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Article Title

Structural and Optical Characterization of Chemically Deposited PbS Thin Films

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Springer Science+Business Media Dordrecht 2016 (This will be the copyright line in the final PDF)

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Silicon

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Fouda

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Suez Canal University

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Physics Department, Faculty of Science

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41522, Ismailia, Egypt

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University of Hail

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Recruitment Department

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Hail 2440, KSA, Hail, Saudi Arabia

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alynabieh@yahoo.com

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Marzook

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Basic Science Department, Faculty of Petroleum and Mining Engineering 43721, Suez, Egypt

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Suez University

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Basic Science Department, Faculty of Petroleum and Mining Engineering 43721, Suez, Egypt

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Basic Science Department, Faculty of Industrial Education 11813, Cairo, Egypt

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Abstract

PbS thin films were deposited on glass substrates by chemical bath deposition method. The effect of varying the film thickness on the structural and optical properties has been investigated. XRD analysis reveals the crystallinity of the deposited PbS films with (200) preferred crystal orientation. Increasing the film thickness enhances the crystallinity of the films as well as decreases the strain and dislocation density. The surface morphology features were dramatically changed from small spherical grains to beads like shape. The absence of impurities in the deposited films were confirmed by energy dispersive x-ray spectrometry (EDX) measurements. The optical constants of the deposited films were calculated and a little decrease in the band gap energy was observed with increasing the film thickness.

60

Keywords separated by ' - '

PbS films - Chemical bath deposition - Surface morphology - XRD

61

Foot note

information

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JrnlID 12633 ArtID 9399 Proof#1 - 05/01/2016

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Silicon DOI 10.1007/s12633-015-9399-z

ORIGINAL

PAPER

ORIGINAL PAPER

2

3

4

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Structural and Optical Characterization of Chemically

Deposited PbS Thin Films

A. N. Fouda 1,2 · M. Marzook 3 · H. M. Abd El-Khalek 1 · S. Ahmed 3 · E. A. Eid 4 ·

A. B. El Basaty 5

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Received: 19 May 2015 / Accepted: 28 December 2015

© Springer Science+Business Media Dordrecht 2016

Abstract PbS thin films were deposited on glass substrates by

chemical bath deposition method. The effect of varying the

film thickness on the structural and optical properties has

been investigated. XRD analysis reveals the crystallinity of

the deposited PbS films with (200) preferred crystal orienta-

tion. Increasing the film thickness enhances the crystallinity

of the films as well as decreases the strain and dislocation

density. The surface morphology features were dramati-

cally changed from small spherical grains to beads like

shape. The absence of impurities in the deposited films were

confirmed by energy dispersive x-ray spectrometry (EDX)

measurements. The optical constants of the deposited films

were calculated and a little decrease in the band gap energy

was observed with increasing the film thickness.

Keywords PbS films · Chemical bath deposition · Surface

morphology · XRD

Q1

Q2

1

A. N. Fouda alynabieh@yahoo.com

Physics Department, Faculty of Science, Suez Canal University, 41522 Ismailia, Egypt

2 Recruitment Department, University of Hail, Hail 2440, KSA Hail Saudi Arabia

3 Basic Science Department, Faculty of Petroleum and Mining Engineering, Suez University, 43721 Suez, Egypt

4 Department of Basic Science, Higher Technological Institute, 10th of Ramadan City, Ramadan Egypt

5 Basic Science Department, Faculty of Industrial Education, Helwan University, 11813 Cairo, Egypt

1 Introduction

PbS is one of the most important IV-VI semiconductors with

narrow band gap of 0.41 eV at 300 K [1], and sufficiently

large Bohr radius of 18 nm [2]. This provides strong quan-

tum confinement of holes and electrons, regulating the band

gap value by controlling the crystallite size according to the

effective mass model [3]. PbS thin films have been a sub-

ject of extensive research due to their wide applications in

gas sensors [4], infrared radiation detectors [5, 6], optoelec-

tronics, solar cells, diode laser, etc [7, 8]. PbS thin films

are p-type semiconductors [9], and their direct band gap are

around 2.2 eV [9]. For these reasons, many research groups

have shown a great interest in the study and enhancement

of this material by various depositional processes. PbS thin

films can be deposited by different chemical and physi-

cal methods, such as vacuum evaporation [10], successive

ionic layer adsorption and reaction (SILAR) [11], electro-

deposition [12], chemical bath deposition (CBD) [13, 14],

etc. Among these, CBD is the most simple, low temperature requirement, low-cost, able to deposit thin films on different types of substrates, and convenient for large area deposition. CBD method is based on successive absorption and reaction

