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Synthesis and characterization of lead sulphide thin films from

ethanolamine (ETA) complexing agent chemical bath
To cite this article before publication: Fekadu Gashaw Hone et al 2018 Mater. Res. Express in press https://doi.org/10.1088/2053-1591/aaad3d

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Page 1 of 16 AUTHOR SUBMITTED MANUSCRIPT - MRX-105612.R2

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Synthesis and characterization of lead sulphide thin films from ethanolamine

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(ETA) complexing agent chemical bath
7 Fekadu Gashaw Honea* and F.B. Dejenea
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University of the Free State, Department of Physics (Qwa Qwa Campus), Phuthaditjhaba, South Africa
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12 * Corresponding author: fekeye@gmail.com
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15 Abstract:
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18 Polycrystalline lead sulphide (PbS) thin films were grown on glass substrates by chemical bath
19
deposition route using ethanolamine (ETA) as a complexing agent. The effects of ETA molar
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21 concentration on the structural, morphological, electrical and optical properties of lead sulphide
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thin films were thoroughly studied. The XRD analyses revealed that all the deposited thin films
were face center cubic crystal structure and their preferred orientations were varied along the
(111) and (200) planes. The XRD results further confirmed that ETA concentration had a
significant effects on the strain, average crystalline size and dislocation density of the deposited
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30 thin films. The SEM studies illustrated the evolution and transformation of surface morphology
31
as ETA molar concentration increased from 0.41 M to 1.64 M. The energy dispersive x-ray
32
33 analysis was used to verify the compositional elements of the deposited thin films. Optical
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35 spectroscopy investigation established that the band gap of the PbS thin films were reduced from
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37 0.98 eV to 0.68 eV as ETA concentration increased. The photoluminescence spectra showed a
38 well defined peak at 428 nm and shoulder around 468 nm for all PbS thin films. The electrical
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40 resistivity of the thin films found in the order of 103 Ωcm at room temprature and decreased as
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42 the ETA molar concentration was increased
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.
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47 .
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49 Key words: Lead sulphide, Chemical bath deposition, Ethanolamine, Resistivity, Thin film
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 AUTHOR SUBMITTED MANUSCRIPT - MRX-105612.R2 Page 2 of 16

1
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3 1. Introduction
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5 Currently there has been an increasing interest on variety of binary semiconductor thin films
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7 especially from the IV–VI groups due to their prospective applications in various optoelectronic
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devices. Lead sulphide (PbS) is an important π-π semiconductor material with direct band gap of

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10 0.41 eV at 300 K and a space group of 𝐹𝑚 3̅ 𝑚 [1]. Moreover, its absorption coefficient
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12 continuously increases from the infrared to the visible region [2]. Due to small effective mass of
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14 holes and electrons and a high dielectric constant; PbS thin films allows strong size-quantization
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effects. Hence, its optical band gap energy can be easily varied from the bulk value to 5.2 eV,

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17 exclusively by changing the material’s dimensionality [3, 4]. Nanocrystalline PbS thin films
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19 have been a theme of substantial research due to their scientific importance in crystalline and
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21 polycrystalline forms like infrared radiation detectors, infrared emitters, solar control coatings,
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gas sensors, diode laser, optical information storage, photodetectors, and LEDs [5-8]. Recently,
the importance in nanocrystalline PbS has been considerably increased due to its potential use in
solar cells and visible light sensors [9]. The properties of chemically deposited thin films depend
strongly on the growth key parameters like the bath temperature, deposition time, complexing
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29 agents, bath pH etc [10, 11]. Complexing agents usually added to the chemical bath to control
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31 the availability of the free cation through thermodynamic equilibrium. The concentration of the
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33 complexing agent is typically adjusted with the metal salt to attain a desired film property such
34
as surface roughness, adhesion and deposition rate [12]. Complexing agent also greatly
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36 influences the structural, electrical, morphological and optical properties of the thin films [13,
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38 14]. There are a lot of reporters available in the literature that shows PbS thin film deposited
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40 from different complexing agents such as ammonia, sodium hydroxide, potassium hydroxide,
41 triethanolamine, hydrazine, trisodium citrate, hexamine etc by chemical bath deposition (CBD)
42
43 method. Moreover, few sulphide thin films including CdS [15] and MnS [16] deposited by CBD
44
45 method using ETA as a complexing agents. However, no literature is available so far that
46
indicate PbS thin film is deposited from ethanolamine (ETA) bath as a complexing agent. Hence,
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48 in the present work we report deposition of PbS thin films by using ethanolamine (C2H7NO) as a
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50 complexing agent via CBD method. Moreover, attempt made to study the effects of
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52 ethanolamine molar concentration on the morphological, optical, electrical and structural
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properties of PbS thin films.
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Page 3 of 16 AUTHOR SUBMITTED MANUSCRIPT - MRX-105612.R2

