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Photovoltaic technical conference THIN FILMS & ADVANCED SOLUTIONS 2011

Effect of indium doping on physical properties of nanocrystallized SnS Zinc


blend thin films grown by chemical bath deposition.
Meriem Reghima(a) , Anis Akkari (a,b)*, Michel Castagn (b) and Najoua Kamoun-Turki(a)

Facult des Sciences de Tunis

(a) Laboratoire de Physique de la Matire Condense, Facult des Sciences de Tunis El Manar, Tunisie (2092), Tunisia.
(b) Institut dElectronique du Sud, Unit Mixte de Recherche 5214 UM2-CNRS (ST2i) - Universit Montpellier 2 Place Eugne Bataillon Bat 21 cc083 F-34095 Montpellier Cedex 05 France.
Corresponding author. Tel: +21698347470; fax: +21671885073
E-mail adress n.kamoun@yahoo.fr

SnS:In thin films have been successfully prepared on Pyrex substrates using low cost chemical bath deposition (CBD) technique with different Indium-doped concentration (y = [In]/[Sn]= 4%, 6%, 8% and 10%). The structure, the surface
morphology and the optical properties of the SnS:In films were studied by X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscopy (AFM) and spectrophotometry measurements, respectively. To obtain a
thickness of the order of 308 nm for absorber material in solar cell devices, a system of multilayer have been prepared. It is found that the physical properties of tin sulphide are affected by Indium-doped concentration. In fact, X ray
diffraction study showed that the better cristallinity in zinc blend structure with preferential orientations (111)ZB and (200)ZB , was obtained for y equal to 6%. According to the AFM analysis we can remark that low average surface roughness
(RMS) value of SnS(ZB) thin film is obtained with In-doped concentrations equal to y = 6%, is about of 26 nm. Energy dispersive spectroscopy (EDS) showed the existence of In, S and Sn in the films. Optical analyses by means of transmission
T() and reflection R() measurements show 1.57 eV as a band gap value of SnS:In(6%). On the other hand, In doped tin sulphide exhibits a high absorption coefficient up to 2.5 106 cm-1 , indicating that SnS:In can be used as absorber thin
layer in photovoltaic structure such, SnS:In/In2S3:Al/SnO2 (F) and SnS/ZnS:/ SnO2 (F) where ZnS and In2S3 are chemically deposited in a previous works. In this study the hetero-junctions SnS/In2S3 (Al) and SnS/ZnS(In) are analyzed.

y=[In]/[Sn] FWHM d(111)


(%)
[2th.]

d(nm) dis (*1010 cm-2) nc (*1018 cm- 3) RMS


(nm)

0.227

3.345

45

4.9

2.5

31

0.227

3.356

45

4.9

3.2

26

0.252

3.359

38

6.9

4.4

48

10

0.252

3.355

38

6.9

4.7

33

ZB

Table 1 Variation of indium dopped SnS spaincing d(111)


, grain size d,
dislocation density dis , number of crystallites per unit surface area nc
for(111)ZB reticular plan and average surface roughness as a function of the
indium doping concentration y=[In]/[Sn] .

At first glance, this crystallographic investigation can be resumed to be the


best cristallinity of tin sulphide thin film system with grain size of about
using indium doping concentration equal to 6%.

Figure 1. pattern of doped thin layers system


obtained by for different y=[In]/[Sn]=4,6,8 and 10%
concentrations . Each system is formed by three
successive depositions runs which each one having
the same indium doping concentration and grown
for 4h .

Figure 2. 2D and 3D AFM topography of indium doped tin sulphide


multilayer formed by three successive thin films prepared by CBD for
y=[In]/[Sn] equal to 6%.

Y=[In]/[Sn] (%)

Figure 3. MEB (a) and SEM cross-section (b) images of


SnS:In multilayer system grown by CBD after three
successive depositions and for y=[In]/[Sn]=6%.

10

Sn (%)

77.77

73.59

75.56

76.41

S (%)

20.88

20.56

19.92

20.38

In (%)

1.36

5.85

4.52

3.21

In/Sn(%)

1.7

7.9

5.9

4.2

In the same line, SnS:In thin films


was also Chemically analyzed by
energy dispersive spectroscopy
(EDS), we selected several points
on the surface and the atomic
percentage of Sn, S, In and In/Sn,
values are gathered in table 2. It is
obvious shown that In element
exists.