of species on the substrate surface from aqueous solution containing Pb2+ and S2. Film growth takes place by clus- ter mechanism or ion-by-ion. In this method, we can deposit a good adhesive films with different optical and structural properties by optimizing the bath temperature [15], reactant pH [16], reagent concentration [17], and deposition time [18]. A comparative study has been performed on proper- ties of PbS thin films grown by CBD, TEA was used as the complexing agent in one of the baths, and PbS films were prepared without Triethanolamine (TEA) [19]. Ubale et al.

prepared without Triethanolamine (TEA) [ 19 ]. Ubale et al. 24 25 26 27 28 29

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presented the synthesis of nanocrystalline PbS thin films

using CBD method where concentration of Pb 2+ and S 2

ions, temperature and pH were optimized to obtain good

quality of PbS thin films on glass [9].

In this work, PbS thin films were deposited by CBD with

different film thicknesses at room temperature. The structu-

ral and optical properties of the prepared films were stud-

ied by using X-ray diffraction (XRD), scanning electron

microscopy (SEM), and UV-VIS-NIR spectrophotometer.

2 Experimental

Lead sulfide thin films have been synthesized on glass sub-

strates using CBD method. The glass substrate was cleaned

using ultrasonic baths of acetone, dichloromethanol and

methanol. Then, we rinsed it with deionized water. CBD

solution was prepared by sequential addition of 2.5 ml (0.5

, 2.5 ml (2 M) of sodium

hydroxide (NaOH), 1 ml (1 M) of triethanolamine (TEA)

C

temperature (25

total volume of the solution reached 70 ml, and the pH was

11. The cleaned substrates were vertically immersed in 100

ml beaker, containing the CBD solution. The reactions of

C), deionized water was added until the

S. At room

M) of lead acetate Pb(CH 3 COO) 2

6

H

15

NO

3

, and 3 ml (1 M) of thiourea CH

4

N

2

the PbS formation on the glass substrate are given as:

[Pb(CH 3 COO) 2 .3H 2 O + 2NaOH ] → Pb(OH)

+2Na(CH 3 COO) + 3H 2 O

SC(NH 2 ) 2 + 2H 2 O :OH

−→ H 2 S (g) + CO 2(g)

+2NH 3(g)

:OH

−→ S 2 + H 2 O

2

(1)

(2)

2Pb(OH) 2 +2[C 6 H 15 NO 3 ] n 2[Pb(T EA) n ]+ 2H 2 O+O 2 (3)

 

80

[Pb(T EA) n ] → Pb 2+ + n (TEA)

(4)

 

81

Pb 2+ + S 2 PbS

(5)

The samples labeled S1, S2, S3 and S4 for deposition

82

times of 1h, 2h, 3h, and 4h respectively. The deposited

83

films were cleaned in an ultrasonic bath with deionized

84

water. The obtained films were homogeneous without color

85

degradation, and good adherent to the substrate. The color

86

of the films was light brown for S1 and going darker with

87

increasing the deposition time.

88

The structure and the average particle size of the

89

deposited lead sulfide films were determined by X-ray 90

diffraction (XRD) using a P-analytical X’PERT PRO Mate-

rials Research Diffractometer. Data were collected in the

2θ/θ geometry and were recorded in the range of 20 – 70

using Cu Kα

(Fig. 1).

The surface morphology of the PbS films was stud- 96

ied using a FEI QUANTA FEG 250 scanning electron 97

microscopy (SEM). Film thickness was measured using 98

interference microscopy and further confirmation was per-

formed from side-view of SEM images as shown in Fig. 4.

The thicknesses of S1, S2, S3, and S4 were 47, 83, 105, and

133 nm respectively.

