Materials Chemistry and Physics 269 (2021) 124766

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Investigation of structural and optical properties of Pb1-xCoxS nanocrystals

embedded in chalcogenide glass
R.S. Silva a, *, E.V. Guimarães a, **, R.E.S. Melo a, A.S. Silva a, A.C.A. Silva b, N.O. Dantas b, S.
A. Lourenço c
a
Instituto de Ciências Exatas, Naturais e Educação (ICENE), Departamento de Física, Universidade Federal do Triângulo Mineiro, 38025-180, Uberaba, Minas Gerais,
Brazil
b
Laboratório de Novos Materiais Nanoestruturados e Funcionais, Instituto de Física, Universidade Federal de Alagoas, Maceió, 57072-970, AL, Brazil
c
Laboratório de Dispositivos Fotônicos e Materiais Nanoestruturados (DFMNano), Departamento de Física, Universidade Tecnológica Federal do Paraná (UTFPR),
86036-370, Londrina, Paraná, Brazil

H I G H L I G H T S

• Co2+-doped PbS NCs were growth in borosilicate host glass.

• Structural and optical properties of Pb1-xCoxS NCs are investigated for x = 0.00, 0.10, and 0.16.
• Crystal Field Theory indicates the location of the Co2+ ions in tetrahedral sites.
• Quantum confinement and interaction exchange sp-d between PbS and Co2+ ions are observed.

A R T I C L E I N F O A B S T R A C T

Keywords: Diluted magnetic semiconductor Pb1-xCoxS nanocrystals with nominal concentrations of Co (x = 0.00, 0.10 and
Co2+-doped 0.16) embedded in a chalcogenide glass matrix were synthesized by the low-cost fusion-nucleation method that
PbS allows for the manipulation, control, and tuning of the structural, optical, and electronic properties. Trans­
Nanocrystals
mission electron microscopy images showed the formation and growth of the Pb1-xCoxS nanocrystals to be
Glass
dependent on the thermal annealing time at 500 ◦ C. Energy dispersive X-ray spectroscopy analysis confirmed the
chemical elements Pb, S and Co in the nanocrystal. X-ray diffraction measurements showed characteristic peak
patterns of the PbS rock-salt crystal structure with displacement to greater angles of the plane (111) with the xCo
doping. Magnetic force microscopy measurements showed the magnetic phase-contrast patterns, providing
additional evidence of incorporation of Co into the PbS structure. The energy parameters of the crystal field
strength (Δ = 3898 cm− 1), Racah (B = 794 cm− 1) and spin-orbit coupling (λ = - 555 cm− 1) that are part of the sp-
d exchange interactions of Co2+ ions in tetrahedral sites [CoS4]6- in Pb1-xCoxS nanocrystals were determined by
UV-VIS-NIR optical absorption spectra and the crystalline field theory from the Tanabe-Sugano diagram for d7
ion in a ligand tetrahedral.

1. Introduction
Narrow-gap semiconductors have been explored technologically in
sensors, LEDs, solar cells, among others, due to their structural, elec­
tronic, optical, and thermal properties [1–5]. The properties of nano­
sized materials differ from Bulk due to the broken translational
symmetry, the large surface area of atoms, structural defects, and sur­
face anisotropy [6]. Semiconductor nanocrystals (NCs) can improve
such properties and increase light absorption with band gap energy
changes [7]. The quantum confinement effect of nanocrystals doped
with magnetic ions enables the tuning of the band gap for different
energies and enhances the technological applications of diluted

* Corresponding author. Departamento de Física, Instituto de Ciências Exatas, Naturais e Educação, Universidade Federal do Triângulo Mineiro, 38025-180,
Uberaba, MG, Brazil.
** Corresponding author.
E-mail addresses: ricardo.silva@uftm.edu.br (R.S. Silva), edervgol@gmail.com (E.V. Guimarães).

