THE OPTICAL PROPERTIES OF THE POLYMER-CAPPED ZnS:Mn NANO THIN FILMS

Tran Minh Thi(a), Pham Van Ben(b), Nguyen Minh Vuong(c)

(a)
Faculty of Physics, Hanoi National University of Education, Vietnam
(b)
Faculty of Physics, National University of Hanoi, Vietnam
(c)
Laboratory of center, Quy Nhon University, Vietnam
Abstract:
The ZnS:Mn nanopowder and the polyvinyl alcohol (PVA)-capped ZnS:Mn thin films were prepered by wet chemical process and dip-coating method.
The microstructure of samples was investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the prepared
samples were the Sphalerite structure with average particle size about 3 nm.
The X ray diffraction spectra shown that PVA does not affect the microstructure of ZnS powder. The optical properties of samples were studied by
measuring the absorption and photoluminescence spectra in the wavelength range from 300 nm to 900 nm at room temperature. The direct band gap of PVA-
capped Mn doped ZnS nanocrystalline thin films were calculated for different PVA concentration in the samples. The values of direct band gap is about 3.75 eV.
The time-resolved-luminescence spectra and fluorescence lifetime of polymer-capped ZnS:Cu nanocrystalline thin films were also investigated. The results
allow us to explain their optical properties by quantum confinement effect of ZnS nanoparticles in the polymer PVA matrix [4][6].

• Introduction • K is a constant
K ( hν − E g )
n
2

The direct band gap of nano-materials may be controled by α= (1) • Eg is the direct band gap
doping, polymer coating and change of preparing conditions [1][2]. hν
• n = 1 for direct band gap
Polymer also has a role as the protected environment for ZnS semiconductor
nanoparticles. The optical propertiers of ZnS nanoparticles change  The crystallites of size could be determined using the relation
considerably when dispersing them into polymer matrix with optimal given below [4][6]:
concentration. Eg (bulk) = 3.6 (eV)
me*mh*
In this paper we report results on the optical properties of h 2
1,8e 2 µ= *
∆ E g = E g ( film) − E g (bulk ) = − (2) me + mh *
polymer-capped 9% Mn doped ZnS thin film with different PVA
concentrations. The study on influence of PVA concentration to 8µ r 2
εr m = 0,34mo , m = 0,24mo
*
e
*
h

luminescence spectra, grain size and direct band gap of this film is also m0 is the mass of free electron
presented
 From (1) equation and Fig. 3, we can calculete the direct band gap
II- Experiments of the M-PVA2, M-PVA4 and M-PVA5 samples. From (2) equation, We
The high pure chemical solutions were used such as: first solution
calculated the crystallites of size for this thin films.
was Zn(CH3COO)2.2H2O 0.1M, second solution was Mn(CH3COO)2.4H2O.  The calculated results were given in table 1 .
0.1M and third solution was Na2S.9H2O. 0.1M. Catalysis was CH3OH:H2O
Table 1: The direct band gap and the crystallites of size of
for first and second solutions (ratio 1:1). Produce polymer-capped Mn M-PVA2, M- PVA4, M- PVA5 samples
doped ZnS nanocrystalline thin films with different PVA concentration:
Thin film M-PVA2 M-PVA4 M-PVA5
First solution and second were mixed with appropriate ratio. Then PVA
amount of 1g, 2g, 4g, 5g was disolved in 100 ml of first and second Eg(eV) 3.86 3.77 3.73
mixed solution. The mixed solution with PVA heated at 80oC, then r(nm) 3.9 5.5 7.4
decrease to 300K. The third solution was added drop by drop in a ⇒ The results show that the values Eg decreased and the crystal
reaction vessel.
The PVA-capped Mn doped ZnS thin films were produced by spin- size increased when PVA concentration increases.
coating method in glass substrate with centrifugation speed 3000 rpm. ⇒ The results show M-PVA2 thin film is best with Eg = 3.86 eV and
III- Result and discussion α

 The 9% Mn doped ZnS nano-powder was analysed by X-ray r = 3.9 nm.

I PL = A.( I EX ) n diffraction (XRD) in Fig 1. The analysed results show that :
- Samples have Sphalerite structure. Lattice constant a = 5.4 Å.
- The diffraction 3 peaks: (111), (220), (311).
- The crystallites of size is about 3 nm by Scherrer formula.

Fig. 1: The XRD of ZnS sample (a)
and 9%Mn doped ZnS sample (b)
Fig. 2 is the SEM of M-PVA4 thin film.
- Grain size about 100 nm.
- That is the polymer in sphere form which coated outside
the ZnS:Mn nano- particles .
3.1- Absorption and PL spectra
Fig. 5: The PL spectra of M-PVA2 sample at 300K Fig. 6: The dependent of Ln(IPL ) on the Ln(Iex)
with the exciting wavelengh of 325nm and different of M-PVA2 sample
exciting power density
Fig. 5 presents the PL spectra of the M-PVA2 thin film with the
exciting wavelengh of 325nm and different exciting power density.
Fig. 2: The SEM image of M-PVA4 thin film The maximum positions of the D1, D2, D3 bands were nearly not
changed when the power density increased from 0,13 W/cm2 to 0,64
W/cm2. But their intensity changed as following law:
I PL = A.( I EX ) n
with n ≈ 0,7 (Fig. 6).
3.2. The time-resolved-luminescence spectra and fluorescence
lifetime of M-PVA2 thin film
6000
D1 a M-PVA2
b M-PVA4
5000
c M-PVA5

4000
Intensity(a.u)

3000
D2
a
2000
b D3
c
1000

Fig. 7: the time-resolved-luminescence spectra Fig. 8: The decreasing of photoluminescence

0
300 400 500 600 700 800 of the green band at 300 K with 337 nm exciting of M-PVA2 thin film at wavelength 450 at 300
Wavelength(nm) K with exciting wavelength of 337nm.
wavelength for M-PVA2
Fig. 3: The absorption spectra of M- PVA2M- ⇒ Fig.7. The peaks of band shifted towards the lower energy and
Fig. 4: The spectra of thin films with exciting
PVA4 and M-PVA5 thin films wavelength 325nm and 0.32W/cm2
their intensity decreased (about 5 times) when the delay time
 Fig. 3 presents the absorption spectra of the M-PVA2, M-PVA4 and increase from 60 ns to 114 ns. It is the typical characteristic of the
M-PVA5 thin films. The relation between absorption coefficient and donor-acceptor emission recombination.
energy of photon can be presented by following equation [3][4][6]: ⇒ Fig.8. The luminescence lifetime about 22 ns at wavelength 450
nm.
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