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An insight into optical properties of Pb:CdS system (A Theoretical Study)

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Page 1 of 24 AUTHOR SUBMITTED MANUSCRIPT - MRX-112329.R2

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4 An Insight into Optical Properties of Pb:CdS system (A Theoretical

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5 Study)
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9 M. Junaid Iqbal Khan*, Zarfishan Kanwal*, M. Nauman Usmani*, M. Zeeshan*, Masood Yousaf$

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11 *
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Laboratory of Theoretical and Experimental Physics, Department of Physics, Bahauddin
13 Zakariya University, Multan, 60800, Pakistan.
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15 Department of Physics, Division of Science and Technology, University of Education,
16 Township, Lahore, 54770, Pakistan.

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Email: drjunaid.iqbalkhan@bzu.edu.pk
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20 Cell: +923006889132
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Abstract

In current work, we explored optical properties of Pb doped CdS system by employing PBE-
GGA approximation. To accomplish computational work, we supposed various supercell
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30 configurations and in these supercells, Cd atoms were substituted by Pb atoms. It was found that
31 by varying supercell configurations, optical properties of Pb doped CdS system were changed.
32
33 The study was performed using Wien2K code by employing density functional theory.
34
35 Calculated data for optical absorption in the case of 1.56% Pb concentration (~ 2 × 2 × 2
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37
supercell) showed redshift as compared to pure CdS while for 6.25% (~ 1 × 1 × 2 supercell) and
38 3.12% (~ 1 × 2 × 2 supercell) Pb concentrations, it showed a blueshift. Moreover, optical
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40 absorption increases in visible region but traces oscillatory behavior in the UV region. However,
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42 it was noticed that doping Pb into host CdS lattice enhanced opto-electrical properties and hence
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CdS:Pb system behaves as an ideal material for QDs based solar cells, photo-detector and
45 photosensitive applications.
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Keywords: Cadmium Sulfide, Pb doping, DFT calculations, Density of states, Optical Properties
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 AUTHOR SUBMITTED MANUSCRIPT - MRX-112329.R2 Page 2 of 24

1
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3 1. Introduction
4

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6 Semiconductor families such that III-V and II-VI are well known and contain most of the
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8 materials on which current research related to electronics [1], optoelectronics [2] and spintronics
9 [3] is carried out. Out of these semiconductors, II-VI group have stretched considerable attention

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11 in current research due to exceptional applications and extensive uses in modern technological
12
13 fields. II-VI class semiconductors have substantial implications in the field of photonics, light
14
15
sensing and device fabrication. II-VI group semiconductors have potential uses and applications
16 in solar cells, light detection devices, X-ray detection, photovoltaic [4] and optoelectronic

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18 devices. Number of experimental and theoretical studies has been conducted in order to
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20 investigate physical properties of semiconductors for postulating their uses in recent
21
technological era. Hence, II-VI group semiconductors have provided spacious insight in
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technology and reshaped future of device making.

Cadmium Sulfide (CdS) is n-type semiconductor belonging to II-VI family of semiconductors[5]

and is popular in recent research due to extensive uses in nanotechnology [4]. It has astonishing
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29 physical and optical properties which extend its uses in the detection of visible light and in
30
31 heterojunction solar cells [6]. It has brought enormous boost in technological advancement and
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33 extended applications in various emerging fields such as biosensing devices [7, 8], photo
34 electroluminescent displays [9], thin films transistors [10], gas detectors [11], vacuum UV
35
36 lenses [12], photo voltaic light emitting diodes [4, 13, 14] photoelectrochemical solar cells [15,
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38 16] and photovoltaic cells [17]. Moreover, biological sensors, infrared photoconductors and
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nonlinear electroluminescent displays are other extending applications of CdS which prove it as
41 a promising candidate for device fabrication in field of energy or light sensing.
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43
44 CdS structurally occurs in three different forms which are zincblende, wurtzite and rocksalt.
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46
These three structural forms are defined by different structure constants and lattice parameters.
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47 Zincblende and wurtzite structures [18-20] are found in polymorphous form and are energetically
48
49 degenerate. On the other hand, rocksalt structures are found in nanocrystalline form.
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51 Nanocrystalline phases of rocksalt CdS [21, 22] carry special mandate in semiconductor physics
52
due to their exceptional electronic and optical properties [23, 24]. Rocksalt structure of CdS is
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54 approved for research due to its nano phase existence, abundant natural occurrence and stability
55
56 [25]. CdS nanostructures such as nanodots, nanowires and nanorods have more significance in
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Page 3 of 24 AUTHOR SUBMITTED MANUSCRIPT - MRX-112329.R2

1
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3 research and exhibit stunning applications in photonic switching, optoelectronic devices and
4

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5 photovoltaic cells. However, these nanostructures have also been used in biolabeling, bioimaging
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7 and other areas related to biotechnology [26, 27]. Due to appealing advantages and emerging
8
9
potential uses of rocksalt CdS, M. Junaid Iqbal Khan et al. have studied these structures in detail

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10 [27-33].
11
12
13 Effect of certain dopants on CdS may enhance electronic, magnetic, optical, electrical, and
14
15
piezoelectric properties [23, 30, 34, 35]. Most of appealing properties of nanostructured CdS
16 emerge due to doping which causes change in defects and electron density distribution [36].

