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AUTHOR'S
PROOF
Article Title
Article Sub-Title
Journal Name
Silicon
Family Name
Particle
Given Name
Suffix
Fouda
A. N.
Organization
Division
Address
12
Organization
University of Hail
13
Division
Recruitment Department
14
Address
15
alynabieh@yahoo.com
16
Family Name
Marzook
17
Particle
18
Given Name
19
Suffix
10
11
20
Corresponding
Author
Author
M.
Organization
Suez University
21
Division
22
Address
23
None
24
Family Name
Abd El-Khalek
25
Particle
26
Given Name
27
28
Author
H. M.
Suffix
Organization
29
Division
30
Address
31
None
32
Family Name
Ahmed
33
34
35
Author
Particle
Given Name
Suffix
S.
AUTHOR'S PROOF
36
Organization
Suez University
37
Division
38
Address
39
None
40
Family Name
Eid
41
Particle
42
Given Name
43
44
Author
E. A.
Suffix
Organization
45
Division
46
Address
47
None
48
Family Name
El Basaty
49
Particle
50
Given Name
51
Suffix
52
Author
A. B.
Organization
Helwan University
53
Division
54
Address
55
None
56
Received
19 May 2015
57
Schedule
58
Revised
Accepted
28 December 2015
59
Abstract
60
Keywords
separated by ' - '
61
Foot note
information
AUTHOR'S PROOF
Silicon
DOI 10.1007/s12633-015-9399-z
ORIGINAL PAPER
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A. N. Fouda
alynabieh@yahoo.com
Q1
Q2
1 Introduction
24
25
U
N
C
O
R
R
EC
TE
D
PR
O
O
F
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AUTHOR'S PROOF
Silicon
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2 Experimental
Lead sulfide thin films have been synthesized on glass substrates 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
M) of lead acetate Pb(CH3 COO)2 , 2.5 ml (2 M) of sodium
hydroxide (NaOH), 1 ml (1 M) of triethanolamine (TEA)
C6 H15 NO3 , and 3 ml (1 M) of thiourea CH4 N2 S. At room
temperature (25 C), deionized water was added until the
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
the PbS formation on the glass substrate are given as:
[P b(CH3 COO)2 .3H2 O + 2NaOH ] P b(OH )2
Q3
79
(1)
:OH
+2NH3(g) S 2 + H2 O
[P b(T EA)n ] P b
2+
(2)
2.5 ml (0.5 M) of
lead acetate
+ n (T EA)
(4)
81
P b2+ + S 2 P bS
(5)
PR
O
O
F
57
U
N
C
O
R
R
EC
TE
D
56
2.5 ml (2 M) of
sodium hydroxide
1 ml (1 M) of triethanolamine
3 ml (1 M) of
thiourea
Water
added
After 1 hour
After 2 hours
4 glass plates
immersed
After 4 hours
After 3 hours
S4
S1
S2
S3
82
83
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86
87
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104
105
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Q4
AUTHOR'S PROOF
(311)
(222)
(220)
(200)
(111)
Silicon
S4
S3
S2
S1
20
30
40
50
60
D=
110
111
115
116
117
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120
121
122
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124
125
(6)
U
N
C
O
R
R
EC
TE
D
109
0.9
cos
PR
O
O
F
Fig. 2 X-ray diffraction patterns for the S1, S2, S3, and S4
108
114
70
2 (degree)
107
112
113
(S1)
(S3)
(S2)
(S4)
126
127
128
129
130
131
Q5
AUTHOR'S PROOF
Silicon
Sample
(h k l)
d(A)
a(A)
(PDF: 05-0592)
(111)
(200)
(220)
(311)
3.427
2.968
2.099
1.790
5.936
5.936
5.936
5.936
(111)
(200)
(220)
(311)
3.449
2.977
2.102
1.796
5.9746
5.9536
5.9465
5.9559
9.5
(111)
(200)
(220)
(311)
3.448
2.977
2.104
1.791
5.972
5.954
5.951
5.939
9.9
(111)
(200)
(220)
(311)
3.441
2.976
2.105
1.794
5.960
5.952
5.953
5.948
11.6
(111)
(200)
(220)
(311)
3.431
2.963
2.098
1.789
5.942
5.927
5.933
5.934
12.7
S1
S2
S3
132
133
134
135
U
N
C
O
R
R
EC
TE
D
S4
1
D2
(7)
(8)
D (nm)
1020 (lines/cm2 )
103
t1.1
t1.2
t1.3
t1.4
t1.5
1.108
3.78
t1.6
t1.7
t1.8
t1.9
1.02
3.63
t1.10
t1.11
t1.12
t1.13
0.743
3.12
t1.14
t1.15
PR
O
O
F
Q6
0.62
t1.16
t1.17
2.84
t1.18
t1.19
t1.20
t1.21
(9)
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143
AUTHOR'S PROOF
Silicon
EDX (S1)
U
N
C
O
R
R
EC
TE
D
PR
O
O
F
EDX (S2)
EDX (S3)
EDX (S4)
1
1
= ln
t
T
Fig. 5 EDX measurements for S1, S2, S3, and S4
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(10)
145
(11)
189 Q7
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191
AUTHOR'S PROOF
Silicon
Fig. 6 Variation of
transmittance and reflectance
with wavelength for S1, S2, S3,
and S4
100
60
1
2
3
4
80
50
40
R%
T%
60
40
30
20
20
0
1
2
3
4
10
400
600
800
1000
1200
400
600
[nm]
196
197
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199
200
201
202
203
204
205
206
16
2.0x10
16
1.8x10
16
1.6x10
S(1)
S(2)
S(3)
S(4)
16
1.4x10
1200
mh
r
2r 2 me
(12)
PR
O
O
F
195
1000
Where me and mh are the effective masses of the electron in the conduction band and the hole in the valence
band, respectively; r is the radius of the particle; and
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 Eg to lower
energies [27, 28].
