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Optical Materials 85 (2018) 425–437

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Growth and characterization of ammonium nickel-copper sulfate T


hexahydrate: A new crystal of Tutton's salt family for the application in
solar-blind technology
Santunu Ghosha,∗, Alessandro H. Limaa, Leonã S. Flôresb, Tiago S. Pachecoa, Ananias A. Barbosaa,
Saif Ullaha, João P.A. de Mendonçaa, Luiz F.C. Oliveirab, Welber G. Quirinoa
a
Department of Physics, Federal University of Juiz de Fora, Juiz de Fora, 36036-330, MG, Brazil
b
Department of Chemistry, Federal University of Juiz de Fora, Juiz de Fora, 36036- 330, MG, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: We have obtained the mixed crystals ammonium nickel-copper sulfate hexahydrate compounds which exhibits
Solar-blind filters 98% transmittance in the ultraviolet region, a promising material for UV light filters and UV sensors for solar-
Crystal growth blind technology. These crystals belong to the family of Tutton's salt having empirical formula (NH4)2NixCu(1-x)
Hirshfeld surface (SO4)2.6H2O and they were synthesized by employing growth from the slow evaporation of aqueous solution
Thermogravimetric analysis
technique. The crystallographic parameters, three-dimensional Hirshfeld surface analysis and the calculation of
UV–Vis spectroscopy
two-dimensional fingerprint plots of the sample crystal (NH4)2Cu(SO4)2.6H2O were determined with the help of
Near-infrared spectroscopy
single crystal X-Ray diffraction. The X-ray powder diffraction of the pulverized samples were carried out at
ambient temperature, 200 °C and 350 °C with the purpose to observe the change in the crystalline structure when
subjected to higher temperatures. The thermal analysis of the samples was conducted in the temperature range
30–900 °C with the help of thermogravimetric analysis (TGA), which provides the information about the thermal
stability and decomposition process during the heat treatment. Some of our sample crystals demonstrated high
dehydration temperature up to 108 °C and they can be considered as an excellent candidate for UV light filters
for high temperature applications. The direct and indirect band gaps of the samples were determined from
UV–Vis spectra with the help of Tauc's equation. The overtones and combinations of fundamental vibrations of
the functional groups our sample crystals were investigated by utilizing near-infrared spectroscopy in the wa-
velength range 830–2500 nm.

1. Introduction reactor. On the other hand, due to the man-made chemical activity
there is a depletion in ozone layer [3], as a result we are suffering an
The ultraviolet region from 200 to 300 nm wavelength range is interrelated impending health risks [4–7] by the increasing level of
solar-blind because it is strongly absorbed by the ozone layer in the harmful UV radiation in our environment [8,9]. The solar-blind UV
upper atmosphere, as a result of that, the intensity of solar UV radiation sensors can be used for UV inspection in everyday usable food products
in the solar-blind region near to the surface of the earth is almost zero. and the detection of UV radiation in hazardous industrial waste.
The utilization of certain kind of materials as UV light filters which UV light filters exhibits maximum transmission in the ultraviolet
provides full absorption in other subbands of the UV and visible region, region and strong absorption in all other wavelengths. Initially glass
offers a unique opportunity for the design of a whole new class of highly filters were used for UV light filters, since they are transparent in the
sophisticated devices for diagnostic equipment. Development of this wavelength range 300–500 nm, but this reduces the efficiency of the
type of technology was termed as “solar-blind” technology [1,2] and is glass light filters used in the solar-blind devices based on the detection
widely used for the defense purposes. These types of devices are ex- of UV radiation in the 200–300 nm spectral region. After that, various
tensively used in the area of remote sensing as required for missions like materials, such as aluminium gallium nitride (AlGaN) [10–13], silicon
aircraft protection, sniper shoot detection, modern missile approach carbide (SiC) [13–16] and diamonds [17–19] have been used for the
warning system, terrorist attack surveillance, as well as in nuclear next-generation solar-blind photodetectors. In recent years it has been


Corresponding author.
E-mail address: santunug@gmail.com (S. Ghosh).