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18 Numbers of studies have been conducted in both experimental and theoretical scope in order to
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20 predict electronic, optical and related properties of doped CdS system [37-40]. CdS has appealed
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enormous attention in current research due to extensive uses in recent device making based on
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cheaper technological advancement, low cost, power efficiency, extraordinary optoelectronic
properties and in making efficient photoconductive and photosensitive devices. Hence, due to
these reasons CdS is a subject of research for both experimentalists and theoreticians.
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29 Through research review, it has been noticed that large number of experimental studies on CdS
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31 [41-46] have been conducted but theoretical findings have not been focused enthusiastically [29,
32
33 47, 48]. Theoretical studies based on density functional theory (DFT) employed within certain
34 simulation packages are not robustly focused for comprehension of large atomic systems and to
35
36 understand their relevant physical properties [49-51]. Doping lead (Pb) into CdS is interesting
37
38 and important as it shows good optical, electronic and magnetic properties [52]. Lead (Pb) is a
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post transition metal which is used for applications of quantum dot solar cell and is able to
41 control absorption of light in 600-3000 nm range [53, 54]. M. Anbarsai et al. have presented
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43 experimental study (spray technique) on structural, morphological and optoelectronic properties
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45 of Pb doped CdS and performed EDX, XRD, SEM, electrical and optical studies. Both red and
46
blue shift is observed and optical transparency is increased with decrease in electrical resistivity
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48 [55]. K. Veerathangam et al. have reported an experimental study (SILAR) on photovoltaic
49
50 performance of Pb-doped CdS quantum dots for solar cell applications and explained results of
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52 EDX, SEM and XRD. Their study reveals that Pb doped CdS quantum dot (QDs) solar cells have
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53 maximum power conversion efficiency [53]. Banerjee M. et al. have carried out an experimental
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55 study on effect of lead doping on structural and optical properties of nanostructured CdS films
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3 and presented results using XRD and UV-viz spectroscopy. R. Gutiérrez et al. have done
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5 experimental study (chemical bath) for finding structural and optical properties of CdS:Pb+2
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7 nanocrystals. They explained results of SEM, EDX, FTIR, XRD, absorbance, transmittance and
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9
raman spectroscopy. They concluded that absorption shows blueshift, XRD spectrum shows

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10 crystalline nature and SEM results indicate improvements in cyrstallinity [56]. In addition,
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12 Hamid S. Al-Jumaili has elucidated an experimental study (chemical bath deposition) on
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14 structural and optical properties of nanocrystalline PbCdS thin films [57]. His findings were
15
accomplished using XRD, AFM, SEM and UV-Vis spectroscopy. He incorporated refractive
16

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17 index, extinction coefficient and dielectric constant. Moreover, blueshift in absorption spectrum
18
19 is observed which validates Pb doped CdS a good material for photo-detector and solar
20
21 applications. Through literature survey, we found more experimental studies on Pd doped CdS
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system, conducted through various experimental methods but no theoretical study based on
certain simulation packages including Wien2K, VASP, CASTEP etc has been reported to date.
Hence, this reason is a prime motivation for us to perform current study. Moreover, no
computational study particularly focused on rocksalt CdS structures using Wien2K code has
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29 been conducted and it is the reason which motivated authors to work on doping Pb into CdS.
30
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32 In current research, we shall demonstrate optical properties including optical absorption,
33
34
reflectivity, conductivity, extinction coefficient, refractive index, and dielectric constant of Pb
35 doped rocksalt CdS system. Perdew-Burke-Ernzerhof parameterized generalized gradient
36
37 approximation (PBE-GGA) has been employed within framework of DFT using Wien2K code.
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We calculated total density of states (TDOS) and partial density of states (PDOS) in order to
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understand electronic behavior of CdS:Pb system. In our computational study, we are interested
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42 in observing possible changes in optical and electronic properties with increase in supercell size
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44 upon Pb doping into CdS. Entire results have been compared with existing literature findings and
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46 found to have good agreement. Challenges of the computational field have been met through first
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47 principle calculations. Several interesting facts regarding CdS:Pb system have been explored
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49 within context of manuscript which may provide enough physical details for readers and can
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51 explain future scope of this material in optoelectronic and photo-conductive industry.
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3 2. Computational Method
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6 For DFT calculations in current study, we have chosen rocksalt structure of CdS. We studied
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8 electronic and optical behavior of CdS:Pb system with 6.25% (1 × 1 × 2), 3.12% (1 × 2 ×
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2) and 1.56% (2 × 2 × 2) Pb concentrations. For all these concentrations, we observed electronic

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11 behavior of CdS:Pb system by studying plots for total density of states (TDOS) and partial
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13 density of states (PDOS). Computational work has been conducted using Wien2K code
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15 employed within framework of DFT. Supercells are simulated with Fm-3m space group and 𝛼 =
16 𝛽 = 𝛾=90°. Cd atoms are substituted with Pb atoms at second Cd site in all concentrations. The

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18 method of full potential linearized augmented plane wave (FP-LAPW) [58] is implemented in
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20 Wien2K code [59] in order to perform theoretical calculations. This method proved to be precise
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22 and efficient approach for finding solution of Kohn-Sham equations [60] within framework of
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DFT and it helps for simulation of materials [61]. PBE-GGA (Perdew-Burke-Ernzerhof,
Generalized gradient approximations) is an exchange correlation potential and is used to
calculate total energy [62]. This functional (PBE-GGA), emerges to be very useful for
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meaningful improvement of lattice constant, crystal structure and to deal with the ground state
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30 properties. We supposed (5s24d10), (3s23p4) an (6s26p2) states of (Cd, S, Pb) respectively as
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32 valence states while rest of the states are considered as core states and are designated as frozen
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34 states. Potential is constant and spherically symmetric inside muffin-tin (MT) sphere while
35 maximum angular momentum expansion value for the wavefunction is l=10. We have used
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37 Gaussian smearing of 0.1 eV. A single Pb atom (dopant) is substituted at Cd cationic sites in
38
each supercell of 16 (~ 1 × 1 × 2), 32 (~ 1 × 2 × 2) and 64 (~ 2 × 2 × 2) atoms. Augmented
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41 plane wave (APW) with local valence orbitals are utilized with wave functions while charge
42 densities and potentials are expanded in spherical harmonics inside muffin-tin (MT) spheres. In
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44 MT spheres, the basis sets are illustrated by the radial solution of one particle Schrödinger
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46 equation and their energy derivatives multiplied by the spherical harmonics. Integration of
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Brillouin zone (BZ) is conducted using method of modified tetrahedron [63] in the irreducible
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49 wedge of simple cube. Relativistic effects are not included in current study. Entire calculations
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51 for all supercell configurations are performed for 1000 k-point sampling accomplished by opting
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53 Monkhorst-Pack [64]. Relaxation of internal atomic positions is accomplished using self-