https://doi.org/10.1016/j.matchemphys.2021.124766
Received 23 March 2021; Received in revised form 16 May 2021; Accepted 20 May 2021
Available online 25 May 2021
0254-0584/© 2021 Elsevier B.V. All rights reserved.
R.S. Silva et al.
magnetic semiconductor nanocrystals (DMS) NCs [1,8]. The new prop­
erties that define the DMS NCs are consequences of the magnitude of the
d-d interactions between neighboring magnetic ions and the sp-d ex­
change interactions between the localized magnetic ions and the spin of
the polarized charge carriers in the host nanocrystal crystal lattice as a
function of size and concentration of the magnetic dopant [1,9–13].
Lead sulphide (PbS) is a semiconductor material with a crystalline
structure (rock-salt) FCC (a = 5.93 Å) [14], a band gap of 0.41 eV and an
exciton Bohr radius of 20 nm [15]. Different quantum confinement re­
gimes change the band gap from 0.41 eV (3024 nm) PbS bulk to around
0.95 eV (1300 nm) quantum dots PbS [16,17]. Size-dependent PbS NCs
are considered an efficient sensitizer, covering the spectral range from
visible (VIS) to near-infrared (NIR) [18–20]. These materials can be
applied as photodetectors [21] and photovoltaic cells in the
near-infrared region [22]. While the PbS bulk behaves diamagnetically,
PbS NCs may show ferromagnetism d0 of unpaired spins due to intrinsic
defects (vacancies) in the crystal lattice. Already the transition metal
cobalt has the following electronic configuration for the free ion Co2+
3d7 in spectral terms in increasing order of energy: 4F, 4P, 2H, 2G, 2F,
2D, 2P. Consequently, with spin 3/2 magnetic moment. Under the action
of a tetrahedral crystal field (Td), the fundamental term 4F and the
excited 4P and 2G split in spectral term components 4A2 + 4T1 + 4T2, 4T1
and 2A1 + 2E + 2T1 + 2T2, respectively. Materials with Co2+ ion in Td
sites have a deep blue color and optical absorption bands in the visible
and near-infrared [23,24]. According to the crystal field theory, spin
allowed d-d electronic transitions of the Co2+ ion in the crystal host
(PbS) can be identified [23–26]. In a crystal solid, the Co dopant tends to
be easily accommodated in PbS lattice sites because the ionic radius of
Co2+ (0.72 Å) is smaller than the radius of Pb2+ (1.19 Å) [23,27]. The
incorporation of Co2+ transition metal ions in PbS NCs (forming
Pb1-xCoxS NC) gives rise to new physical properties attributed to the
potential (s-d) and kinetic (p-d) exchange interactions between the sp
bands of the host semiconductor (PbS) and the d orbitals of the Co2+
ions. This allows great possibilities for technological applications from
different fields, such as in catalysis, biotechnology/biomedicine [28], as
well as in the production of new optoelectronics [1,29] and spintronic
[30–34] nanodevices.
We have reports of synthesis Co-doped PbS thin films prepared by the
chemical bath deposition technique [35], the spray technique using a
perfume atomizer [36] and Co2+ doped PbS nanoparticles by the hy­
drothermal method [37]. DMS NCs with x control of 3d magnetic ions
and DMS NCs as a function of the x-transition metal concentration
grown in a glass matrix have been studied in: Pb1-xMnxS [16,29],
Pb1-xCoxSe [23], Cd1-xCoxS [38], Zn1-x-yMnxCoyTe [39], Bi2-xCrxTe3 [40]
and Bi2-xCoxS3 [24]. In this work, Pb1-xCoxS NCs with different Co
concentrations were grown in a stable and transparent chalcogenide
glass template (SNABP) by the economical fusion-nucleation and ther­
mal annealing techniques. The objective was to select a thermally stable
host matrix that allows observing, tuning and controlling the repro­
ducible growth of the Pb1-xCoxS NCs to assist in understanding the
physical properties for possible technological applications. X-ray
diffraction (DRX), transmission electron microscopy (TEM)/Energy-­
dispersive X-ray spectroscopy (EDS or EDX), atomic force micro­
scopy/magnetic force microscopy (AFM/MFM) and UV-VIS-NIR
absorption spectroscopy (OA) were used to investigate the structural,
morphological, magnetic, optical and electronic properties of these new
materials. The characterizations informed the crystalline structure,
doping, crystal size, chemical composition, magnetic phases, band gap,
confinement energy, sp-d exchange interactions, and d-d transition
characteristic of the Co2+ ion located at Td sites (CoS4]6-) in the
Pb1-xCoxS NCs.
2. Samples and experimental procedures
All chemical reagents used as starting materials in the DMS NCs