https://doi.org/10.1016/j.optmat.2018.09.004
Received 28 July 2018; Accepted 2 September 2018
0925-3467/ © 2018 Elsevier B.V. All rights reserved.
S. Ghosh et al. Optical Materials 85 (2018) 425–437

observed that, the crystals of Tutton's salt can be used to locate and compared their results with the neutron diffraction experiment per-
track the sources of ultraviolet light energy and can be used as a pro- formed at 9 K.
mising material for UV light filters [2,20] in solar blind technology. In the present article, we are reporting the crystal growth of am-
The family of Tutton's salts are the isomorphic hydrated complexes monium nickel copper sulfate hexahydrate crystals by using growth
crystalize in the monoclinic system with centrosymmetric space group from the aqueous solution by slow evaporation technique. The mor-
P21/c [Z = 2] [21,22], with empirical formula M2M′(SO4)2.6H2O or phological and structural characterization of our sample crystals were
M2M′(SeO4)2.6H2O, where M is an univalent cation which may be Cs+, carried out with the help of X-ray diffraction and thermogravimetric
K+, NH4+, Rb+, Tl+ and M′ is a bivalent cation of the first transition analysis. The optical spectroscopy of the samples has been investigated
series metals Co+2, Cr+2, Cu+2, Fe+2, Mn+2, Ni+2, V+2, Zn+2. The with the help of UV–Vis and near-infrared spectroscopy.
unit cell of Tutton's salt contains one or more octahedral hexahydrate
complexes [M′(H2O)6]2+ in the crystal unit cell where, M′ is situated at 2. Materials and methods
the inversion center and surrounded by six water molecules through a
slightly distorted octahedral formed by the Jahn–Teller effect [23–26]. There are different techniques available to grow the crystals of the
The Jahn-Teller effect is a geometric distortion; if the ground state Tutton's salt, such as, diffusion gel technique in silica hydro-gel media
electronic configuration of a non-linear complex is orbitally degenerate [53], Sankaranarayanan–Ramasamy (SR) method [47] and super-
the complex will distort so as to remove the degeneracy and achieve a cooling and forced convection technique [75]. In our present work,
lower energy. This type of distortion is typically observed among oc- sample crystals were obtained by employing conventional isothermal
tahedral complexes [27,28] where the two axial bonds can be shorter or evaporation of aqueous solution crystal growth method. For the pre-
longer than those of the equatorial bonds. paration of the solution reagents, ammonium sulfate were (NH4)2SO4
The low dehydration temperature and high hygroscopicity are the fixed at 5 g, and the mass of the nickel sulfate NiSO4.6H2O and the
main drawbacks of the crystals of the Tutton's salt for the applications copper sulfate Cu(SO4)7H2O were obtained from the stoichiometric
in solar blind filters. It has been observed that, nickel sulfate hexahy- ratio given by the empirical formula (NH4)2NixCu(1-x) (SO4)2.6H2O.
drate (NSH) crystals demonstrates same type of UV transmission char-
acteristics as that of other Tutton's salt, but they also exhibit better (NH 4)2 SO4 + Ni(SO4 )6 H2 O+ Cu(SO4 )7 H2 O⇄ (NH 4)2 NixCu(1 − x)(SO4 )2.6
thermal stability and higher dehydration temperature, which is suitable H2 O+ ↑ H2 O
for UV light filters for high temperature applications. For the first time,
The purity of nickel sulfate is 99%, whereas purity of ammonium
α-nickel sulfate hexahydrate crystal (α-NSH) was studied for solar blind
sulfate and the copper sulfate is 98%. The quantities of the reagents
UV light filters [29]. There are some very important studies about the
were used in the crystal growth process is shown in the Table 1. To
crystal growth, morphological and structural analysis, optical spectro-
obtain the mixed ammonium nickel-copper sulfate hexahydrate (AN-