54 consistency criterion involving energy convergence, charge convergence, step convergence and
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gradient convergence which are fixed at values 10-3 eV, 10-2C, 10-3 eV and 10-4 eV/Å
4

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5 respectively. When structure is fully relaxed then bond length values found to be, Cd-S 2.721 Å,
6
7 Cd-Pb 3.59 Å and Pb-S 1.89 Å. However, value of a change from 5.43 Å to 5.440 Å for 1.56%
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9 Pb, 5.444 Å for 3.25% Pb and 5.441 Å for 6.25% Pb concentrations is found. This expansion of

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11 lattice is due to the replacement of lower radius element Cd+2 (0.94Å) by the higher ionic radii
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13 element Pb+2 (1.2 Å) [55].
14
15 Results and Discussions
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18 Electronic Properties
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20 Figure 2, represent band structure of pure CdS, 1.56%, 3.12% and 6.25% Pb concentrations.
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Band structures illustrate that addition of Pb replacing Cd into host CdS lattice shrinks the
bandgap. In the region of conduction band near to Fermi level, impurity states are generated
because of which states overlap with each other and exhibit conducting nature. However,
bandgap as calculated through DFT are smaller than experimental bandgap. It is due to fact
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29 associated with limitations of DFT which considers relatively uniform distribution of electrons.
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31 So, DFT bandgaps serves to be lower limit to the actual bandgap [32, 65].
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52 Fig. 1. Band structure of (a) pure CdS, (b) 6.25%, (c) 3.12% and (d) 1.56% Pb concentrations
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54 Cadmium sulfide has semiconducting properties and due to this reason it has been extensively
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56 used in modern advancement related to technology. Emerging physical properties of CdS under
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3 doping may advocate this material as best suitable for mirco and nano applications. We explore
4

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5 evolution of electronic properties by studying TDOS and PDOS as illustrated in fig. 2. Detailed
6
7 analysis of TDOS and PDOS exhibits that resulting properties of CdS:Pb system emerge due to
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9
hybridization of dopant (Pb) and host (CdS) orbitals. In extending arguments about DOS plots, it

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10 is clear that contributing orbitals are Pb s and p while for S it is p-orbital.
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13 Density of states (DOS) provides occupancy of various states in particular energy interval. It is
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15
comprised of orbitals of individual atoms in specific supercell configuration. In current research
16 work, we calculated PDOS and TDOS of Pb doped CdS system and the separation between

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18 valence and conduction band (fig. 2) is represented by dotted line, called Fermi energy. Adding
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20 impurity atoms (Pb) into the host CdS lattice may contribute enough number of electrons which
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are present in conduction holes in vicinity of Fermi level. This role is exactly explained by DOS
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plots.
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PDOS plots of Pb doped rocksalt CdS system for all Pb concentrations (1.56%, 3.12%, 6.25%)
and for pure CdS have been shown in fig. 2. These plots explain transition of electrons from
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29 valence to conduction band and give contribution of orbitals (s,p,d) of individual atom of CdS:Pb
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31 system. In case of pure CdS (fig. 2(a)), contribution of S p-states and Cd d-states are clearly seen
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33 in region of valence band maxima while in minima of conduction band, S p-states and Cd s-
34 states are present. In fig. 2, transition of electrons is clearly noticed from valence to conduction
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36 band. Different states of Cd, S and Pb atoms are distributed in energy range -15.00 eV to 10.5
37
38 eV. It is clear that dopant (Pb) states are present in narrow and wider distribution in valence
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band and hybridized with sulfur p-states. First region containing wider peaks lies in range -13.6
41 eV to -12.5 eV of energy and have presence of majority of Cd d-states, S s-states and Pb d-states.
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43 It has minimum impact of Cd s-states, S p-states and Pb p-states. Second region is located in
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45 energy range -9.8 eV to -7.0 eV where majority of states from Cd p-states, S p-states and Pb s-
46
states are noticed with least contribution of Cd s-states, S s-states and Pb d-states. As energy
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48 increases further, then third region is observed in energy interval -6.0 eV to -0.1 eV. It has clear
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50 impact of Cd p-states, S p-states and Pb s-states with least contribution of Cd s-states, S s-states
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52 and Pb d-states. Through analysis, we come to know that Cd p-states, S p-states and Pb s-states
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53 impart maximum contribution and in turn enhances electronic and optical properties of Pb doped
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55 CdS rocksalt system. Dominance of various states of dopant (Pb), Cd and S over wide energy
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3 range are responsible for band gap energy and are responsible for good conductivity of CdS:Pb
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5 system. Dopant (Pb) s-states are found near to maxima of valence band and crosses Fermi level.
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7 Hybridization of Pb 6s-states and S 3p-states is clearly observed as these states located at valence
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9
band maximum. Impurity states are extending at Fermi level with one hump in case of

