ruvalcaba-manzo2020
ruvalcaba-manzo2020
ruvalcaba-manzo2020
Optical Materials
journal homepage: http://www.elsevier.com/locate/optmat
Invited Article
A R T I C L E I N F O A B S T R A C T
Keywords: The purpose of this paper is establishing two stables and originals formulations routes for the synthesis of
Thin films cadmium carbonate (CdCO3) by chemical bath deposition (CBD) and the analysis of the physical properties of the
Cadmium carbonate synthesized materials, such as optical, chemical, structural and morphological properties by using character
Otavite
ization techniques such as optical absorption by diffuse reflectance, X-ray Diffraction (XRD), X-ray Photoelectron
Spectroscopy (XPS), Scanning electron microscopy (SEM) and Raman. The direct bandgaps values related to
direct transitions of electrons from the valence band to the conduction band of CdCO3 thin films are 3.81 and
3.79 eV. By X-ray diffraction (XRD) technique was determined as a hexagonal structure with space group R-3c
(167) for CdCO3 thin films. Finally, the expected chemical composition of CdCO3 thin films was proving by the
low- and high-resolution X-ray Photoelectron Spectroscopy (XPS) spectra. The Raman spectra show five vibra
tional characteristics frequencies of CdCO3 and evidencing that the synthesized thin films correspond to CdCO3.
* Corresponding author.
E-mail address: [email protected] (S.G. Ruvalcaba-Manzo).
https://doi.org/10.1016/j.optmat.2020.110295
Received 15 June 2020; Received in revised form 15 July 2020; Accepted 31 July 2020
Available online 19 August 2020
0925-3467/© 2020 Elsevier B.V. All rights reserved.
S.G. Ruvalcaba-Manzo et al. Optical Materials 109 (2020) 110295
Table 1
List of used compounds and the aggregation order to grow (A) cadmium car
bonate, CdCO3, thin films.
Compounds Molar concentration Volume
1. CdCl2 0.5 M 5 mL
2. Na₃C₆H₅O₇ 0.5 M 20 mL
3. NH4OH 2M 15 mL
4. NaHCO3 1M 5 mL
5. H2O – 55 mL
Table 2
List of used compounds and the aggregation order to grow (B) cadmium car
bonate, CdCO3, thin films.
Compound Molar concentration Volume
1. CdCl2 0.5 M 5 mL
2. Na₃C₆H₅O₇ 0.5 M 30 mL
3. H2O – 35 mL
4. Sodium borate buffer (pH 10) – 5 mL
5. NaHCO3 1M 5 mL
Cadmium chloride (CdCl2, purity 99%, CAS: 7790-78-5), as a metal NaHCO3 + H2 O → NaOH + H2 CO3
source, sodium citrate (Na3C6H5O7, purity 99%, CAS: 6132-04-36),
ammonium hydroxide (NH4OH, concentration 40%, CAS: 1336-21-6), NaHCO3 + H2 O → NaOH + CO2 + H2 O → NaOH + H +1 + HCO−3 1
as a OH source and sodium bicarbonate (NaHCO3, purity 100%, CAS:
144-55-8) as a carbonate source of the reaction. Aqueous solutions were 2NH4 OH + 2NaOH + 2Cl− 1 → 2O− 2
+ 2H2 O + 2NaCl + 4H2 + N2
prepared using deionized water.
2
CO2 + O− + H2 O → CO−3 2 + H2 O
(B) Formulation for CdCO3
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S.G. Ruvalcaba-Manzo et al. Optical Materials 109 (2020) 110295
2.3. Characterization
3. Results
• Optical absorption
The absorption spectra of CdCO3 (A) and (B) versus 1a) wavelength
and 1b) energy are showed in Fig. 2. The absorption edge for CdCO3 (A)
corresponds to wavelengths lower than 370 nm and an absorption edge
for wavelengths lower than 380 nm for CdCO3 (B) thin film. Further
more, in the absorption spectra as a function of the energy of the photon
is observed an increasing absorption threshold for higher energy than
3.5 eV and is related to the main electronic transitions or fundamental
absorption.
Meanwhile, in Fig. 3 is shown the optical bandgap (Edgap) for CdCO3
(A) and (B) thin films estimated from (αℎv)2 versus energy (ℎv) curve,
where α is the optical absorption coefficient, and the photon energy (ℎv).
By extrapolating the straight-line of the plots of CdCO3 (A) and (B) for
zero absorption value gives the values for direct transitions of 3.81 eV
Fig. 2. Absorption spectrum as a function of (a)wavelength and (b)energy for and 3.79 eV, respectively, and are in concordance with the bandgap
CdCO3 (A) and (B) thin films. value reported in the literature for CdCO3 ~3.86–4 eV [7,20].
Fig. 3. Direct bandgap plot for (A) and (B) cadmium carbonate thin film, CdCO3, calculated by Tauc method.