synthesis procedure and grown in a glass matrix were obtained from the
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Materials Chemistry and Physics 269 (2021) 124766
company Sigma-Aldrich with the following standards of purity: SiO2
(99.9%), Na2CO3 (99.5%), Al2O3 (99.9%), B2O3 (99.98%), PbO (99%), S
(99,5%) and Co (99.9%). The chalcogenide glass matrix of chemical
composition 40SiO2. 30Na2CO3. 1Al2O3. 24B2O3. 5PbO (mol %), named
SNABP, provided an excellent template for the growth of Pb1-xCoxS NCs.
The samples were prepared by the fusion-nucleation method by adding
the nominal quantities 2 [S] (% by weight of SNABP) plus x [Co] (% by
weight of Pb) with respect to (1 - x) Pb with x = 0.00, 0.10 and 0.16. The
powdered chemical precursors were mixed and taken to a furnace for
heating at 1200 ◦ C for 30 min in an alumina crucible and in a carbon-
rich atmosphere, which is of fundamental importance since it reduces
oxidation of the glass matrix precursors. This reduction further increases
the concentration of available Pb2+, S2− and Co2+ ions, which is
necessary for the formation and growth of Pb1-xCoxS NCs. Thus, the melt
resulting from mixing in the crucible undergoes rapid cooling below
room temperature to form a supersaturated viscous solution composed
of the precursor ions Pb2+, S2− and Co2+ (solute) dissolved in the SNABP
glass matrix (solvent). The newly formed glass template was subjected to
thermal annealing at 500 ◦ C for 2, 4, 6, 8, 10 and 12 hs (the temperature
and the annealing time are decisive parameters for the stable and uni­
form control of the desired size of the NCs in the vitreous matrix) [15].
This step provides the necessary energy for the phase transition in the
supersaturated viscous solution of the glass matrix, and consequently
the kinetic growth of precipitated Pb1-xCoxS NCs (solid phase) due to the
controlled diffusion thermodynamic process of the dissolved precursor
ions in the SNABP glass matrix [41,42].
Instrumental analyses via TEM/EDS, XRD, AFM/MFM and OA UV-
VIS-NIR were used to characterize the samples. All measurements
were performed at room temperature. The identification of the crystal­
line structure of the Pb1-xCoxS NCs was revealed using X-ray diffraction
patterns obtained with an XRD-6000 Diffractometer (Shimadzu) using
the monochromatic radiation line Cu-Kα1 (λ = 1.54056 Å). TEM mi­
crographs and EDS were taken using a JEM-2100 (JEOL, 200 kV) to
investigate the formation, size, shape, growth, and chemical composi­
tion of the thermally annealed NCs. The samples were processed to a fine
powder and taken on a copper plate to perform the measurement due to
the dielectric template’s characteristics. Information about the magnetic
phase formed in the Pb1-xCoxSe NCs was obtained by a Shimadzu
Scanning Probe Microscope (SPM-9600). AFM/MFM images were
scanned with nominal resolution in the vertical z-direction for topo­
graphic images of 0.01 nm and for horizontal images of 0.2 nm. The
tapping mode was used to obtain the sample surface topography, and the
lift mode was used for the magnetic phase. In the lift mode, the
tip− sample distance varied by tens to hundreds of nanometers. Optical
absorption band spectra of the Pb1-xCoxS NCs in the 400–2000 nm range
were recorded with a Shimadzu UV-VIS-NIR spectrometer, model UV-
3600, operating between 190 and 3300 nm.
3. Results and discussion
3.1. Structural and morphological analysis
Fig. 1 a) shows XRD patterns of the Pb1-xCoxS NCs grown in the
SNABP glass matrix for three different cobalt concentrations xCo (x =
0.00; 0.10; 0.16). The samples were thermally annealed at 500 ◦ C for 12
h. The broad shoulder on the curve of the XRD Diffractograms present in
the characterization of the samples refers to the SNABP glass matrix. The
formation of crystal phases is not observed for non-doped SNABP glass.
The observed diffraction peaks are compatible with the powder
diffraction standard JCPDS card No. 05–0592 for the face centered cubic
rock-salt structure (CFC) of PbS with a constant lattice = 5.936 Å [43,
44]. This is represented by the data from the PbS bulk analysis at the
bottom of Fig. 1 a). Despite the amorphous character of the vitreous
matrix that interfered with the observation of diffraction peaks for
quantum dots, the high crystallinity of the Pb1-xCoxS NCs is revealed by
the intensity sharpness of the XRD peaks oriented preferentially towards
R.S. Silva et al. Materials Chemistry and Physics 269 (2021) 124766