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10 6.25% concentration and with two humps in case of 3.12% concentration. But in case of 1.56%
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12 Pb concentration in CdS lattice, these states become sharp and are restricted near to Fermi level.
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14 Comparison of all supercell configurations shows that Pb addition into host CdS lattice induces
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impurity states in vicinity of Fermi level and charge density increases by creation of additional
16

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17 charge carriers independent of doping position [32, 66].
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20
21
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23
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25
0.4
0.3
(a) Pure CdS EF
an S-s
PDOS (states / eV)
0.8
0.6
0.4
0.2
0.0
(b) 6.25 % Pb concentration

-14 -12 -10 -8 -6 -4 -2 0

EF

2 4 6
------- Pb-s
------ Pb-p
------ Pb-d

8 10
PDOS (states / eV)

------- S-p 0.8

0.2
26 0.1
0.6
------ S-s
------ S-p
0.4
27 0.0
-14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 0.2
28 ------ Cd-s 0.0
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0.4 ------ Cd-p 0.8 -14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10
29 0.3 ------ Cd-d 0.6
------ Cd-s
------ Cd-p
0.2
30
------ Cd-d
0.4
0.1
0.2
31 0.0
-14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 0.0
32 Energy (eV)
-14 -12 -10 -8 -6 -4 -2 0
Energy (eV)
2 4 6 8 10

33 0.8
(c) 3.12 % Pb concentration EF ------ Pb-s
0.8
0.6
(d) 1.56% Pb concentration EF ------Pb-s
0.6
34 0.4
------ Pb-p
------ Pb-d 0.4
------ Pb-p
------ Pb-d
PDOS (states / eV)
PDOS (states / eV)

35 0.2 0.2
0.0
0.0
36 0.8 -14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 0.8 -14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10
-------S-s ----- S-s
37 0.6
0.4
------ S-p
0.6
0.4
------ S-p

38 0.2 0.2
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39 0.0
0.8 -14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10
0.0
0.8 -14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10
40 0.6
-------Cd-s
------ Cd-p
0.6
------ Cd-S
------- Cd-p
0.4 0.4
41
------ Cd-d ------- Cd-d

0.2 0.2
42 0.0 0.0
-14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10
-14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10
43 Energy (eV) Energy (eV)
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45
46 Fig. 2. PDOS of Pb doped CdS system for, (a) Pure CdS, (b) 6.25%, (c)3.12% and (d) 1.56% Pb
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47 concentrations.
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49
50
51
Optical Properties
52
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53 Optical properties related to CdS carry importance due to its extensive uses in devices based on
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55 nanotechnology. It serves as window layer material for many applications in the field of
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3 optoelectronic and solar energy. Optical properties of CdS nanoparticles are very important in
4

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5 reflecting new trends in nanotechnological advancements due to Quantum confinement effects.
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7 Pb doped CdS system attracts attention as Pb+2 ions enhance quantum trap for the excited
8
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electrons. However, most of the photoluminescence properties of CdS:Pb system appear due to

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10 interaction between holes and electrons of CdS nanoparticles where CdS serves as host for the
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12 localized dopant level.
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15
Traits for optical properties of Pb doped CdS for various supercell configurations have been
16 expressed in figs. 3-5 and observations are recorded as optical absorption, conductivity, index of

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18 refraction, reflectivity, extinction coefficient and dielectric constant. Various optical plots (figs.
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20 3-5), explaining optical behavior of CdS:Pb system found to have good agreement with already
21
reported experimental work. Figure 3(a) represent plots for optical absorption of Pb doped CdS
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25
26
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28
constant [32, 49, 67],
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system for 1.56%, 3.12% and 6.25% Pb concentrations in addition to pure CdS. Absorption
coefficient (𝛼(𝜔)) is dependent on the real (𝜀1 (𝜔)) and imaginary part (𝜀2 (𝜔)) of the dielectric
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29 1/2
30 𝛼(𝜔) = √2 [√𝜀²1 (𝜔) + 𝜀²2 (𝜔) − 𝜀1 (𝜔)] .
31
32
33 Absorption plots depicted in fig. 3(a), demonstrate energy (frequency) dependent absorption
34
35 spectra where we observe an increasing and decreasing trend. Spectrum of absorption may
36 appear as a result of excitation of electrons from valence to conduction band [68] and shifting of
37
38 exciton peaks toward lower energy (higher wavelength) region may be due to the quantum
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40 confinement effects [30, 69]. Quantum confinement effect results in an increase in transition
41
42
energy of exciton and blueshift in the absorption spectrum. Excitation of phonons also causes the
43 change in absorption spectrum. These quantum confinement effects are more pronounced in case
44
45 of 1.56% Pb concentration (~2 × 2 × 2 supercell configuration) where correlation and
46
interaction effects become more significant. Absorption spectrum is plotted over wide range of
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48
energy (0-6 eV) and is extended from infrared to the ultraviolet region of the electromagnetic
49
50 spectrum. Absorption plots for all supercell configurations show rising trend up to certain energy
51
52 value and then decrease afterwards. It is observed that absorption trend for 3.12% Pb
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54 concentration is shifted toward right in comparison to pure CdS and has maximum absorption at
55 4.8 eV (∼ 258 nm). Hence, absorption trait for 3.12% concentration shows blueshift. On the
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3 other hand, absorption trend for 1.56% Pb concentration is shifted toward larger wavelength in
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5 comparison to pure CdS and shows redshift. Absorption edge for 1.56% Pb concentration
6
7 corresponds to energy value of 4.46 eV (∼ 277 nm) [55]. This redshift may be due to decrease in
8
9 difference of energy levels with applied electric field. Weaker carrier confinement results in