95

94

93

92

91

˚

radiation (λ = 1.54 A) at 45 kV and 40 mA

99

100

101

102

The elemental composition of the films was determined

by the energy-dispersive X-ray analysis (EDX) using a FEI

QUANTA FEG 250. The measurements were extended to

optical characterizations in the wavelength range from 380

103

104

105

106

Fig. 1

describe the procedure PbS

films preparation

Schematic diagram

2.5 ml (0.5 M) of

2.5 ml (2 M) of

lead acetate

sodium hydroxide

of 2.5 ml (2 M) of lead acetate sodium hydroxide 1 ml (1 M) of tri-

1 ml (1 M) of tri-

1 ml (1 M) of tri- 3 ml (1 M) of thiourea

3 ml (1 M) of thiourea

ethanolamine

Water added
Water
added

Q4

After 1 hour After 4 hours 4 glass plates immersed After 2 hours After 3
After 1 hour
After 4 hours
4 glass plates
immersed
After 2 hours
After 3 hours
S1
S4
S2
S3

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S4 S3 S2 S1 20 30 40 50 60 70 INTENSITY (arb. units) (111) (200)
S4
S3
S2
S1
20
30
40
50
60
70
INTENSITY (arb. units)
(111)
(200)
(220)
(311)
(222)

Fig. 2

2θ (degree)

X-ray diffraction patterns for the S1, S2, S3, and S4

temperature are shown in Fig. 2. All the films are

polycrystalline with (200) preferred crystal orienta- 113

112

tion. The characteristic reflection peaks of PbS are observed

114

at 25.8 , 29.9 , 42.9 , and 50.9 for (111), (200), (220),

115

and (311) planes, respectively. An increment in the peak

116

intensity can be observed with increasing the film thickness

117

for S1, S2, and S3. In the case of S4, irregular trend was

118

observed and this can be attributed to the surface topogra-

119

phy of the sample as shown in Fig. 3. Similar behavior was

120

reported by other groups [17].

121

Generally with increasing the film thickness, an enhance-

122

ment in the crystallinity was established. The crystal- 123

lite size was calculated using the well-known Scherrer’s formula:

125

124

D =

0.9λ

β cos θ

(6)

107 to 1200 nm using a UV/VIS/NIR double beam spectropho-

108 tometer (JASCO V-570).

109 3 Results and Discussion

110 Representative XRD of PbS films with different film

111 thickness which deposited on glass substrates at room

Where

full width at half maximum of the peak (in radians),

the

λ

is

the

wavelength

(1.5406

˚

A),

β

is

and θ is the Bragg’s diffraction angle. PbS films ex-

hibited a remarkable increase in the crystallite size

with increasing the film thickness and it can be attributed to

the coalescence between neighboring islands during com-

pacted deposition and atomic mass transport. Moreover, the

Fig. 3

S1, S2, S3, and S4

SEM

photographs of the

(S1)

(S2)

(S3) (S4)
(S3)
(S4)

126

127

128

129

130

131

transport. Moreover, the Fig. 3 S1, S2, S3, and S4 SEM photographs of the (S1) (S2)

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Table 1

size

lattice strain values of the PbS

films

(hkl), d, a, crystallite

, Dislocation density, and

Sample

(h k l)

˚

d( A)

˚

a( A)

D (nm)

δ × 10 20 (lines/cm 2 )

ε × 10 3

t1.1

(PDF: 05-0592)

S1

S2

S3

S4

(111)

(200)

(220)

(311)

(111)

(200)

(220)

(311)

(111)

(200)

(220)

(311)

(111)

(200)

(220)

(311)

(111)

(200)

(220)

(311)

3.427

2.968

2.099

1.790

3.449

2.977

2.102

1.796

3.448

2.977

2.104

1.791

3.441

2.976

2.105

1.794

3.431

2.963

2.098

1.789

5.936

5.936

5.936

5.936

5.9746

5.9536

5.9465

5.9559

5.972

5.954

5.951

5.939

5.960

5.952

5.953

5.948

5.942

5.927

5.933

5.934

9.5

9.9

11.6

12.7

1.108

1.02

0.743

0.62

3.78

3.63

3.12

2.84

t1.2

t1.3

t1.4

t1.5

t1.6

t1.7

t1.8

t1.9

t1.10

t1.11

t1.12

t1.13

t1.14

t1.15

t1.16

t1.17

t1.18

t1.19

t1.20

t1.21

132

133

134

135

dislocation density can be derived from the crystallite size

using the formula [20]:

δ =

1

D 2

(7)

The lattice strain (ε) of S1, S2, S3, and S4 was calculated

from the relation [19]:

ε = β cos θ

4

(8)

The calculations were extended to the micro strain within

the samples to demonstrate the effect of dislocation density

on the film quality. The decrease in the strain with increas-

ing the film thickness reflects the relaxation of thicker

films [21].