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3 2. Experimental procedure and characterization of PbS thin films
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5 Lead sulphide thin films were deposited on well cleaned glass substrate by CBD method. CBD
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7 is one of the most suitable routes to produce uniform, adherent and good reproducibility thin
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films [17]. Lead nitrate (𝑃𝑏(𝑁𝑂3 )2 ), ethanolamine (𝐶2 𝐻7 𝑁𝑂), potassium hydroxide (𝐾𝑂𝐻)

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10 and thiourea (𝐶𝑆(𝑁𝐻2 )3 ) were used as reactive chemicals in the present study. All the chemicals
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12 were Sigma–Aldrich product and the percorces solutions were prepared in deionized water of
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14 resistivity 17.2 MΩ cm. The chemical bath was prepared using 10 ml (0.03 M) of Lead nitrate as
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Pb2+ source, 10 ml (0.125 M) thiourea as S2- source and ethanolamine used as complexing agent.

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17 Four differnt chemical baths were prepared by changing the molar concentration of ethanolamine
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19 from 0.41M to 1.64 M at the interval of 0.41 M. The pH of the baths was adjusted by adding
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21 very small amount of potassium hydroxide slution. Finally sufficient amount of deionized water
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was added to make the total volume of the bath 50 ml and the deposition carried out at a bath
temperature of 55 0C for 25 min. The prepared chemical bath solution was initially colorless then
it chang to gray as the deposition proceeded. The prepared films were smooth, specularly
reflective and gray in color. The structural analysis carried out by Bruker D8 advance
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29 diffractometer with CuKα (1.5406 Å) radiation at room temperature. Energy dispersive X-ray
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31 analysis (EDX) attached with a JEOL-JSM-7800F scanning electron microscope (SEM) used to
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33 study the elemental composition and surface morphology of the samples. The room temperature
34
photoluminescence (PL) measurements were carried out by F-7000 FL Spectrophotometer.
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36 Perkin Elmer Lambda 950 UV–Vis–NIR Spectrophotometer within the wavelength range of 250
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38 nm – 2000 nm was used to determine the optical band gap of the deposited thin films. The
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40 electrical conductivity and resistivity measurements were conducted by applying dc-two point
41 probe using silver as ohmic contacts.
42
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44 3. Results and discussion
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46
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47 3.1 Structural characterization

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49 Figure 1 shows the XRD profiles of PbS thin films for various ETA molar concentrations. The
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51
diffraction pattern confirmed that the prepared samples were FCC crystal structure (JCPDS Card
52 No: 078-1058, Galena). The XRD diffraction pattern (Fig.1) also exhibited distinct diffraction
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54 peaks matching to reflections from the (111), (200), (220), (311), (222) and (420) planes.
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5 1000 (111)
6 (200)
7 900
8 (220)
9 800 (311) (222)
(420) d) 1.64 M

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10
11 700
12
Intensity Count (A.U)

13 600
14 c) 1.23 M
500
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400
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18 300 b) 0.82 M
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20 200
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100

0
20 30 40
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2 theta (degree)

Fig. 1: The XRD diffractograms of PbS for varieous ETA molar concentration
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a) 0.41 M

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This advocates that, PbS phase is stable and its formation is not dependent on ETA molar
33 concentration. Interestingly, noticed that varying ETA concentration produced noticeable effects
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35 on the preferential orientations of the crystal. PbS films synthesized from 0.41 M and 0.82 M,
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37 shows a preferential orientation along the (200) plane but it was changed to the (111) plane for
38
1.23 M and 1.64. This may be an evidence of the crystallites growth along different preferential
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40 orientations depending on the molar concentrations of ethanolamine and favor the three
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42 dimensional growth of the deposited thin films. On the basis of the thermodynamics principle the
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44 surface energies related to various crystallographic planes are generally different thus the growth
45 rates on various facets are subjugated by the surface energy which might be the cause for
46
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47 preferential orientation variation [18]. Hence, the XRD result reveled that increasing the
48
49 concentration of ethanolamine may enhance the occurrence of variation of system total free
50
51
energy while the films are growing. The lattice parameters for deposited thin films were
52 calculated from Eq. 5 and the results are presented in Table 1.
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54 𝑎
(𝑑ℎ𝑘𝑙 ) = ℎ2 + 𝑘 2 + 𝑙 2 ..................................................................... 1
55 ℎ𝑘𝑙
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Page 5 of 16 AUTHOR SUBMITTED MANUSCRIPT - MRX-105612.R2