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10 redshift of absorption spectrum and is observed in quantum dots which may be created due to
11
12 effect of electron-hole interactions [70, 71]. Beyond maximum absorption (4.46 eV), the
13
14 oscillatory trend is observed which becomes almost constant for higher energy values [29]. This
15
16
oscillatory trend is due to many body interactions and it depends upon the transition strength. As

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17 it is assumed that the orientation of transition dipoles are random with respect to the direction of
18
19 exciting electromagnetic field. Blueshift in absorption spectrum is referred as increase in particle
20
21 size and is a signature of formation of nanostructure [30, 57, 72]. Absorption coefficient is more
22
23
24
25
26
27
28
an
pronounced in the UV region [66]. Hence, we conclude that 1.56% Pb concentration
corresponding to 2 × 2 × 2 supercell configuration exhibits redshift in absorption while for
6.25% and 3.12% Pb concentrations, absorption is blue shifted. Blueshift in absorption spectrum
shows resemblance with the results reported by Banerjee et al. in [73] and R. Gutiérrez et al. [56]
dM
29 while the difference is due to the reason that, they focused on obtaining results by experimental
30
31 methods whereas we performed this through Wien2K code with PBE-GGA approximations
32
33 employed within the framework of DFT. However, as number of atoms is increased in the lattice,
34
35
it can induce more energy states (as evident in fig. 2 (d)) close to Fermi level in order to absorb
36 photon energy and likewise, the absorption increases [55]. Absorption of CdS:Pb material
37
38 enables its uses in tuning most of scintillating features of various opto-electronic materials [74].
pte

39
40
41 Reflectivity 𝑅(𝜔) of Pb doped rocksalt CdS system has been shown in fig. 3(b) and can be
42 calculated by the formula [32, 67],
43
44
2
45 √𝜀1 (𝜔) + 𝑖𝜀2 (𝜔) − 1
46 𝑅(𝜔) = [ ] .
√𝜀1 (𝜔) + 𝑖𝜀2 (𝜔) + 1
ce

47
48
49
50 The graph shows variation in reflectivity trends for pure CdS along with 6.25%, 3.12% and
51 1.56% corresponding 1 × 1 × 2 ,1 × 2 × 2 and 2 × 2 × 2 supercell configurations. Reflectivity
52
Ac

53 is plotted by taking energy in range 0-6 eV. Major reflectivity peaks are arising below 5 eV and
54
55 for higher energy values, reflectivity becomes almost constant. These plots show gradual
56
57
58
59
60
Page 11 of 24 AUTHOR SUBMITTED MANUSCRIPT - MRX-112329.R2

1
2
3 increase in reflectivity with increase in energy but decreases after maximum reflectivity value.
4

pt
5 Reflectivity trend for 6.25% Pb concentration (~ 1 × 1 × 2 supercell configuration) increases in
6
7 steps. First it shows gradual increase up to 2.0 eV which decreases suddenly and then increases
8
9
up to 4.3 eV. It decreases further (after 4.3 eV) and attains constant trend for rest of higher

cri
10 energy values. However, maximum reflectivity for 1.56% Pb concentration correspond to 4.4 eV
11
12 energy and an oscillatory trend is observed which is slightly different from rest of supercell
13
14 configurations because of involvement of correlation and interaction terms. Reflectivity peak for
15
3.12% Pb concentration (~ 1 × 2 × 2 supercell configuration) is obtained at 4.8 eV which
16

us
17 decreases further as energy increases. Reflectivity peaks for all concentrations correspond to
18
19 plasmons and emerges due to interband transitions from valence to conduction band or it may be
20
21 due to oscillations of free electrons in a collective manner [66]. However, variation in reflectivity
22
23
24
25
26
27
28
an
trend for 3.12% and 1.56% Pb concentrations in the low energy region (1.2 eV-2.3 eV) may be
associated with reasoning of transitions of band edge which are emerging as result of absorption
[32]. Owing to exceptional optical reflectance, these materials may be utilized as window
materials with excellent transparency [28, 32]. Moreover, lower reflectivity values exhibited by
dM
29 this material enable its uses in coating related to anti-reflection of optical devices including
30
31 binoculars, lenses etc [29, 75].
32
33
34 Fig. 3(c) represents traits for optical conductivity of pure CdS along with case of 6.25% (1 × 1 ×
35 2), 3.12% (1 × 2 × 2 ) and 1.56% ( 2 × 2 × 2) Pb concentrations in rocksalt CdS lattice. It is
36
37 denoted by σ(ω) and can be calculated in term of dielectric constant ε(ω) [32, 67],
38
pte

39 ω
40 σ(ω) = −i 4π |ε(ω) − 1|.
41
42
43 All plots for the conductivity are calculated using wien2K code employed within framework of
44
DFT and it is clear that conductivity increases with increase in energy (eV). In general, similar
45
46 trends (increasing behavior) for conductivity are observed with slight shift of peaks in all cases.
ce

47
48 Conductivity behavior of 3.12% Pb concentration shows broader peaks while for 1.56% Pb
49
50 concentration, a sharp peak is observed. Conductivity trend for pure CdS increases up to 4.3 eV
51 and decreases afterwards but becomes almost constant for higher energy values [28, 32].
52
Ac