The refractive index (n) is related to the optical reflectance (R), by the following relation [29]:
1
2
4R
1+R
2
+
n=
k
(13)
2
1R
(1 R)
U
N
C
O
R
R
EC
TE
D
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16
193
Where A is constant, h is Plancks constant, is the frequency of photon, and Eg is the energy gap. The variation
of (h)2 versus h (photon energy) is shown in Fig. 7. The
extrapolation of the curve is used to calculate the energy
gap [26]. As the thickness decreases, the calculated band
gap energy for the prepared samples ranges from 2.34 to
2.75 eV as tabulated in Table 2. The energy gap decreases
with increasing the film thickness. This is related to the
increment in the crystallite size with increasing the film
thickness. Although, the reported band gap energy of bulk
PbS ranges from 0.4 to 0.6 eV. The obtained higher values can be attributed to the quantum confinement effect.
After certain limiting size of particle size which associated
with the exciton Bohr radius, the space between band levels is changed. The Brus Model of nano-structure band gap
( h )
192
800
[nm]
k=
1.2x10
16
1.0x10
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
(14)
15
8.0x10
15
6.0x10
15
4.0x10
t2.1
Sample
Thickness (nm)
Eg (eV)
t2.2
S1
S2
S3
S4
47
83
105
133
2.75
2.61
2.44
2.34
t2.3
15
2.0x10
0.0
1.5
2.0
2.5
3.0
h [eV]
Fig. 7 Plot of (hv)2 vs. hv of S1, S2, S3, and S4
3.5
4.0
t2.4
t2.5
t2.6
AUTHOR'S PROOF
Silicon
8
1.4
6
5
4
3
2
1
2
3
4
1
400
600
800
226
227
228
229
230
231
232
233
234
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0.6
0.4
0.2
400
600
800
1000
1200
[nm]
2 = 2nk
60
8
1
2
3
4
50
1
2
3
4
7
6
40
30
4
3
20
2
10
0
1
400
600
800
[nm]
1000
1200
400
600
240
241
242
243
244
245
246
247
(15)
225
0.8
0.0
1200
U
N
C
O
R
R
EC
TE
D
224
1.0
[nm]
223
1000
1
2
3
4
1.2
PR
O
O
F
222
extinction coefficient ( )
800
[nm]
1000
1200
248
249
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251
252
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254
255
AUTHOR'S PROOF
Silicon
4 Conclusions
257
268
The effect of varying the film thickness on the structural, surface morphology and optical properties of PbS
films was investigated. The deposited films by chemical
bath deposition were polycrystalline with (200) preferred
crystal orientation. The thicker films exhibited bigger crystalline size which influences on the optical constants. The
purity of the films were confirmed by EDX measurements
and the surface morphology is changed from small spherical shaped grains to bigger agglomerated rod like grains
with increasing the film thickness. The change of refractive
index with wavelength reflects the possibility of usage in
optoelectronic devices.
269
References
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Tuning the synthesis of ternary lead chalcogenide quantum dots
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2. Ma W, Luther JM, Zheng H, Wu Y, Alivisatos AP (2009) Photovoltaic Devices Employing Ternary PbSx Se1x Nano-crystals.
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4. Patil SV, Deshmukh PR, Lokhande CD (2011) Fabrication
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Risbud SH, Lee HWH (1996) ZnO nanoparticles embedded in
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9. Ubale AU, Junghare AR, Wadibhasme NA, Daryapurkar AS,
Mankar RB, Sangawar VS (2007) Thickness dependent structural, electrical and optical properties of chemically deposited
nanopartical PbS thin films. Turk J Phys 31:279286
10. Kumar S, Sharma TP, Zulfequar M, Husain M (2003) Characterization of vacuum evaporated PbS thin films. Phys B 325:8
16
11. Preetha KC, Murali KV, Ragina AJ, Deepa K, Remadevi TL
(2012) Effect of cationic precursor pH on optical and transport
properties of SILAR deposited nano crystalline PbS thin films.
Curr Appl Phys 12:5359
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AUTHOR'S PROOF
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