scopy and vibrational spectroscopies of NSH crystals, such as, po-
CUSH) crystals, we have varied the concentration of Cu(II) by 10%,
tassium cobalt nickel sulfate (KCNSH) [30–38], potassium nickel sulfate
30%, 50%, 70% and 90%. In addition, we have also prepared the so-
hexahydrate (KNSH) [39–41], cesium nickel sulfate hexahydrate
lution to obtain pure crystals of ammonium nickel sulfate hexahydrate
(CNSH) [42], rubidium nickel sulfate hexahydrate (RNSH) [43,44],
(ANSH) and ammonium copper sulfate hexahydrate (ACUSH). The
guanidine carbonate doped nickel sulfate hexahydrate [45], α-nickel
calculated masses of the reagents were placed in a beaker and then we
sulfate hexahydrate (α-NSH) [29,46–49], potassium manganese nickel
have added approximately 100 ml deionized water (re-
sulfate hexahydrate (KMNSH) [50,51], zinc nickel sulfate hexahydrate
sistivity = 18.2 MΩ and pH = 7). The dilution of the reagents was oc-
(ZNSH) [52], Zn (II) doped ammonium nickel sulfate hexahydrate [53],
curred with the help of magnetic stirrer, where the temperature was
potassium zinc nickel sulfate hexahydrate (PZNSHH) [54], ammonium
varied from 60°C to 70 °C throughout the process. After dilution, the
nickel sulfate hexahydrate (ANSH) [2,55–57], ammonium nickel cobalt
solution was filtered and then brought to a greenhouse where the
sulfate hexahydrate (ACNSH) [58–61].
temperature was maintained at 40 °C.
There is a considerable amount of studies of the crystals of copper
The single-crystal X-ray diffraction measurement for ammonium
Tutton's salt. Stoneham et al. [62] reported a calculation of the spin-
copper sulfate hexahydrate crystal ((NH4)2Cu(SO4)2.6H2O) have been
lattice relaxation of Cu+2 in potassium zinc copper Tutton's salt on the
performed using a Supernova Agilent diffractometer with CCD detector
basis of crystal field model. Breen et al. [63] and Hoffman et al. [64]
through MoKα radiation at room temperature. The data collection,
investigated the spin-lattice relaxation of the octahedral complex of
reduction, unit cell refinement, and absorption correction have been
copper by using electron paramagnetic resonance (EPR) and electron-
obtained by using Crysalis RED software (Oxford Diffraction Ltda,
spin-echo (ESE) methods; Zhou et al. [65] used EPR spectroscopic
version 171.38.41) [76]. The structures have been solved and refined
measurements to determine the magnitude of the electron-electron
using the SHELX-14 program package [77] and the figures have been
exchange energy of Cu atoms in ammonium copper Tutton's salt. Bosi
produced using Mercury 3.9 [78], ToposPro package [79,80] and
et al. [66] and Ballirano et al. [67,68] reported the structural features of
CrystalEXplorer [81] softwares. All non-hydrogen atoms were refined
Cu Tutton's salt, whereas Simmons et al. [69] reported high pressure
anisotropically. Hydrogen atoms connected to oxygen were placed in
and low temperature single crystal neutron diffraction study of deut-
idealized positions and treated with the rigid model. Hydrogen atoms
erated and hydrogenous hexaaquacopper sulfate. Schultz et al. [70]
from water molecules were directed by difference maps and refined
reported the influence of pressure on the unit cell parameters of deut-
erated ammonium copper(II) sulfate hexahydrate at various tempera-
Table 1
tures from 50 to 325 K obtained from pulsed neutron powder diffrac-
The variation of nickel and copper compositions and the masses of NiSO4.6H2O
tion. Cha et al. [71]investigated infrared hole burning of ammonium and CuSO4.7H2O used in the preparation of the solutions.
copper Tutton's salt with the help of tunneling kinetics and Jahn-Teller
distortions. Soumati et al. [72] presented the growth, characterization Ni x (%) NiSO4.6H2O (g) Cu (1-x) % CuSO4.7H2O (g)