53 Conductivity trends for 6.25% and 1.56% supercell configurations shows small humps in low
54
55 energy region (1.0 eV-2.4 eV) which may appear due to interaction of Pb with S atoms as
56
57
58
59
60
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1
2
3 evident from DOS plots (figs. 2), where hybridization of dopant and S orbitals can be clearly
4

pt
5 seen. Hence, due to states localization as observed in PDOS, the CdS:Pb system exhibits good
6
7 conductivity. However, maximum conductivity for 6.25%, 3.12% and 1.56% Pb concentrations
8
9
is noted at 4.1 eV, 4.29 eV and 4.35 eV energy values respectively. Moreover, well defined

cri
10 peaks appearing in the UV spectrum of conductivity may emerge due to interband transitions
11
12 [30, 67].
13
14
15
In optics, extinction coefficient (k) is very important physical quantity and is related to
16 absorption of light as shown by the formula [30, 32],

us
17
18
𝛼𝜆
19 𝑘 = 4𝜋.
20
21
22 Where (𝛼, 𝑘) is absorption and extinction coefficient respectively. Due to interconnection of 𝛼
23
24
25
26
27
28
an
and 𝑘, we observe a great resemblance between plots presented in figs. 3(a) and 3(d). Fig. 3(d)
depicts change in extinction coefficient with increase in photon energy (0-6 eV). k values
increases with increase in energy and it is due to quantum confinement effects [32], which are
dM
29 further related to variation in crystallite size as experimentally observed by L. Soliman et al. in
30
31 [76]. Extinction coefficient plots are obtained by direct solution (through DFT) of many-body
32
wave function. It shows energy absorption on surface of materials [77]. The plots of k for pure
33
34 CdS and 3.12% Pb concentration shows steady increase but for the case of 6.25% and 1.56% Pb
35
36 concentration, small humps in low energy region (1.1 eV-2.4 eV) are noted which emerge due to
37
38 quantum effects. In case of 1.56% Pb concentration, decrease in peak intensity occurs due to
pte

39 atomic correlation and interactions. These extinction peaks may be associated with density of
40
41 states which are localized near the Fermi level and caused by addition of impurity atoms as
42
43 evident from DOS plot (fig. 2). The k maximum values indicate maximum attenuation
44
impurities. High extinction coefficient values represent high cross section of absorption. It also
45
46 illustrates absorption of light at defect sides [31]. Extinction coefficient vanishes for lossless
ce

47
48 materials but in our case non zero values of k represent loses inside material. Extinction
49
50 coefficient, k values (0.10-0.16) as obtained through DFT calculations are smaller than
51 experimental value (0.5) for pure CdS obtained at 632.8 nm (1.96 eV) [30, 78]. 0-2.8 eV energy
52
Ac

53 range has k values 0-0.5 except for higher Pb concentration (6.25%). The extinction coefficient
54
55 edge for 1.56% Pb concentration is shifted towards higher wavelengths and is related to high
56
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Page 13 of 24 AUTHOR SUBMITTED MANUSCRIPT - MRX-112329.R2

1
2
3 absorption in that region [57]. However, k increase with corresponding energy values, represents
4

pt
5 electron transfer probability across mobility gap [31]. Our result of extinction coefficient for pure
6
7 CdS including 6.25%, 3.12% and 1.56% Pb concentrations show reasonable agreement with the
8
9
experimental findings of Hamid S. Al-Jumaili but the difference between two studies may be due

cri
10 to assumption that our findings are based on theoretical study (DFT) of rocksalt CdS using
11
12 Wien2K code by employing PBE-GGA approximations while his study is based on experimental
13
14 findings obtained using chemical bath technique.
15
16

us
0.55
17 (a) CdS:Pb System (b) CdS:Pb System

Reflectivity (Arbitrary Units)

140
Absorption (Arbitrary Units)

Pure CdS
18 120
Pure CdS
6.25%
0.50 6.25%
3.12%
19 3.12%
1.56% 0.45 1.56%
100
20
0.40
21 80

22
23
24
25
26
27
11000
60

40

20

0
0

(c)
1 2 3
Energy (eV)
CdS:Pb system
4 5
an
6
0.35

0.30

0.25
Extinction Coefficient (Arbitrary Units)

0 1 2 3 4
Energy (eV)
5 6
Conductivity (Arbitrary Units)

(d) CdS:Pb System

28 3.0
dM
10000 Pure CdS Pure CdS
29 9000
6.25%
3.12%
2.5
6.25%
3.12%
30 8000 1.56% 1.56%
2.0
31 7000
6000
32 5000
1.5

33 4000
1.0
34 3000

35 2000 0.5
1000
36 0 0.0
37 0 1 2 3
Energy (eV)
4 5 6 0 1 2 3 4 5 6
Energy (eV)
38
pte

39
40 Fig. 3. Plots for, (a) optical absorption, (b) Reflectivity, (c) Conductivity and (d) extinction
41
42
coefficient of Pb doped CdS
43
44 Refractive index (n) is an important quantity which gives information about behavior of light
45
46
inside any material. It gives detailed information about optical properties of any material when
ce

47 light is incident on it. When light pass through different medium, its velocity changes which in
48
49 turn cause change in refractive index of material. Fig. 4 shows variation in refractive index for
50
51 various Pb concentrations (1.56%, 3.12%, 6.25%) including pure CdS. It is clear from fig. 4, that
52
index of refraction increases with increase in energy (eV). Maximum value of index of refraction
Ac

53
54 is 4.1 at energy value of 3.78 eV (328 nm). Increase and decrease in value of n with increase in
55
56 energy is noted. For pure CdS thin films, experimental value of refractive index is 2.38 at 1.96
57
58
59
60
 AUTHOR SUBMITTED MANUSCRIPT - MRX-112329.R2 Page 14 of 24