Table 2. EDS analysis of indium doped tin sulphide multilayer thin films formed by three
successive thin layers, prepared by CBD for different y=[In]/[Sn] concentrations ratios.
The hetero-structure is obtained after four distinct steps which are:
1)Deposition by spray of the front contact layer SnO2:F thin film (of low
electrical resistivity and of high optical transmittance) on substrate.
2)Deposition by CBD of the n-type In2S3:Al or ZnS:In window layers [2,3].
3)Deposition by CBD of the SnS absorber material [1].
4)Painting of the electrical back contact for I(V) characteristics (silver dag).

Figure 4. Spectral shapes of transmission T()


and reflection R()
of In doped SnS(ZB) multilayer formed by three successive thin
layers prepared for y=[In]/[Sn]=4,6,8 and 10% .

Y=[In]/[Sn] (%)

Figure 5. Plot of versus photon energy (h)2/3


of indium doped tin sulphide multilayer formed by three
successive layers grown for different indium concentration
y=[In]/[Sn]=4,6,8 and 10% .

10

Figure 6. Schematic representation of fabricated Hetero-junction


structure: (1):SnO2:F, (2): In2S3:Al or ZnS:In, SnS and (4):Ag.
Figure 7. The characteristics in the dark and under
illumination of the elaborated hetero-junction

Photovoltaic parameter

1.76

1.62

1.57

1.59

1.59

Table 3. Optical band gap energy (Eg) of indium doped SnS (ZB) multilayer system grown by for different
y=[In]/[Sn] concentrations. Each system is formed by three successive depositions runs which each one has
the same indium doping concentration and grown for 4h .
Optical band gap energy of the SnS(ZB) thin film prepared for different indium doping concentration .y =[In]/[Sn] = 4%, 6%, 8% and 10%. are
calculated and summarized in table 3. It is clearly shown that the optical properties of tin sulphide are affected by In-doped concentration. In
fact, the optical band gap E. is decreased from 1.76 eV for undoped SnS thin film [1] to 1.57 eV for SnS:In thin film doped with indium
concentration ratio equal to y =[In]/[Sn] = 6%, this value is nearly equal to the theoretical optimum value of 1.50 eV for efficient light
absorption.

SnS(ZB)/ZnS/In(10%)

Imax (A)

5x10-5

Vmax (V)

0,13

4.8

9,98x10-5

8.48x10-6

Voc (mV)

211

10

Rs (K)

89x103

44x104

Rsh (K)

20x106

39x104

0,30

0,17

2,9x10-5

9x10-12

1,2x10-4

8.9x10-11

Isc (A)/cm2
Eg (V)

SnS(ZB)/In2S3:Al(40%)

FF

3x10-6

Is (A)
Iph (A)
Table 4. parameters of the hetero-junctions

Multilayer of doped SnS thin films have been prepared on Pyrex substrates by CBD technique. It is found, after three deposition runs, that the thickness of the film is relatively uniform with an average thickness close to 308 nm. Indium
doping of multideposited layer of SnS thin film affect the structural and optical properties of these layers. Indeed, for y =[In]/[Sn] equal to 6%, we obtained the better cristallinity with zinc blend structure and grain size equal to 45 nm, the
lower value of average surface roughness is obtained which is equal to 26 nm. Moreover, it is noted that in case of y = 6% tin sulphide exhibit a high absorption coefficient in the fort absorption region (> 2.5 10 cm-1) and the better optical
band gap Eg= 1.57 eV which is nearly equal to the optimum theoritical value of 1.50 eV for efficient light absorption. Therefore, the SnS:In thin films are suitable for absorber layers in solar cells. The fabrication of p n heterojunction
including this binary absorber such as SnS:In/ In2S3 (Al)/ SnO2 (F) and SnS:In/ZnS(In)/ SnO2 (F) where ZnS and In2S3 are chemically deposited in a previous works , could be tested as an alternative cell in comparison with CuInS2/ CdS ones.
Other physical characterizations especially electrical ones are in progress to reach better thin films with no higher resistivity by means of an appropriate heat treatment under controlled atmosphere.

[1] A. Akkari, C. Guasch, N. Kamoun-Turki, Journal of Alloys and Compounds 490 (2010) 180183.
[2] Anis Akkari, Cathy Guasch, Najoua Kamoun-Turki and Michel Castagne, journal of material science, uncorrected proof . (May 2011) .
[3] T. Ben Nasr, N. Kamoun-Turki, C. Guasch, Materials Chemistry and Physics 96 (2006) 8489.