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3 From Table-1, it was noticed that the lattice parameter of the deposited PbS thin films are almost
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5 similar with the standard value. This suggested that the films grown on the glass slid without
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7 stress at the interface. Debye-Scherrer formula [18] applied to calculated the average crystalline
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size (D) from the (111) and (200) planes and found in the range of 35 nm to 41 nm. These

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10 values showed that D increased while the ETA concentration increased (see Table-1). Weight
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12 difference method was used to estimate the average film thickness and found in the range of 785
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14 nm to 1083 nm as ETA concentration increased to 1.64 M. Other structural parameters strain and
15
dislocation density was calculated from the formulas in Refs. [19, 20] and their results are
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17 systematically listed in Table-1.
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21 Table-1: XRD parameters and optical band gap of the PbS thin films
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ETA Conc.

0.41 M

0.82 M
Lattice constant (Å)

standard
5.936

5.936
calculated
5.933

5.938
D (nm)

35.89

37.12
anStrain (ε )
lines-2m-4

9.255 x10-3

8.617 x10-3
Dislocation
density (δ)
lines/ m2
7.763 x1014

7.257 x1014
Band gap
(eV)

0.98

0.90
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30 1.23 M 5.936 5.932 39.78 6.213 x10-3 6.319 x1014 0.78
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1.64 M 5.936 5.926 41.17 5.326 x10-3 5.899 x1014 0.68
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35 It was observed that the strain and dislocation density were reduced with ETA concentration (see
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Table -1). This may be attributed to an enhancement of crystallite size due to a decrease in the
38 occurrence of grain boundary during crystal growth [21].
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42 3.2. Compositional and morphology study
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44 3.2.1 Compositional analysis
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46 Figures 2 shows the representative EDX spectra of PbS films for 0.41 M and 1.64 M. Both the
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48 EDX spectra showes strong intense peaks from S and Pb elements (see Fig. 2) which confirem
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the formation of PbS thin films. It is good to mansion here that, the EDX results do not show
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51 any significant changes on the nature of the peak intensity with the variations of ETA molar
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20 Fig. 2: EDX spectra of PbS thin films for 0.41 M and 1.64 M ethanolamine concentration
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3.2.2 Morphology study
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High resolution FESEM micrographs of PbS thin films deposited from different ETA molar
concentration are illustrated in Fig.3. The PbS thin film deposited at 0.41 M ETA concentration
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(see Fig.3a) shows small nanocrystalline with different sizes are covers the entire substrate
30 uniformly. Besides, large, isolated and agglomerated clusters of spherically shaped grains were
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32 observed on some parts of the micrograph. This indicates that none uniform grain growth rate at
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34 this ETA concentration. The formation of such aggregate grains on the surface of thin film is a
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distinctive future of chemical bath deposition method. The formation of these aggregates may
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37 come either from nucleation around impurity molecules on the substrate surface or form the
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39 cluster-by-cluster growth mechanisms of CBD technique or both. Extremely compact and well
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41 adherent plate-like morphology of different sizes and shapes found at 0.82 M concentration (see
42 Fig.3b). Moreover, the deposited thin film covers the surface of the substrate homogeneously
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44 without any visible surface defects. As the ETA concentration increased to 1.23 M and 1.64 M
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46 (see Fig.3c and 3d), the grain sizes were noticeable increased, which is consistent with the XRD
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results. Few voids are observed on 1.23 M and 1.64 M ETA concentration. This may be due to
49 the shift of growth mechanism to cluster-by-cluster at relatively high ETA concentration which
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51 exhibit large grains and voids. It was noticed that increase in ETA concentration from 0.41 M to
52
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to a mixture of triangle (blue circle) and octahedral shapes (red circle). For face center cubic
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56 (fcc) phase of the PbS crystals generally nucleates as tetra-decahedron seeds, exposing six (1 0 0)
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Page 7 of 16 AUTHOR SUBMITTED MANUSCRIPT - MRX-105612.R2