The lattice parameter (a) of S1, S2, S3, and S4 was calcu-

lated for the cubic structure of PbS with inter-planer spacing

(d) using

1

d

2

=

h

2

+ k 2 + l 2

a 2

(9)

Fig. 4

electron microscopy (SEM) of S3, and S4

Cross-sectional scanning

+ l 2 a 2 (9) Fig. 4 electron microscopy (SEM) of S3, and S4 Cross-sectional
+ l 2 a 2 (9) Fig. 4 electron microscopy (SEM) of S3, and S4 Cross-sectional

136

137

138

139

140

141

142

143

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E DX (S1)

E DX (S2) E DX (S3) E DX (S4)
E
DX (S2)
E
DX (S3)
E
DX (S4)

Fig. 5

EDX measurements

for S1, S2, S3, and S4

144 For (200) plane, the calculated lattice parameters are 5.953, 5.954, 5.952, and 5.927 for S 1 , S2, S3, and S4

respectively, which are comparable to the bulk lattice 145

parameter (a = 5.936) [22]. The dependence of a, d, and

146

dislocation density on the film thickness are summarized in

147

Table 1.

148

Figure 4 shows cross sectional view of samples S3, and

149

S4 which used to confirm the previously measured thick-

150

ness by interference microscope. The surface morphology

151

of the deposited films are shown in Fig. 3. Isolated islands

152

with intermediate spaces can be seen. For S1, regularly

153

well-organized small grains can be observed. With increas-

154

ing the film thickness, beads like shape and agglomeration

155

of grains is distinguished. S2, S3 and S4 images evidence

156

that elongated grains are randomly oriented and coalescence

157

at different regions. With increasing the film thickness the

158

surface roughness increases due to the growth of isolated

159

islands together and agglomeration effect was observed 160

beside elongation of needle shapes. 161

Compositional analysis was determined by EDX (energy

162

dispersive spectrometry) measurements. Figure 5 shows the

EDX patterns of S1, S2, S3, and S4. The patterns dis-

play several mean peaks at different energy values, which

correspond to the Pb and S elements. It is observed that the

atomic or weight concentration of each element varies with

increasing the film thickness which can be attributed to the

rate of chemical reaction. It was clear that the composition

of the deposited films contains the elements of Pb and S

beside the peaks of glass. It is well known that the compo-

sition of glass consists of 75 % SiO 2 , sodium oxide Na 2 O,

sodium carbonate Na 2 CO 3 , calcium oxide CaO, and sev-

eral minor additives [23]. The transmittance and reflectance

spectra recorded for S1, S2, S3, and S4 are shown in

Fig. 6. The drop in the reflectance around the band edge

is related to the increase in transmission, and the observed

interference behavior is related to the film thickness and sur-

face morphology. The reflectance decreases with increasing

the film thickness in the spectra range from 400 to 1100

nm which can be attributed to the morphological fea- 181

tures. The grain size increases with increasing the film 182

thickness [20]. The transmission edge is shifted toward longer wave- length with increasing the film thickness. The band edge shift is related to the decrease in the direct band gap energy. The absorption coefficient was calculated using the following equation [23]:

188

187

186

185

184

183

180

179

178

177

176

175

174

173

172

171

170

169

168

167

166

165

164

163

α

= 1 ln T

t

1

(10)

Where t is the film thickness and T is the transmittance. The band gap energy of S1, S2, S3, and S4 were calculated using the Tauc equation [24, 25]:

αhυ = A(hυ E g ) 1/2

(11)