Fig. 1. a) Standard XRD measurements for SNABP

and SNABP: Pb1-xCoxS glass matrix samples thermally
annealed at 500 ◦ C for 12 h compared to the PbS bulk
diffraction pattern (JCPDS No. 05.0592). b) Magnifi­
cation of the region close to the peak (111) showing
the shift to greater 2θ angles as the xCo concentration
increases from 0.00 to 0.16. The dotted curves in a)
and b) are a guide to the eye. c) Dependence of the
lattice parameter in the crystal plane (111), as a
function of the xCo concentration.

the crystal plane (111). The peak of high-intensity XRD (2 0 0) can be
identified for the NC sample of Pb1-xCoxS (x = 0.16), confirming the
structure of the rock-salt crystal and the successful growth of the NCs. No
peaks of any other constituents or impurities were found, prevailing the
main characteristics of the diffraction patterns. However, the associated
effects in the doping process of incorporating Co2+ ions into PbS NCs
show a small displacement of the peak (1 1 1) towards a greater
diffraction angle with increasing xCo concentration in the structure of
the Pb1-xCoxS NCs. These data are shown in Fig. 1 b). Similar behaviors
were observed in Pb1-xCoxSe [23], Cd1-xCoxS [38] and Zn1-xCoxO [45]
NCs. The change in the 2θ diffraction angle is due to the activation en­
ergy for the diffusion of substitutional Co2+ ions through vacancies or
interstitial holes generated by the fusion-nucleation with annealing of
500 ◦ C for 12 h in the PbS semiconductor NCs [23,46]. According to

Fig. 2. TEM images, size histogram and EDS of Pb1-xCoxS NCs grown in SNABP glass thermally annealed at 500 ◦ C for 4 h in a), b) and c) x = 0.00; e), f) and g) x =
0.10 and i), j) and k) x = 0.16. The white circle on the TEM images indicates the region where the EDS measurement was performed on the samples. d), h) and l) show
TEM images of Pb1-xCoxS NCs grown in SNABP glass thermally annealed at 500 ◦ C for 12 h.