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3 facets and eight (1 1 1) facets to minimize the total surface energy [22]. Hence, the final shape of
4

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5 the crystal determined due the competitive growth rate of the two facets. Thus, the different
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7 growth rates along the (111) and (200) plans during the film growth stage leads the formation of
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the mixture of triangular and octahedral PbS morphologies. Similar observation was reported by

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10 [1, 18]. This important futuer reveialed that variation of ETA concentration play significant
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12 effect to produce PbS thin films with different sizes and shapes.
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Fig. 3: High resolution SEM micrographs of PbS thin films for different ETA concentration
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3.3 Optical band gap determination
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51 Stern relation which is given by [19] used to estimate the optical band gap energy of the thin
52
films.
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54 𝑛
(𝐴ℎ𝑣)2 = [𝑘(ℎ𝑣 − 𝐸𝑔 )] .............................................................. 2
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 AUTHOR SUBMITTED MANUSCRIPT - MRX-105612.R2 Page 8 of 16

1
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3 where n is a constant either 4 for indirect transition or 1 for direct transition and k is a constant;
4

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5 n was taken the value 1 because PbS has direct transition [23]. Figure 4 displyed the Stern plot
6
7 of (𝐴ℎ𝑣)2 versus (ℎ𝑣) for PbS thin films at differnt ETA molar concentration. The intercept of
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9 the interpolation of the linear region of the (𝐴ℎ𝑣)2 versus (ℎ𝑣) plot with the x-axis gives the

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10 band gap of the thin films and the estimated values are tabulated in Table-1. The films have a
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12 steep optical absorption feature (see Fig.4), which shows good homogeneity in the shape and size
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14 of the grains near the band edge [24]. The optical band gap values are found to vary from 0.68
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eV to 0.98 eV with increasing ETA concentration (see Fig. 4). This result verified that band gap

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17 was decreased when ETA concentration was increased. This trend gives the opportunity of band
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19 gap engineering of chemically synthesized PbS films by varie ETA concentration. The observed
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21 variation of optical band gap ascribed to the change of microstrain, crystallite size and
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5
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dislocation density of the samples with complexing agent molar concentration [25].
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29 4
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32 0.41 M
0.82 M
33 3
1.23 M
2

34
(Ahv) (eV)

1.64 M
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2

36 2
37
38
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39 1
40
41
42
43 0
0.50 0.75 1.00 1.25 1.50
44
Photonenergy (eV)
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46
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48 Fig.4: (𝐴ℎ𝑣)2 vs photonenergy (ℎ𝑣) plot of PbS thin films for various ETA concentration
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51 The band gap tunability of the thin films having larger crystallite sizes beyond the quantum
52
confinement regime may have different mechanisms [26]. For instant defects like grain
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54 boundaries, interstitials, vacancies etc. may act as trap centers and influence the optical
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56 absorption [27].
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3 3.4 Photoluminescence studies
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6 Lead sulphide thin films photoluminescence (PL) study carried out at excitation wavelength of
7
8 390 nm and the emission spectra are presented in Fig. 5. The PbS thin films PL spectra showed a
9 sharp defined peak at 428 nm and shoulder at 468 nm. The intense UV emission peak at 428 nm

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11 may be due to the direct transition from the valence to conduction band [28]. The small emission
12
13 bands at 468 nm ascribed by trapped electrons transition from the donor level to the valence band
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15
[29, 30]. The PL peak intensity increment was observed while ETA concentration decreased
16 which might be due to the passivation of the surface vacancies and non-radiative recombination

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17
18 sites [28]. Several research results also verified that the luminescence intensity depends on the
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20 crystalline size. The materials with smaller crystallites size showed higher luminescence
21
intensity compared to the larger crystallites [31].
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140

120
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Ext @ 390nm
dM
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30 100
31
0.41 M
32
Intencity Count (a.u)

0.82 M
33 80
1.23 M
34 1.64 M
35 60
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38 40
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40 20
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43 0
44 425 450 475 500 525 550 575 600 625
45 Wave length (nm)
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Fig. 5: PL emission spectrum of PbS thin films for various ETA concentration
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52 In the preasent study ETA concentration and the crystalline size has direct relation. As the
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54 crystalline size decreases the amount of ions quickly increases on the surface of the thin film.
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3 Moreover, the rate of carrier recombination increases as the size decrease due to the increase in
4