and thermal analysis of potassium copper sulfate hexahydrate crystals. 100 9.9450 0 –
In addition, there are some computational studies also available, such 90 8.9520 10 0.9430
as, Beagley et al. [73] performed Ab initio molecular orbital calculations 70 6.9740 30 2.8340
on the free octahedral copper complex in D2h symmetry, on the other 50 4.9746 50 4.7224
30 2.9850 70 6.6123
hand Chandler et al. [74] calculated the structure factor by using ab
10 0.9940 90 8.5020
initio quantum-mechanical calculations on individual isolated ions near 0 – 100 9.4475
to the Hartree-Fock limit in a deuterated copper Tutton's salt and

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with O-H = 0.85 Å, and Uiso(H) = 1.5 Ueq(O). Table 2


Powder x-ray diffraction analysis were performed in a Bruker dif- Crystallographic data and the structure refinement parameters of the single
fractometer (D8 Advance) using monochromatic Cu-Kα radiation crystal (NH4)2 Cu (SO4)2.6H2O.
source (λ = 1.5406 Å). The measurements were taken place with 40 kV Crystal Data
and 40 mA for cathode voltage and current, respectively, in the range
from 5 to 90°(2θ) with the steps of 0.02°. We have performed X-ray Empirical Formula (NH4)2 Cu (SO4)2.6H2O
Molecular Weight (g/mol) 399.85
diffraction of the pulverized samples of our crystals at ambient tem-
Crystalline system, Space Group Monoclinic, P21/c
perature, 200 °C and the 350°. For X-ray powder diffraction at higher a (Å) 6.2354(4)
temperatures, samples were sprayed and placed in crucibles and taken b (Å) 12.4002(7)
to the oven where they remained for approximately 1 h 15 min at 200 °C c (Å) 9.1709(6)
and 2 h at 350 °C. Thermogravimetric analysis (TGA) were carried out β (°) 106.600(7)
V(Å3) 679.54(8)
by using a SHIMADZU DTG-60 equipment. Powder samples were he- Z 2
ated from 30 to 900 °C with a heating rate of 10 °C/min under a ni- D (Mg/m3) 1.638
trogen atmosphere with a rate flow of 50 mL/min. Absorption Coefficient, μ (mm−1) 3.16
The UV–Vis transmittance spectra were obtained by using an UV- F (000) 344
Measurement Parameters
VIS-NIR spectrometer from Shimadzu UV-1800 dual beam. To perform
Range for data collections θ (°) 3.286–29.612
UV–Vis experiment, sample crystals were polished to reduce thickness Limiting Indices −8 ≤ h ≤ 8, −16 ≤ k ≤ 16, −12 ≤ l ≤ 12
ranging from ∼1 to 2 mm. The UV transmittance data of the sample Type of Radiation Mo Kα
crystals with 100% Ni, 10% Cu, 30% Cu and 50% Cu compositions were Wavelength. λ (Å) 0.71073
collected in the wavelength range 190–1100 nm. The near-infrared Temperature (K) 295 K
Measured Reflections 14596
spectroscopy measurement was performed in the wavelength range Independent Reflections 1811
830–2500 nm and the experiment was carried out with the help of Refinement Parameters
BRUKER VERTEX 70 spectrophotometer. Refinement Method Full-matrix least-squares on F2
Rint 0.061
R [F2 > 2 σ (F2)] 0.036
3. Results and discussion wR (F2) 0.100
Goodness-of-fit (S) 1.06
We have obtained single crystals with natural and well-developed Δρmax, Δρmin 0.71, −0.68
faces throughout the composition range, as shown in the Fig. 1. The
coloration of the crystals changes from green to those with low con-
centration of copper to bluish green to blue to those with high con- α = γ = 90°, β = 106.600(7)°, V = 679.54(8) Å3, Z = 2,
3
centration of copper. The dimensions of our sample crystals varied from D = 1.638 mg/m . The crystallographic data and the structure refine-
4 × 2.4 × 1.3 cm3 to 0.6 × 0.6 × 0.3 cm3. The percentage of Cu com- ment parameters are shown in the Table 2. The asymmetric unit and the
positions mentioned throughout the text can be assumed as the per- crystal packing view of the above sample along a axis is shown in Fig. 2,
centage of copper used for the preparations of solutions for the crystal whereas the ORTEP projection of the crystal with atom numbering is
growth. shown in the Fig. 3. The unit cell of the crystal consists of an octahedral
symmetry [Cu(H2O)6]2+ formed by six H2O molecules with Cu+2 ion at
the inversion center, a SO42- tetrahedra which is connected with [Cu
4. X-ray diffraction
(H2O)6]2+ unit through O-H⋯O bonds and a NH4+ tetrahedra which is
bonded with O of SO42- with N-H⋯O hydrogen bonds. The whole
Single crystal X-Ray Diffraction of (NH4)2Cu (SO4)2.6H2O reveals
structure has an alternative octahedral and tetrahedral layered packing
that, this crystal belongs to a monoclinic space group P21/c with crystal
arrangement. From the Table 3, we can see that, the Cu-O bond-lengths
parameters, a = 6.2455(2) Å, b = 12.4002(7) Å, c = 9.1709(6) Å,

Fig. 1. Image of our sample crystals obtained from the crystal growth technique with different compositions of Ni and Cu. (A) 100% Ni (B) 10% Cu (C) 30% Cu (D)
50% Cu (E) 70% Cu (F) 90% Cu (G) 100% Cu.