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S.G. Ruvalcaba-Manzo et al. Optical Materials 109 (2020) 110295
Fig. 4. a) XRD diffractogram of CdCO3 (A) and (B) thin films and b) PDF #42–1342.
• X-ray diffraction (XRD) crystallographic planes: (0 1 2), (1 0 4), (0 0 6), (1 1 3), (2 0 2), (0 2 4), (0
1 8), (1 1 6), (1 2 2), (1 0 10), (2 1 4), (2 0 8), (3 0 0) and (0 0 12),
The X-ray diffraction characterization (XRD) technique is employed respectively, reported in the reference (PDF 42–1342, ICSD 20181). The
to determine the crystal structure of materials, lattice parameters, and preferential orientation for CdCO3 (A) and (B) thin film is in the plane (0
crystal size. The structure of CdCO3 (A) and (B) films was confirmed 1 2) and (1 0 4), respectively. With this information, it is possible to
with a diffractometer using a CuKα radiation source with a wavelength estimate the crystallite size from the Debye Scherrer formula for the
of 1.5406 Å. peaks labeled with the Miller indices (0 1 2) and (1 0 4) of the samples
To confirm the crystalline structure for CdCO3 thin films, Fig. 4 CdCO3 (A) and (B), respectively.
shows the diffractograms of CdCO3 thin films (A) and CdCO3 films (B).
0.9λ
The CdCO3 (A) diffractogram was transferred vertically for comparative D=
β cos θ
purposes. The XRD patterns of CdCO3 samples are in concordance with a
hexagonal polycrystalline structure [3,20,21] with space group R-3c where D is the crystallite size, β is full width at half maximum (FWHM)
(167), reported in the literature (PDF# 42–1342, ICSD 20181). Th in radians, λ is the wavelength of the X-ray source (CuKα = 1.5406 Å)
vertical axis corresponds to the intensity in arbitrary units versus the and θ is the diffraction angle. β was calculated and in the case of CdCO3
variation 2θ angle in degrees. Well-defined diffraction peaks are related (A) it has a value of 0.324 and for CdCO3 (B) is 0.486.
to a good crystallinity while width of the diffraction peaks are related to
crystallite size whose are observed at positions 2θ = 23.42◦ , 30.24◦ , 0.9(1.5406 Å)
32.88◦ , 36.32◦ , 40.06◦ , 43.72◦ , 48.06◦ , 49.46◦ , 49.86◦ , 58.16◦ , 60.76◦ ,
D(A) = ( ) ( ) = 250.40 Å
π
(0.324) 180 cos 23.42
61.68◦ , 62.96◦ , 65.44◦ and 69.18◦ which are in concordance with the 2
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S.G. Ruvalcaba-Manzo et al. Optical Materials 109 (2020) 110295
Fig. 5. XPS spectrum from 0 to 1100 eV region under low-energy resolution conditions for (A) and (B) CdCO3 sample.
metal carbides. On the other hand, Fig. 6b) shows are in concordance
0.9(1.5406 Å)
D(B) = ( ) ( ) = 169.32 Å with the obtained at the C 1s level in Fig. 6a). The O 1s level shows the
π
(0.486) 180 cos 30.24
2
presence of four oxygen components in the CdCO3 (A) sample corre
sponding to oxygen contamination with a binding energy of 531 eV,
The approximate sizes of the crystallite formations oriented at (0 1 2) CdCO3 with binding energy at 531.4 eV, and substrate components, such
and (1 0 4), are 25 nm and 17 nm, respectively. as CaO and SiO2 at 529 and 532.9 eV binding energy values, respec
tively. Graph 6c), shows peaks corresponding to an electronic doublet of
• X-ray Photoelectron Spectroscopy (XPS) CdCO3 3d5/2 and 3d3/2 with binding energies 405.1 and 411.75 eV for
CdCO3 (A) thin film and doublet separation of Δexp = 6.75 eV.
In the characterization of X-ray photoelectron spectroscopy (XPS) for As can be seen in Fig. 6d), C 1s level reveals the presence of three
the CdCO3 (A) and (B) thin films, to verify the elemental composition of carbon species in CdCO3 (B) sample studied, attributed to the adventi
CdCO3 thin films the XPS spectra were taken by using (Mg Kα) X-ray tious carbon contamination (285 eV), CdCO3 (289.3 eV), and the third
radiation as the excitation source. The analysis range of binding energy one (288 eV) corresponding to carbon compound such as C– – O. The
is from 1100 to 0 eV, as is shown in Fig. 5. Furthermore, in XPS spectra is deconvolution of the carbon spectrum indicates the differences between
observed the presence of the principal elements contained in the thin (A) and (B) formulations of CdCO3. In addition to adventitious carbon
films as Cd, C, and O. The element sodium (Na, 1s) also appears and is contamination and CdCO3, in the (B) formulation is observed a carbon
attributed to the sodium citrate, Na₃C₆H₅O₇, employed as a complexing compound, C– – O, and it means the presence of residuals in the film [7,
agent, and to the carbonate source, NaHCO3. In the case of CdCO3 (B) 22]. Also, in Fig. 6e) is shown the presence of oxygen contamination,
thin films, the sodium is also from the sodium borate buffer employed as CdCO3, and substrate components of thin film. In the case of CdCO3 thin
OH ions precursor. Meanwhile, oxygen and carbon (C, O) can also be films (B) in Fig. 6f), the electronic doublet gap is Δexp = 6.77 eV for Cd 3
environmental contaminants. The presence of silicon (Si) is due to the d.
substrate employed to thin-film deposit. Therefore, this led to an anal
ysis of high-resolution XPS (called multiplex), in the region of binding • Scanning electron microscopy (SEM)
energies of the elements that are assumed to be principal. See Fig. 6.
