312
The Authors would like to extend their sincere apprecia- (1998), 37.
tion to the Deanship of Scientific Research at King Saud Uni- [18] H AN H.C., K IM I.J., TAI W.P., K IM J.K., S HIM M.S.,
versity for its funding of this research through the Research S UH S.J., K IM Y.S., J. Korean Ceram. Soc., 40 (2003),
Group Project No. RGP-VPP-293. 1113.
[19] K IM I.J., H AN H.C., L EE C.S., SONG Y.J., TAI
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[13] NATSUME Y., S AKATA H., H IRAYAMA T., YANAGIDA Received 2014-12-31
H., J. Appl. Phys., 72 (9) (1992), 4203. Accepted 2015-06-12
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