3
R.S. Silva et al.
Bragg’s law, increasing the angle θ decreases the distance dhkl from the
crystalline plane (111) and, consequently, in the lattice parameter a =
5.936 Å of the CFC structure. In Fig. 1 c), we can see that the linear
experimental dependence of the process follows Vergard’s law for con­
centrations x = 0.00; 0.10 and 0.16 [47,48]. The change in the
diffraction peak of the crystalline plane (111) caused by a change in the
lattice constant is due to the replacement of Pb2+ (ionic radius of 1.19 Å)
by Co2+ (0.72 Å) in the rock-salt crystalline structure of the PbS. The
results clearly show that a probable relaxation with the incorporation of
Co2+ in tetrahedral sites and the compressive deformation induced by
the host’s glass matrix on the surface of the NCs does not significantly
distort the PbS crystal lattice amidst diluted concentrations of Co2+ ions
[38,49]. The structure is preserved for the Pb1-xCoxS semimagnetic NCs
due to the low concentration of Co ions.
The formation, growth, size, shape, and chemical composition of the
Pb1-xCoxS NCs in the SNABP glass matrix was confirmed by images and
analysis by TEM/EDS (Fig. 2). In Fig. 2 a) x = 0.00; 2 e) x = 0.10 and 2 i)
x = 0.16, one can see images of the Pb1-xCoxS NCs grown on SNABP glass
with thermal annealing at 500 ◦ C for 4 h. The images show Pb1-xCoxS
NCs somewhat spherical, with approximately uniform size and
Fig. 3. 2D AFM/MFM images 400 × 400 nm of Pb1-xCoxS NCs grown in the SNABP glass matrix thermally annealed at 500 ◦ C for 12 h in concentrations x = 0.00 (a;
b), x = 0.10 (c; d) and x = 0.16 (e; f). The topographic sample with size distribution (left panel) and magnetic phase (right panel) identifies the orientation of the total
magnetic moment of the Pb1-xCoxS NCs.
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Materials Chemistry and Physics 269 (2021) 124766
monodispersed in the SNABP glass matrix. It is expected that samples
synthesized in the process will have the same average diameter due to
the same growth kinetics of the NCs. Under the same thermodynamic
conditions, xCo2+ magnetic ions in the nominal quantity mentioned also
do not influence the average radius of the NCs [38]. The white circle in
these TEM images indicates the region where the EDS measurement was
performed on the samples. Gaussian adjustments were made to the size
distribution histograms in relation to the Pb1-xCoxS NCs identified in
images 2 a), 2 e) and 2 i). The average diameter (D) and size dispersion
(σ) were estimated and recorded as D (σ) 4.2 nm (0.7 nm), 4.2 nm (0.3
nm) and 3.7 nm (0.3 nm) in Fig. 2 b) x = 0.00; 2 f) x = 0.10 and 2 j) x =
0.16, respectively. Fig. 2 c), the EDS analysis of the white circle area in
Fig. 2 a), for x = 0.00, shows the Pb and S elements that give rise to the
PbS NCs in the SNABP host glass. In the EDS analysis of Fig. 2 g) and 2 k),
a characteristic Co peak at 6.91 KeV indicates the successful doping of
the PbS NCs with Co2+ ions in the white circle area analysis of x = 0.10
and x = 0.16. In all analyses by EDS, the samples were deposited on a
copper screen where the most intense signal (Cu) characteristic of the
element is observed at around 8 KeV. The intensity of the EDS peaks for
the elements Pb and S observed in the measurements shown in Fig. 2 c)
R.S. Silva et al.
and 2 g) and 2 k) decreases with increasing xCo dopant concentration.
This phenomenon shows the gradual substitutional incorporation of
Co2+ ions in the sites of the crystalline structure of PbS. Pb1-xCoxS NCs
grown on SNABP glass with thermal annealing of 500 ◦ C for 12 h with
diameter (D) of approximately 9.1 nm, 6.3 nm and 5.7 nm are shown in
the images in Fig. 2 d) x = 0.00, 2 h) x = 0.10 and 2 l) x = 0.16,
respectively. In Fig. 2 d), 2 h) and 2 l), the value of the interplanar space
d200 = 0.296 nm attributed to the crystal plane (200) characteristic of
the PbS semiconductor rock-salt structure is identified, as evidenced
previously in the XRD. The average diameter and size dispersion of the
TEM images of the Pb1-xCoxS NCs grown on the SNABP glass were
analyzed by the ImageJ software [50]. As the diameters of the Pb1-xCoxS
NCs are smaller than the exciton Bohr radius of the PbS (aBexc. = 20 nm),
it is concluded that they are in a strong quantum confinement regime
[15,51]. The quantum effect and the formation of DMS NCs evidenced
by TEM/EDS were also verified in the systems SNABP:Pb1-xCoxSe [23],
SNAB:Bi2-xCoxS3 [24] and SNABP:Pb1-xMnxS [29].
MFM increases the evidence of cobalt ions in the crystalline network
of PbS NCs. The magnetic mapping of the sample occurred by the par­