S4 were calculated using the Tauc equation [ 24 , 25 ]: αhυ = A(hυ −

189

190

191

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2

)

h

Fig. 6

transmittance and reflectance with wavelength for S1, S2, S3,

and S4

Variation of

100 60 1 2 80 3 50 4 40 60 30 40 20 1 20
100
60
1
2
80
3
50
4
40
60
30
40
20
1
20
2
10
3
4
0
0
400
600
800
1000
1200
400
600
800
1000
1200
λλ
[nm]
λ
[nm]
R%

192 Where A is constant, h is Planck’s constant, υis the fre-

is the energy gap. The variation

versus (photon energy) is shown in Fig. 7. The

195 extrapolation of the curve is used to calculate the energy

196 gap [26]. As the thickness decreases, the calculated band

197 gap energy for the prepared samples ranges from 2.34 to

198 2.75 eV as tabulated in Table 2. The energy gap decreases

199 with increasing the film thickness. This is related to the

200 increment in the crystallite size with increasing the film

201 thickness. Although, the reported band gap energy of bulk

202 PbS ranges from 0.4 to 0.6 eV. The obtained higher val-

203 ues can be attributed to the quantum confinement effect.

204 After certain limiting size of particle size which associated

205 with the exciton Bohr radius, the space between band lev-

206 els is changed. The Brus Model of nano-structure band gap

194 of (αhυ)

193 quency of photon, and E

g

2

2.0x10

1.8x10

16

16

1.6x10 16

1.4x10

16

1.2x10 16

1.8x10 1 6 1 6 1.6x10 1 6 1.4x10 1 6 1.2x10 1 6 1.0x10 1

1.0x10 16

8.0x101 6 1 6 1.6x10 1 6 1.4x10 1 6 1.2x10 1 6 1.0x10 1 6

15

6.0x10

15

4.0x10

2.0x10

15

15

0.0

S(1) S(2) S(3) S(4)
S(1)
S(2)
S(3)
S(4)

1.5

2.0

2.5

3.0

3.5

4.0

h

5 1 5 0.0 S(1) S(2) S(3) S(4) 1.5 2.0 2.5 3.0 3.5 4.0 h [eV]

[eV]

Fig. 7

Plot of (αhv) 2 vs. hv of S1, S2, S3, and S4

gives the relation between bulk band gap and nano-structure

band gap:

E g (nano) = E g (bulk) + h 2 π 2 2r 2

1

m

e

+

1

m

h 1.78e 2 ξr

(12)

207

208

and m h are the effective masses of the elec-

tron in the conduction band and the hole in the valence

band, respectively; r is the radius of the particle; and

ξ is the dielectric constant of PbS (value of 17.3). Due

to the quantum localization (i.e. the kinetic energy) of

the second term, Eg is shifted to higher energies. The

third term represents the screened Coulomb interaction

between holes and electrons, which shifts E g to lower

energies [27, 28].

The refractive index (n) is related to the optical reflec-

tance (R), by the following relation [29]:

Where m

e

209

210

211

212

213

214

215

216

217

218

219

1

n = 1 + R 1 R

Where (k) is the extinction coefficient which is related to

the absorption coefficient (α) and the wavelength (λ) by: 221

220

+

(1 R) 2 k 2

4R

2

(13)

k

=

αλ

4π

(14)

Table 2

Energy gap values of S1, S2, S3, and S4

t2.1

Sample

Thickness (nm)

E g (eV)

t2.2

S1

47

2.75

t2.3

S2

83

2.61

t2.4

S3

105

2.44

t2.5

S4

133

2.34

t2.6

t 2 . 3 S2 83 2.61 t 2 . 4 S3 105 2.44 t 2

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UNCORRECTED PROOF

Fig. 8

index (n) and extinction coefficient (k) with wavelength for S1, S2, S3, and S4

Variation of refractive

8 1.4 1 7 2 1.2 3 6 4 1.0 5 0.8 4 0.6 3
8
1.4
1
7
2
1.2
3
6
4
1.0
5
0.8
4
0.6
3
0.4
2
1
2
0.2
1
3
4
0
0.0
400
600
800
1000
1200
400
600
800
1000
1200
[nm]
λ
[nm]
λλ
)n(xednievitcarfer
e tniciffeocnoitcnitxe
()