1
2
3 eV (632.8 nm) [28, 30, 31]. But in current DFT calculations, values of refractive index are higher
4

pt
5 than the experimental value. Index of refraction for various Pb concentrations as obtained using
6
7 DFT calculations, during substitution of Cd with Pb atoms in host CdS lattice are, 3.10 ~ 6.25%,
8
9 3.19 ~ 3.12% and 3.4 ~ 1.56%. However, n for pure CdS as obtained in current computational

cri
10 study is 2.9 [31, 32]. Increased value of n may be connected to crystallite size which increases
11
12 due to decrease in microstrain [79]. Variations in refractive index may emerge due to dispersion
13
14 of light as it permeates deeper inside the material and may have successive interactions with
15
16
various atoms of different supercell configurations as presented in our study. The refractive

us
17 index, n bears value greater than one due to reason that when photon enters into a material then
18
19 they get slowed down by successive interactions with the electrons. As the Pb concentration ~
20
21 1.56% corresponds to 2 × 2 × 2 supercell configuration which contains maximum number of
22
23
24
25
26
27
28
an
atoms (64 atoms in the supercell) making it denser than the supercells with higher Pb
concentrations (i.e. 3.12% and 6.25% with lower number of atoms i.e. 32 and 16 respectively in
the supercell) and hence large number of photon get slowed down while passing through material
due to interactions with larger number of atoms (electrons) leading to an increase in the
dM
29 successive internal reflections, which in turn increases the refractive index. In addition, density is
30
31 directly related with refractive index so denser medium will show higher refractive index. In
32
33 general, in any supercell with larger number of atoms, the electron density is also increased, and
34
35
consequently, refractive index increases [74]. However, in case of 6.25% Pb concentration
36 (1 × 1 × 2 supercell), the CdS:Pb system contains only a total of 16 atoms and so the interaction
37
38 of light radiations with these atoms depicts different behavior as compared to that with more
pte

39
40 atoms. Higher values of refractive index of CdS:Pb system may leads to its potential uses in the
41
field of solar cells, anti-reflection coatings, photodetectors, environmental sensors, opthalmics,
42
43 building displays and have wide applications in areas related to photonics [80, 81]. In
44
45 experimental scope, variation in n may appear due to effect of successive internal reflections and
46
it may further be connected to the reason of trapping photons by grain boundaries [82, 83]. Our
ce

47
48 findings match with the results presented by Hamid S. Al-Jumaili [57] but the difference may be
49
50 due to fact that our calculations are based on computations (DFT) using Wien2K code carried
51
52 out by employing PBE-GGA approximations while his findings are based on experimental
Ac

53
54
framework (chemical bath technique).
55
56
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58
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Page 15 of 24 AUTHOR SUBMITTED MANUSCRIPT - MRX-112329.R2

1
2
3
4

pt
Pure CdS
5

Refractive Index (Arbitrary Units)

4.0
6.25%
6
3.12%
7 1.56%
8 3.5
9

cri
10
11 3.0
12
13
14 2.5
15
16

us
17 2.0
18
19
20 1.5
21 0 1 2 3 4 5 6
22 Energy (eV)
23
24
25
26
27
28
an
Fig. 4. Refractive Index of Pb doped CdS system for, (a) Pure CdS, (b) 6.25%, (c) 3.12% and (d)
1.56% Pb concentrations.

Electric field is responsible for the optical transitions between occupied and unoccupied states.
dM
29 Knowing this fact, most of the optical properties like extinction coefficient and dielectric
30
31 constant are very important to study for any physical system. Optical properties are related to the
32
33 medium and can be calculated from the complex dielectric function 𝜀(𝜔) = 𝜀𝑟 (𝜔) + 𝑖𝜀𝑖 (𝜔).
34 Many body wave function upon direct solution provides imaginary part of dielectric function
35
36 (εi (ω)) and so the real part of dielectric function (εr (ω)) may be calculated in term of
37
38 imaginary part via Kramers-Kronig transform [32, 67].
pte

39
2
40 4π2 2
41 εi (ω) = 2 2 ∑ ∫ 3
|MC,V (k)| δ (ECk − EVk − ℏω)d3 k,
42 m ω BZ (2π)
C,V
43
44 2 ∞ ω∕ εi (ω)
εr (ω) = 1 + π ρ0 ∫0 dω.
45 ω∕2 −ω2
46 Where subscripts V and C stand for valence and conduction band respectively. ω is the angular
ce

47
48 frequency, k is the reciprocal lattice vector and BZ denotes first brillouin zone. ECk and EVk meant
49
50 for intrinsic energy level of conduction and valence band respectively [49]. Fig. 5(a), represents
51
52 various plots for real dielectric constant (𝜀𝑟 ) in case of pure CdS and for various Pb
Ac

53
concentrations 6.25%, 3.12% and 1.56% corresponding to 1 × 1 × 2, 1 × 2 × 2 and 2 × 2 × 2
54
55 supercell configurations respectively. It exhibit material ability to allow external electromagnetic
56
57
58
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1
2
3 field to pass through it. 𝜀𝑟 for all cases is plotted by taking energy in the range 0-6 eV, along
4

pt
5 abscissa. Dielectric trends for pure CdS and 3.12% Pb concentration are almost similar but we
6
7 observe different trends in case of 6.25% and 1.56% Pb concentrations. Since, dielectric constant
8
9
is given in term of square of the refractive index so we find a great similarity between both plots

cri
10 presented in figs. 4 and 5(a).
11
12 𝜀(𝜔) = 𝑛2 .
13
14 Dielectric trend resembles to graph of refractive index due to smaller k² values compared to n²
15
16
[57]. The graphical trend of 3.12% Pb concentration increases to 3.2 eV and suddenly decreases

us
17 to 4.5 eV. Then it shows small rise (at 4.8 eV) in dielectric curve and decreases further to 5.9 eV
18
19 which becomes almost constant for higher energy values. In case of 6.25% Pb concentration,
20
21 dielectric constant trait steadily increases and decreases upon increase in energy with dielectric
22
23
24
25
26
27
28
an
peaks at energy values, 1.9 eV, 3.6 eV, 4.7 eV and 5.1 eV. Beyond 5.1 eV, the graph adopts
constant trend in region of lower wavelength. However, in zero energy (frequency) limit, we
may define static dielectric constant and its values for pure CdS ~ 8.6 and for various Pb
concentrations into host CdS lattice is, 9.7 ~ 6.25%, 8.7 ~ 3.12% and 11.4 ~ 1.56%. It is
dM
29 obvious that these values of dielectric constant as obtained through DFT calculations are higher
30
31 than experimental value of pure CdS of 2.43 [49]. Decreases in dielectric constant may be better
32
33 explained with dipoles which are present and do not follow change in ac applied electric field
34
35
[32, 84]. Low value of dielectric constant is reasoned with polarizable bond breaking [85].
36 Moreover, increase in static dielectric constant is due to addition of Pb atoms which are
37
38 substituting Cd atoms in host CdS lattice [57].
pte