allel and antiparallel orientation of the total magnetic moment of the Co
atoms on the surface due to the interaction forces with the atoms of the
MFM probe’s magnetic tip. Fig. 3 shows images of MFM 2-D 400 × 400
nm from topographic measurements with size distributions (3 a; 3 c; 3 e)
and the corresponding magnetic phases (3 b; 3 d; 3 f) for Pb1-xCoxS NC
samples grown in the SNABP glass matrix with annealing at 500 ◦ C for
12 h in xCo concentrations (x = 0.0; 0.10 and 0.16). The presence of
magnetization in the samples at different regions on the surface of the
Pb1-xCoxS NCs grown in glasses can be seen in the light/dark contrast in
the images in Fig. 3 due to the repulsion/attraction of the magnetized tip
towards the NCs, represented in the vertical bar scale by the north/south
magnetic pole [52]. Such contrasts in the MFM images occur due to the
force gradient occurring in the region of hundreds of nanometers in
height between the tip of the MFM and the magnetization of the sample
Fig. 4. Room temperature UV–VIS–NIR OA spectra of Pb1-xCoxS NCs embedded in the SNABP glass matrix for samples with xCo-concentrations of a) 0.00 e b) 0.10,
annealed for 2 h–10 h at 500 ◦ C. The inset in (b) shows the unit cell of the Co-doped PbS crystal structure. c) Tanabe-Sugano diagram for C/B = 4.5; 3 d7 (Td) with
vertical solid line in Δ/B = 4.9, Δ = 3898 cm− 1 and B = 794 cm− 1 signaling the spin allowed and forbidden transitions.
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Materials Chemistry and Physics 269 (2021) 124766
surface after the topography measurements (touch mode) followed by
the surface scan of the sample (elevation mode). The MFM images reveal
the crystallographic quality and uniform distribution of the total mag­
netic moments of the Pb1-xCoxS NC samples.
In Fig. 3 c) to 3 f), we can effectively observe the sp-d electronic
exchange interactions that contribute to each nanocrystal’s total mag­
netic moment more clearly in places marked by the red rectangles for
samples with Pb1-xCoxS NCs (x = 0.10 and 0.16). The results obtained by
these MFM images are evidence of the replacement and incorporation of
Co2+ ions related to the spins domain in the Pb1-xCoxS NCs. The high
magnitude of the Pb1-xCoxS NC sp-d exchange interactions due to the
accumulation of Co2+ ions close to the surface [38] can be understood as
the self-purification effect [53], which dominates and controls the
doping of semiconductor NCs grown by the fusion-nucleation method
during the thermal annealing of samples at 500 ◦ C [38,46]. The same
contrast does not appear clearly for the sample that contains only PbS
NCs (x = 0.00). However, it shows a low-intensity contrast in the images
of the magnetic phase (Fig. 3 b) as identified by the red rectangles. This
gives evidence of the magnetic behavior of the PbS NCs. MFM images
with similar behavior occurred in Bi2S3 NCs grown on SNAB glass [54].
Recent studies have shown that nanocrystal semiconductors PbS, ZnS,
and Bi2S3 show d0 ferromagnetism associated with unpaired electron
spins due to intrinsic defects (vacancies) [6,55,56]. Paramagnetic states
induced by light attributed to defects have also been detected in PbS NCs
[57].
3.2. Optical absorption and crystal field theory
The shift to larger wavelength of the optical absorption band of the
PbS NCs, grown into SNABP glass matrix subjected to thermal annealing
at 500 ◦ C for 2, 4, 6, 8 and 10 h, are shown in Fig. 4 a), and they show
evidence of the quantum confinement effect [15,29]. The redshift
attributed to the increase in the size of the NCs is in excellent agreement
R.S. Silva et al.
with the MET images and results presented previously. The additional
increase in the heat treatment time gradually increases the diffusion of
Pb2+ and S2− ions and the density and size of PbS NCs. The control of
dimensions by heat treatment (≈500 ◦ C) was observed in PbS [15,29]
and ZnSe [58] quantum dots in glass systems.
In the perturbative treatment of the crystal field theory (CFT) [59],
the energy difference implying crystal field intensity (Δ = 10Dq)
around the Co2+ ion in Pb1-xCoxS NCs can be expressed as follows:
Ze2 〈r4 〉
Dq = , (1)
6R5
where in the expression for Dq, Ze2 are the ligand charge separated by
the metal-ligand distance R and 〈r4 〉 is the average value of the radial
distance of a 3d orbital from the nucleus. When covalency is taken into
account, the observed values can be made to agree well with the
experimental values [60]. In this case, instead of using Equation’s direct
calculations (1) to determine the crystal field split, we deduced the terms
of Δ or Dq by spectroscopic measurements. With some lowest energy,