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5 overlap between the electron and hole wave functions [32] which leads PL intensity increment.
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7 From the PL figure it is observed that the peaks of near band edge transition for all samples
8
9
occurred at shorter wavelengths about 428 nm however the samples have smaller band gaps. We

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10 anticipated that his discrepancy occurred since the PL emissions are produced due to surface trap
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12 states [18, 33] wich caused by dangling bonds or unpassivated surface atoms. Such discrepancy
13
14 have been reported by several researchers which suggest more comprehensive investigation still
15
needed for PbS compound. Kaci et al. [34] observed an intense and broadband emission for PbS
16

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17 thin film at excitation of 230 nm. The broad emission peaks were at 367, 386, 411, 448, 475 and
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19 533 nm. T. Tohidi et al. [18] also reported a broadband emission for PbS thin film prepared at
20
21 differ deposition time and they found two emission peaks at 351 nm and 451 nm with an
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excitation of 320 nm. Pawar et al. [22] also reported emission peaks at 393, 405 and 460 nm with
an excitation wavelength of 416 nm for PbS samples. PL processes are very complicated and can
be strongly affected by factors such as grain size, excitation energy and type of impurity in
materials [32].
dM
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30
31 3.5 Conductivity and resistivity measurement
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33 The effect of ETA molar concentration on electrical conductivity (σ) and resistivity (ρ) of PbS
34
thin films were investigeted by applying dc-two point probe method under dark condution. The
35
36 resistivity measurements of PbS thin films was conducted after confirming the ohmic behavior of
37
38 silver contacts in the temperature range of 300 K to 400 K. The plot of ln ρ with reciprocal of
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40 temperature, (1/T) × 103 (See Fig.6) shows that the resistivity values are decreased with
41 increasing temperature indicating the semiconducting nature of the thin films [35]. It is also
42
43 observed from the figure that the resistivity decreased as ETA molar concentration increased.
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45 This behavior may be atributed to an increase in mobility due to increasing crystallite size with
46
ETA molar concentration [36]. The experimental data also verified that a better conductivity
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48 (≈1.58 x 10-4) was observed for PbS thin film deposited from 1.64 M ETA molar concentration
49
50 (See Table -2 and Fig.6). These properties will make the deposited PbS thin films appropriate for
51
52 various optoelectronic device applications. The variations of conductivity and resisitivity with
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53 crystalline size is presented in Fig.6.

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5 8.85
6 8.80 0.41 M
7 0.82 M LTR
8.75
8 1.23 M
1.64 M
9 8.70

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10 8.65
11
ln() (ohm.cm)

8.60
12
8.55
13
14 8.50 HTR

15 8.45
16

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8.40
17
8.35
18
19 8.30

20 2.5 2.6 2.7 2.8 2.9 3.0 3.1 3.2 3.3

21 1000/T(K )
-1

22
23
24
25
26
27
28
Fig.6: Relation between ln ρ and the reciprocal of the absolute temperature (1000/T) of PbS thin
films for various ETA molar concentration an
dM
29 6.75
30 1.55
31 6.70
32 1.54
33
-1
Conductivity x10 (ohm.cm)
34 6.65
Resisitivity x 10 (ohm.cm)

1.53
35
36
-4

6.60 1.52
37
3

38
1.51
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39 6.55

40
1.50
41 6.50
42
43 1.49
6.45
44
45 1.48
36 37 38 39 40 41
46
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47 Crystalline size (nm)

48
49
50 Fig. 7: Variations of conductivity and resistivity with crystalline size
51
52
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53 From Fig.7 it is observed that conductivity has a direct relation with crystalline size while
54
55 inverse relation with resisitivity. Relatively high resistivity value founds at 0.41 M ETA molar
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3 concentration may be due to its poor crystallinity which indicates the presence of few atomic
4

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5 layers of disordered atoms [37]. Improvement in crystallinity reduces the resistivity of PbS thin
6
7 films due to reduced grain boundary scattering. Since the conductivity (σ) is inversely
8
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proportional to the electron scattering frequency, the conductivity increases with increasing

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10 crystalline size [38]. The results found in the preseant study are well compareble with the
11
12 pervious reports [39, 40]. It is also good to point out here that surface trap states might have
13
14 contribution for the variations of electrical conductivity and resistivity. From Fig.6 it is observed
15
that the plot (ln ρ) versus (1000/T), has two different straight lines with distinct slopes, first in
16