39
40 On the other hand, imaginary part of dielectric constant (𝜀𝑖 ) is an intrinsic fundamental property
41
42
and it exhibit energy absorbance in dielectric medium in electric field due to motion of dipole
43 [86]. It explains linear response of a system being subjected to electromagnetic radiations. In fig.
44
45 5(b), complex part of dielectric constant has been shown as a function of energy (eV). Sum over
46
BZ in equation, 𝜀(𝜔) = 𝜀𝑟 (𝜔) + 𝑖𝜀𝑖 (𝜔), is performed using linear interpolation of a mesh
ce

47
48
containing uniform distribution of points, i.e tetrahedron method. In analysis of 𝜀𝑖 plot, for pure
49
50 CdS, we observe that first critical hump (threshold energy) occurs at 4.2 eV while for 6.25%,
51
52 3.12% and 1.56% Pb concentrations in host CdS system, principle peaks are obtained at 4.0 eV,
Ac

53
54 4.2 eV and 4.3 eV respectively. In case of 6.25% and 1.56 % Pb concentrations, first critical
55 peak of 𝜀𝑖 occurs at threshold energy 2.08 eV and 1.41 eV respectively and is known as
56
57
58
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1
2
3 fundamental absorption edge. Beyond these energy points, we find a rapid increase in 𝜀𝑖 curves
4

pt
5 which may be due to fact associated with abrupt increase in number of points contributing
6
7 toward 𝜀𝑖 [87].
8
9

cri
10 16 20
11 (a) (b)
Re_Dielectric Constant (Arbitrary Units)

15 Pure CdS

Im_Dielectric Constant (Arbitrary Units)

6.25% 18
12 14
3.12%
Pure CdS
13 6.25%
13 12
1.56% 16
3.12%
14 11 14 1.56%
15 10
12
16 9

us
8 10
17 7
18 6 8
19 5 6
20 4
3 4
21 2
2
22
23
24
25
26
27
28
1
0
0 1 2 3
Energy (eV)
4 5

an 6

Fig. 5. Real and Imaginary part of dielectric constant of Pb doped CdS system for, (a) Pure CdS,
(b) 6.25%, (c) 3.12% and (d) 1.56% Pb concentrations.
0
0 1 2 3 4
Energy (eV)
5 6
dM
29
30
31 Table 1. Summary of the results obtained through DFT for CdS:Pb system. The extinction
32 coefficient is measured between photon energy of 0-2.8 eV.
33
34 Optical Properties Recent Findings Other Works
35
36 Photon energies 4.7 eV (263 nm) ~ Pure CdS 4.7 eV (263 nm) ~ Pure CdS [31, 32]
37 corresponding to 5.0 eV (247 nm) ~ 6.25% Pb 3.8 eV (325 nm) [73]
38 absorption maxima 4.8 eV (258 nm) ~ 3.12% Pb
pte

39 4.4 eV (281 nm) ~1.56% Pb

40
41
42
Extinction Coefficient 0-0.5 (0-2 .8 eV) 0.5 [31, 32]
43
44 Refractive Index 2.9 ~ Pure CdS 2.9 ~ Pure CdS[31, 32]
45 3.10 ~ 6.25% Pb 2.6 [57]
46 3.19 ~ 3.12% Pb
ce

47 3.4 ~ 1.56% Pb
48
49
50 Dielectric Constant 8.6 ~ Pure CdS 8.6 ~ Pure CdS [31, 32]
51 9.7 ~ 6.25% Pb 6.7 [57]
52 8.7 ~ 3.12% Pb
Ac

53 11.7 ~ 1.56 % Pb
54
55
56
57
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3
4

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5
Conclusion
6
7 We studied TDOS, PDOS and optical properties of Pb doped CdS system using PBE-GGA
8
9
approximation employed within Wien2K code in the framework of density functional theory.

cri
10 Our results matches with existing literature work. Contributing orbitals are Cd 4d, S 3p and Pb
11
12 6s. For 6.25% and 3.12% Pb concentrations in host CdS lattice, optical absorption shows
13
14 blueshift in comparison to pure CdS while redshift is observed for 1.56% Pb concentrations.
15
Hence, Pb doping into CdS lattice enhances optical properties which emphasizes its uses in QDs
16

us
17 based solar cells, photosensitive and optoelectronic devices.
18
19
20 Acknowledgement
21
22
23
24
25
26
27
28
an
This work is carried out in Department of Physics, Bahauddin Zakariya University, Multan and
authors would like to specially acknowledge the computational facilities of department of
Physics, school of sciences and engineering, Lahore University of Management Sciences
(LUMS), Pakistan.
dM
29
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31
32
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34
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36
37
38
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1
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3 References
4

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5
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ce

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3 17. Y. Al-Douri, Jamal H. Waheb, M. Ameri, R. Khenata, A. Bouhemadou and A. H. Reshak
4

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