spin-allowed transition corresponds to exactly Δ, at least to a first order
approximation. Thus, Δ is simply the energy of this absorption band. All
other spin-allowed transitions in cubic molecules will be functions of Δ
and the Racah interelectronic repulsion parameters B and/or C. After,
the ratio Δ/B is plotted against E/B and graphically represented from
Tanabe-Sugano diagrams [60].
The optical absorption spectra of Pb1-xCoxS NCs grown into SNABP
glass matrix with concentrations of x = 0.10 subjected to heat treatment
of 500 ◦ C in time intervals of 2, 4, 6, 8 and 10 h are shown in Fig. 4 b).
The visible wavelength region of the spectrum has a band around 594
nm, attributed to the spin allowed transition, 4A2(4F) → 4T1(4P) [61–63].
The absorption bands at 537, 562, 619 and 641 nm are due to the spin
forbidden transitions, 4A2(4F) → 2T2 (2G), 4A2(4F) → 2A1 (2G), 4A2(4F) →
2
T1 (2G) and 4A2(4F) → 2E (2G) respectively [61,64]. In the NIR ab­
sorption region, there is a spin allowed transition band, 4A2(4F) →
4
T1(4F) around 1477 nm [65]. The position of the absorption bands in
the optical spectra (Fig. 4 b) of the transitions in the VIS and NIR regions
were mapped by Tanabe-Sugano energy level split diagram (C/B = 4.5)
3 d7 (Td) [23,26] as shown in Fig. 4 c). Valuable interpretations of the
spectra allowed for the determination of the Δ/B = 4.91 ratio of the
crystal field split (Δ = 3898 cm− 1) and the Racah parameter (B = 794
cm− 1) that measures the inter electronic repulsion between the terms 4P
and 4F in discovery of the approximate value of Dq. The calculations of Δ
and B have been performed using the barycenters of the VIS and NIR
bands. Similar values of B and Δ were determined in chalcogenide glass
and oxide glass embedded with Pb1-xCoxSe [23] and Bi2-xCoxS3 [24] NCs
and lead silicate glasses with Co2+ ions [66]. The results show the co­
valent character of the bonds in the [CoS4]6- coordination complex and
the sp-d exchange interactions between the host PbS semiconductor and
the doping Co2+ ions. With the expansion of the electronic cloud, the
Co2+ ions feel a weak binding field of S2− ions. More precisely, at
tetrahedral coordination sites ([CoS4]6-) in the PbS Rock-Salt crystalline
structure. The inset in (b) shows the unit cell of the Co-doped PbS crystal
structure. The reduction of B from its free ion value (B ≈ 1120 cm− 1)
[67] indicates a large measure of electron displacement in the d orbital
towards the ligand, and consequently a greater reduction in interelec­
tronic repulsion and greater covalent character in the chalcogenide
complex. The covalent character in the metal-ligand binding is seen in
Bi2-xCrxTe3 [40], Bi2-xCoxS3 [24] and Zn1-x-yCoxMnyTe [25,39] NCs, and
in the Co2+:PbO–Bi2O3–SiO2 glass system [66].
The spin allowed transition 4A2(4F) → 4T1(4F) can be explained by a
strong first-order spin-orbit coupling interaction of Co2+ and points of
symmetry Γ6, Γ8, and Γ8 + Γ7 that split the excited state 4T1(4F) into
three energy sub states called E21, E22, and E23 due to Td symmetry [26,
63]. The division of bands and energy states due to orbit-spin coupling
were observed in CdSxSe1-x thin films [68], Zn1-x-yCoxMnyTe NCs [25,
39], cobalt cordierite glass [63] and Pb1-xCoxSe NCs [23,26]. Since the
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Materials Chemistry and Physics 269 (2021) 124766
radial functions of the e and t2 orbitals do not differ much, we can only
consider single-electron spin–orbit parameter λ [63,65]. Therefore, the
energy of the electronic states of Co2+ occurs as a function of the in­
tensity of the crystal field Δ, Racah parameter B, and the spin-orbit
coupling constant λ. We only used the NIR sub-bands for the calcula­
tion λ due to uncertainties in the positions of the VIS bands. The energy
distances between the three peaks allow for the λ and 4T1(4F) energy
position. λ is calculated by tuning the position of the sub-bands (E21, E22,
and E23) according to the procedure: E21 = E2(expected) − 1, 5λ; E22 =
E2(expected) + λ; E23 = E2(expected) + 2, 5λ. E2(expected) is equivalent to transi­
tion energy 4A2(4F) → 4T1(4F) without the spin-orbit coupling [63,65].
The value of the spin-orbit parameter calculated from the OA spectra is
equal to λ = - 555 cm− 1 for the Pb1-xCoxS NCs grown in the SNABP glass
matrix. This value is similar to those obtained in Co-doped PbSe NCs (λ
= - 665 cm− 1) [26] and CoAl2O4 spinel crystals (λ = - 613 cm− 1) [63]
both in glassy systems.
The energy positions are cobalt concentration independent. The
characteristic bands of absorption in the wavelength of approximately