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17 the higher temperature range (HTR) and second in the lower temperature range (LTR). Each
18
19 region obeys a different conduction mechanisms dominating at specific temperature intervals.
20
21 The slope of these line leads to determine the thermal activation energy (Ea) in that region. The
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28
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first region HTR, which is known as extrinsic semiconductors, extends from 328 K to 335 K.
The density of carriers in this region is equal to that of intrinsic carriers. The transition here
depends on two parameters; the temperature of the sample and the lattice vibrations. The
temperature increases the number of carriers, and consequently, it leads to increase the
dM
29 conductivity. On the other hand, the lattice vibration creates phonons, which produce electron-
30
31 phonon interaction. This interaction causes encumbering for electrons, so electrons need more
32
33 energy to be activated. This interprets the increasing of activation energy values of the first
34
region [41]. The second region starting from room temperature to 328 K is defined as LTR. It is
35
36 identified as an extrinsic conductivity of semiconductor due to the ionization of impurity atoms.
37
38 At the LTR, the conduction attributed to the thermally assisted hopping of carriers between
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39
40 localized states closes to the Fermi level [42]. The estimated activation energies are tabulated in
41 table-2 and the average activation energies for HTR and LTR are approximately 0.624 eV and
42
43 0.436 eV respectively.
44
45 Table-2: Electrica parameters of PbS thin films for various ETA molar concentration
46 ETA RT Conductivity RT Resisitivity HTR Activation LTR Activation
(Ω Cm)-1 (Ω Cm)
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47 Conc. energy (eV) energy (eV)

48 0.41 M 1.492 x10-4 6.703 x 103 0.651 0.485
49
50 0.82 M 1.525 x10-4 6. 558 x 103 0.635 0.450
51
1.23 M 1.548 x 10-4 6.460 x 103 0.618 0.423
52
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53
1.64 M 1.582 x 10-4 6.320 x 103 0.592 0.386
54
55
56 NB: RT- room temprature, HTR-high temprature region and LTR-low temprature region
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3 From table-2 it is also observed that the activation energy reduced with ETA molar
4

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5 concentration for the two regions this may be due to an improvement of the electrical
6
7 conductivity of the deposited PbS thin films with ETA molar concentration. The decrease in
8
9
activation energy also reflects in the decrease in the band gap of the thin films which is

cri
10 consistent with the results found from optical band gap measurements however there is a
11
12 variation in the estimated values. The above results confirmed that molar concentration of
13
14 complexing agent plays a vital role in the electrical property of the PbS film in present study.
15
16

us
17 4. Conclusion
18
19 Lead sulphide thin films were successfully synthesized using etanolamine as a complexing agent
20
21 using CBD route at 55 0C deposition temperature on silica glass substrates. The present study
22
23
24
25
26
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28
an
confirmed that ETA molar concentration strongly influenced the morphological, structural,
electrical and optical properties of PbS thin films. The XRD results verified that the crystalline
size showed an increasing pattern while dislocation density and strain showed a decreasing
fashion with ETA molar concentration. The EDX analyses established the presence of Pb and S
dM
29 elements in all deposited PbS thin films regardless of ETA molar concentration. The SEM
30
31 studies showed that variation of the complexing agent concentration leads to the morphological
32
33 evolution and transformation from plate-like morphology to a mixture of triangle and octahedral
34
35
shapes. The optical investigations verified that the PbS thin films deposited from ETA
36 complexing agent shows direct band gap transition and the estimated band gap reduced from
37
38 0.98 eV to 0.68 eV when ETA concentration increased to 1.64 M. The photoluminescence
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39
40 intensity is inversely proportional to ETA molar concentration while the electrical conductivity
41
had direct relation. The electrical property study showed that the electrical resistivity decreased
42
43 as ETA molar concentration increased from 0.41 M to 1.64 M. It was also found that PbS thin
44
45 films have two different temperature regions which obey two distinct conduction mechanisms.
46
The estimated average activation energies for HTR and LTR are 0.624 eV and 0.436 eV
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47
48 respectively. All the above results supports that using ethanolanine as complexing agent provide
49
50 another set of deposition condition for the growth of quality PbS thin films by CBD route.
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1
2
3 Acknowledgements
4

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5 Prof. H. C Swart and Prof R. Kroon acknowledged by the authors for supporting us with the
6
7 characterization equipments. The authors also thankful to P. P. Mokoena for EDX and SEM
8
9
measurements.

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