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S. Ghosh et al. Optical Materials 85 (2018) 425–437

Fig. 2. Crystal packing view of (NH4)2 Cu (SO4)2.6H2O


crystal along a axis. The octahedron [Cu (H2O)6]2+ with
magenta color is formed by Cu+2 ion connected with six
H2O molecules. The bronze colored SO42- tetrahedra
connected with [Cu (H2O)6]2+ through O-H⋯O bonds,
whereas blue colored NH4+ tetrahedra are bonded with
O of SO42- ion with N-H⋯O hydrogen bonds. (For in-
terpretation of the references to color in this figure le-
gend, the reader is referred to the Web version of this
article.)

vary from 2.1246 (19) to 1.9867 (19) Å, whereas O-Cu-O bond angles Table 3
ranging from 180 to 88.99(8)°,which indicates that the octahedral Selected bond lengths (Å) and angles (°) between the bonds of (NH4)2 Cu
complex [Cu(H2O)6]2+ is slightly distorted. (SO4)2.6H2O crystal.
In this crystal, the oxygen atoms of the sulfate are receptors of six Cu1—O3 2.0676 (18) Cu1—O1i 2.1246 (19)
hydrogen bonds of the type O-H ⋯ O, where the water molecules Cu1—O3i 2.0675 (18) S1—O5 1.4720 (17)
participate as donors of H. In addition, the oxygen atoms belonging to Cu1—O2i 1.9867 (19) S1—O7 1.475 (2)
the sulfate are also receptors of eight hydrogen bonds of the type N-H ⋯ Cu1—O2 1.9867 (19) S1—O4 1.4756 (19)
Cu1—O1 2.1246 (19) S1—O6 1.452 (2)
O, where the molecules of NH4 act as donors of H, all these bonds are O3i—Cu1—O3 180.0 O2i—Cu1—O1i 89.77 (8)
shown in Table 4. Adjacent copper octahedral units are interconnected O3—Cu1—O1i 88.99 (8) O2—Cu1—O1i 90.23 (8)
by sulphate anion through strong intermolecular O1—H1B⋯O6 and O3i—Cu1—O1i 91.01 (8) O2—Cu1—O1 89.77 (8)
O2—H2A···O4 hydrogen bonding in a supramolecular environment. O3i—Cu1—O1 88.99 (8) O1i—Cu1—O1 180.0
O3—Cu1—O1 91.01 (8) O5—S1—O7 109.76 (11)
These intermolecular bonds extending a chain in a zigzag fashion along
O2i—Cu1—O3 90.71 (9) O5—S1—O4 108.28 (11)
b and c axes and forming a six-membered ring motif R22 (8) which pro- O2—Cu1—O3i 90.71 (9) O7—S1—O4 109.49 (12)
duces graphset (Fig. 4a). Parallel, the O3—H3A···O4 and O1—H1A···O5 O2i—Cu1—O3i 89.29 (9) O6—S1—O5 108.84 (12)
hydrogen bonds forms a dimeric homosynthon R22 (8) connecting the O2—Cu1—O3 89.29 (9) O6—S1—O7 110.89 (13)
zigzag chains by c axes, shown in Fig.4b. O2—Cu1—O2i 180.0 O6—S1—O4 109.54 (13)
Three-dimensional (3D) molecular Hirshfeld surfaces and the two- O2i—Cu1—O1 90.23 (8)

dimensional (2D) fingerprint plots provides a new way of visualizing


Symmetry code: (i) −x+1, −y, −z.
and analyzing intermolecular interactions in molecular crystals, which
is different from conventional methods of crystal structure analysis. The
partitioning the space in the crystals by regions where the crystal
Hirshfeld surface (HS) [82] of a molecule in the crystal is created by
electron density of a sum of spherical atoms for the molecules

Fig. 3. ORTEP projection of (NH4)2 Cu (SO4)2.6H2O crystal with atom numbering. Symmetry code: −x+1, −y, −z.

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S. Ghosh et al. Optical Materials 85 (2018) 425–437