To precise the principal chemical composition of CdCO3 thin films, Fig. 7 shows images obtained from the scanning electron microscopy
high-resolution XPS analysis was performed in the regions of the energy (SEM) for thin films of CdCO3 (A) and (B). a) and b) images correspond
sub-levels C 1s, O 1s, and Cd 3 d, these spectra are shown in Fig. 6. The to superficial micrographs of CdCO3 (A) at two different working scales,
spectrum 6a shows the experimental, fitting curve, and deconvolution 10 and 1 μm, or magnifications of 2000× and 5000×, respectively. The
for CdCO3 (A) sample. There are three carbon species in the 1s state for entire surface area of the substrate is covering by clusters of agglomer
CdCO3 (A), one specie corresponding adventitious carbon contamina ates with elongated shapes of sizes not larger than 10 μm. Micrographs
tion with a binding energy of 284.5 eV, and two other species located c) and d) with magnifications of 2000× and 5000×, respectively, show
approximately in the 289.3 eV and 283 eV in concordance with the the formation of sphere agglomerates of sizes less than 1 μm and are
literature [21,22], and are associated with the presence of CdCO3, and related to CdCO3 (B) thin films. In the literature, different morphologies
SiC, respectively. The presence of SiC is due to the use of argon sput are reported, depending on the conditions and methods of synthesis, and
tering to clean up the thin film surface, promoting the formation of SiC it is possible to find rods, spheres, cubes, or amorphous forms [2,7].
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S.G. Ruvalcaba-Manzo et al. Optical Materials 109 (2020) 110295
Fig. 6. XPS spectra for a) C 1s, b) O 1s and c) Cd 3 d under high resolution conditions for CdCO3 (A) thin film. XPS spectra for d) C 1s, e) O 1s and f) Cd 3 d for CdCO3
(B) thin film.
• Raman and 1719 cm− 1) is related to the combination of symmetric and asym
metric internal vibrations of C–O [7,23]. In formulation (B) of CdCO3,
The Raman spectra in the region between 100 and 1950 cm− 1 by two unidentified frequencies not reported as characteristical frequencies
exciting the samples with 532 nm, shows the values of intensity and of CdCO3 and probably matched with the residues present in the thin
Raman shift of peaks obtained for the CdCO3 samples gives us the fre film. The Raman spectrum of the films obtained by both formulations
quencies associated with the vibrational modes of CdCO3 (A) and (B) in shows more evidence that the synthesized thin films are CdCO3.
Fig. 8. Three vibrational frequencies are related to the CO3 group: vi
bration by symmetric stretching of C–O, A1g (ν1) (1090 and 1086 cm− 1), 4. Conclusions
asymmetric stretching of C–O, Eg (ν3) (1397 and 1392 cm− 1) and in the
plane for the CO3 ion Eg (ν4) (718 and 713 cm− 1); and two bands We reported in this research work two formulations for the synthesis
associated with the translation and libration of the CO3 ions around Cd of CdCO3 thin films by CBD. The results obtained by characterization
atoms, Eg (ν13) (275 and 269 cm− 1) and Eg (ν14) (165 and 159 cm− 1), techniques were enough to identify optically, structurally, and chemi
respectively. The band located at a vibration frequency A1g + Eg (1714 cally the CdCO3 (A) and (B) thin films and are consistent with previously
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S.G. Ruvalcaba-Manzo et al. Optical Materials 109 (2020) 110295
Fig. 7. a) and b) are SEM image for CdCO3 (A), c) and d) are SEM image for CdCO3 (B) in work scale of 10 and 5 μm, respectively.
reported research in the literature. The direct bandgaps calculated from the films obtained by both formulations shows more evidence that the
Tauc’s method are 3.81 and 3.79 eV, respectively. The XRD analysis synthesized thin films are CdCO3.
shows a hexagonal (rhombohedral) polycrystalline structure for (A) and
(B) thin films. From SEM images was observed different morphologies CRediT authorship contribution statement
for each formulation. By XPS spectra was verify the presence of the el
ements contained in the synthesized thin films. The Raman spectrum of S.G. Ruvalcaba-Manzo: conception and design of study, acquisition
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S.G. Ruvalcaba-Manzo et al. Optical Materials 109 (2020) 110295
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