222 The variation of refractive index (n) with λ is shown in

223 Fig. 8a. The retardation of light in the film is very high in the

224 NIR region and decays to relatively low rate in the visible

225 region. The n value of S1, S2, S3, and S4 extended from

226 2.1 to 6.8. The change of refractive index with wavelength

227 open the door to the usage in optoelectronic devices, since

228 the wave propagation is strongly influenced by the distribu-

229 tion of the refractive index. It is clear from the Figure that

230 the refractive index increases as the thickness decreases in

231 the visible region and it decreases as the thickness decreases

232 in the IR region except the smaller film thickness. The

233 scattering of light within the smaller thickness exhibited

234 different trend because of its smaller and uniform grain

235 distribution.

236 The extinction coefficient as a function of the inci-

237 dent wavelength is shown in Fig. 8b. From the figure, we

238 can notice that the extinction coefficient is related to the

239 absorption of light within the films. k values decrease with

increasing the film thickness, due to the increase of the

absorption with increasing the film thickness, which agrees

with previous reports [30, 31]. The spectra of extinction

coefficient for different thickness of S1, S2, S3, and S4

show a dominant peak around 380–416 nm as shown in

Fig. 8b.

The real (ε 1 ) and imaginary ε 2 ) parts of the dielectric

constant of the prepared films can be calculated from [32]:

(15)

ε 1 = n 2 k 2

The variation of these two parameters with wavelength is

shown in Fig. 9. The values of the real part (ε 1 ) increases

with wavelength while the imaginary part 2 ) of the dielec-

tric constant decreases with wavelength of all samples 251

240

241

242

243

244

245

246

247

ε 2 = 2nk

,

248

249

250

except S1. Since the values of the refractive index is larger

than k values, the behavior of ε 1 is similar to n. The variation

of absorption coefficient has a direct effect on the values

of ε 2 .

252

253

254

255

Fig. 9

and imaginary (ε 2 ) parts of dielectric constant with wavelength for S1, S2, S3, and

S4

Variation of the real (ε 1 )

60 8 1 1 7 2 2 50 3 3 4 6 4 40 5
60
8
1
1
7
2
2
50
3
3
4
6
4
40
5
30
4
3
20
2
10
1
0
0
400
600
800
1000
1200
400
600
800
1000
1200
[nm]
[nm]
1
2

AUTHOR'S PROOF

JrnlID 12633 ArtID 9399 Proof#1 - 05/01/2016

Silicon

256 4 Conclusions

257 The effect of varying the film thickness on the struc-

258 tural, surface morphology and optical properties of PbS

259 films was investigated. The deposited films by chemical

260 bath deposition were polycrystalline with (200) preferred

261 crystal orientation. The thicker films exhibited bigger crys-

262 talline size which influences on the optical constants. The

263 purity of the films were confirmed by EDX measurements

264 and the surface morphology is changed from small spher-

265 ical shaped grains to bigger agglomerated rod like grains

266 with increasing the film thickness. The change of refractive

267 index with wavelength reflects the possibility of usage in

268 optoelectronic devices.

chemically deposited at different temperatures. Thin Solid Films

310

441:104–110

311

14. Yang S, Wang S, Fung KK (2000) One-dimensional growth of

312

rock-salt PbS nanocrystals mediated by surfactant/polymer tem-

313

plates. Pure Appl Chem 72:119–126 314

15. Perez´ RG, Tellez´ GH, Rosas UP, Torres AM, Hernandez´ J, Tecor-

315

ralco LLC, Moreno OP (2013) Growth of PbS nanocrystals thin

316

films by chemical bath. J Mater Sci Eng 3:1–13

317

16. Carrillo-Castillo A, Aguirre-Tostado FS, Salasvillasenor A, Mejia

318

I, Gnade BE, Sotelo-Lerma M, quevedo-Lopez´ MA (2013) Effect

319

of chemical bath deposition parameters on the growth of PbS thin

320

films for TFTs applications. Chalcogenide Lett 10:105–111 321

17. Seghaier S, Kamoun N, Brini R, Amara AB (2006) Structural and

optical properties of PbS thin films deposited by chemical bath deposition. Mater Chem Phys 97:71–80

Gode¨

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¨

F, Guneri¨

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