500–700 nm and from 1200 to 1800 nm and the increase in their in­
tensity (Fig. 4 b) show the doping and increase of the Co2+ ions located
in the Td sites ([CoS4]6-) of the PbS NCs incorporated in the SNABP glass
matrix with increasing thermal annealing time. Such phenomena
become even more favorable due to the difference in the size of the ionic
radius between Co2+ (0.72 Å) and Pb2+ (1.19 Å), as shown in the unit
cell of the Co-doped PbS crystalline structure (inset of Fig. 4 b).
The excitonic absorption energy of the thermal annealing PbS NCs
(500 ◦ C) of 2–10 h (1.42–1.13 eV) is above three energy substates E21,
E22, and E23. These three energy levels from the excited state 4T1(4F) of
Co2+ ions are within the quantized states energy gap of the PbS NCs. The
overlap of the sp energy bands of the PbS semiconductor NCs by the d-
d transitions from the fundamental to excited state shows the influence
of the crystal field of tetrahedral coordination of the S2− ([CoS4]6-) li­
gands on the energy states of the Co2+ ion d orbitals. This provides
unique electronic and optical properties depending on the size of the
NCs and the imminent effects of the sp-d exchange interactions evi­
denced by the change in the UV-VIS-NIR spectrum of the DMS Pb1-xCoxS
in relation to non-doped PbS. In the literature, doped glasses with PbSe:
Co [23], Bi2S3:Co [24] and ZnMnTe:Co [39] NCs have optical and
electronic properties similar to the Pb1-xCoxS NCs grown in the SNABP
matrix. Optical absorption results are in agreement with those obtained
by XRD, TEM and MFM, which provide strong evidence of incorporation
of Co2+ ions to replace Pb2+ ions in Pb1-xCoxS NCs.
4. Conclusions
We have successfully reported a low-cost synthesis to produce,
manipulate, control, and tune the structural, optical, and electronic
properties of the Pb1-xCoxS nanocrystals (NCs). Co-doped PbS NCs were
grown in a SNABP glass matrix by the method of thermal melting and
annealing. The experimental characterization techniques and the crystal
field theory confirmed the incorporation of Co2+ ions in the PbS NCs.
TEM images revealed the formation and growth of Pb1-xCoxS NCs in the
samples annealed at 500 ◦ C for 4–12h. The EDS analysis showed the
presence of the chemical elements Pb, S, and Co in the structure of the
Pb1-xCoxS NCs and X-ray diffraction patterns showed the formation of
diffraction peaks characteristic of the PbS rock-salt crystalline structure
and the displacement to greater angles of the d111 interplanar distance
with increasing xCo concentration. The contrast of the magnetic phase
observed in the AFM/MFM measurements was attributed to intrinsic
defects and the magnetic response of the Co2+ ions in the nanocrystal
structure. The effect of quantum confinement is observed in the redshift
of the exciton band in the optical absorption spectra of the PbS NCs. The
change in the optical absorption spectra between PbS and Pb1-xCoxS (x
= 0.10) NCs from the sp-d exchange interactions were investigated by
the CFT with the Tanabe-Sugano diagram for the d7 ion in a ligand
R.S. Silva et al.
tetrahedral. The energy parameters of the crystal field strength (Δ =
3898 cm− 1), Racah (B = 794 cm− 1) and spin-orbit coupling (λ = - 555
cm− 1) characteristics of the spin allowed d-d transitions. This is strong
evidence of Co2+ ions in tetrahedral coordination sites [CoS4] 6-.
We hope that the scientific study will serve as inspiration for new
research and technological applications.
Credit author statement
Designer and conceptualization E. V. Guimarães, S. A. Lourenço, A,
S. Silva and R. S. Silva. Synthetized and characterized the nanocrystals
E. V. Guimarães, R. E. S. Melo and R. S. Silva. Analyzed the results E. V.
Guimarães, R. E. S. Melo, A. S. Silva, S. A. Lourenço, R. S. Silva. Per­
formed XRD and MFM results A. C. A. Silva and N. O. Dantas. Performed
TEM/EDS results LabMic/UFG. All authors have written, read, and
agreed to the published version manuscript.
Declaration of competing interest
There are no conflicts of interest.
Acknowledgements
The authors gratefully acknowledge financial support from the
following Brazilian Agencies: MCTI/CNPq, PDJ/CNPQ, Capes, Fapemig
and Rede Mineira de Química (RQMG). We are also thankful for use of
the facilities for the MFM measurements at the Instituto de Física
(INFIS), the Universidade Federal de Uberlândia (UFU), supported by a
grant (Pro-Equipamentos) from the Brazilian Agency CAPES and TEM
measurements at the Laboratorio Multiusuario de Microscopia de Alta
Resoluçao (Lab-Mic), Universidade Federal de Goiás.
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