Table 4 outside the surface and di, which is distance from a point on the surface
Selected hydrogen bond parameters in the crystal structure of the sample to the nearest nucleus inside the surface. The distance dnorm is the
(NH4)2 Cu (SO4)2.6H2O. normalized contact distance, defined in terms of de, di and the van der
D—H···A D—H/Å H···A/Å D···A/Å < (D-H···A)/° Waals radii of the atoms. In the normalized Hirshfeld surface for the
cocrystal salt [83], the red color regions corresponding to the contacts
N1—H1C⋯O5iv 0.87 1.98 2.8488 (2) 173 at distances lower than the sum of van der Waals radii of the atoms and
N1—H1D···O6ii 0.91 2.13 2.9558 (2) 151
the white color regions on the surface corresponding to the contacts
N1—H1E···O6i 0.71 2.30 2.9869 (2) 165
N1—H1E···O7i 0.71 2.58 3.1278 (2) 136 closest to the sum of van der Waals radii of the atoms, whereas blue
N1—H1F⋯O4i 0.81 2.11 2.8920 (2) 163 color schemes on the surface represents the distance that overcome the
O1—H1A···O5ii 0.95 1.80 2.7424 (2) 174 sum of the van der Waals radii. In our cocrystal salt structure, O⋯H/
O1—H1B⋯O6i 0.93 1.77 2.6889 (2) 170
H⋯O contacts are predominant, presenting a relative contribution of
O2—H2A···O4i 0.89 1.86 2.7472 (2) 170
O2—H2B⋯O7ii 0.84 1.94 2.7006 (2) 151
these intermolecular contacts to the HS area of 69% in the whole crystal
O3—H3A···O4ii 0.90 1.92 2.8131 (2) 173 entity. On other hand, the intermolecular weak interactions involving
O3—H3B⋯O5iii 0.80 2.02 2.7949 (2) 164 H⋯H contacts are contributing 29.9% to the HS area. The respective
decomposed two-dimensional fingerprint plots are depicted to re-
Symmetry code: (i) x,1/2- y, −1/2 + z; (ii) x, y, −1 + z; (iii) 1 + x, y, z; (iv) spective HS generated and displays the characteristic spikes from
1- x,1/2 + y,1/2- z. Legend: D = donor, H = hydrogen and A = acceptor.
O—H⋯O strong hydrogen bonds, as well the diffuse region between the
spikes, attributed to weak H⋯H dispersive forces. The crystal structure
dominates the corresponding sum over the crystal. The 2D fingerprint
has been primarily stabilized by conventional intermolecular O—H⋯O
plot of the 3D Hirshfeld surface is a sophisticated method for simpli-
hydrogen bonding, forming a three-dimensional supramolecular net-
fying the complex information contained in a molecular crystal struc-
work in the solid state.
ture into a single plot, which provides a 'fingerprint' of the inter-
The x-ray powder diffraction diffractograms of the mixed crystals
molecular interactions in the crystal. The three-dimensional HS surface
with pure ones is shown in the Fig. 6. The single and sharp diffraction
and two-dimensional fingerprint plot of [Cu (H2O)6]2+ octahedra
peaks represent the good crystalline perfection and they also confirm
(Fig. 5(a)), SO42- anion (Fig. 5(b))), NH4+ cation (Fig. 5(c)) and the
the absence of macroscopic defects, such as, structural grain boundaries
whole crystal entity (Fig. 5(d)) of our single crystal (NH4)2Cu
in the crystalline structure. The small displacement of the peaks is ob-
(SO4)2.6H2O is shown in the Fig. 5.
served in Fig. 6, it is due to the change in crystallographic plane which
Fingerprint plot of the Hirshfeld surface was calculated based on de,
occurs due to the variation of Cu compositions, causing a distortion of
which is the distance from a point on the surface to the nearest nucleus
the crystalline structure and small variations in its network parameters.

Fig. 4. Ring motifs observed in the structure of the (NH4)2 Cu (SO4)2.6H2O crystal (a) A zigzag chain of ring motif generated by intermolecular O—H⋯O hydrogen
bonds. (b) Dimeric ring motif generated by intermolecular O—H⋯O hydrogen bonds, connecting the zigzag chain by c axes.

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S. Ghosh et al. Optical Materials 85 (2018) 425–437

Fig. 5. 3D Hirshfeld surface mapped with dnorm and the 2D fingerprint plots (a) [Cu(H2O)6]2+ octahedral complex (b) SO42- anion and (c) NH4+ cation (d) The HS of
a whole cocrystal salt entity. Fingerprint plots were resolved into the O⋯H reciprocal contacts and H⋯H contacts.

minutes (less than 15 min), that was sufficient time for the samples to
react with the atmospheric oxygen to promote the color change. At
higher temperatures, these types of crystals lose all the water molecules
and become anhydrous salt [84], having a distinct crystalline structure.
Therefore, it is to be assumed that, during the heat treatment some solid
state chemical reactions have occurred in such a way that a re-
arrangement of the structure or the formation of a new phase occurs
among the remaining constituents, forming a new crystalline compound
of lower but detectable crystallinity. From the Fig. 8 we can see that, at
higher temperatures, the mixed crystals with higher concentration of
copper shows the better crystallinity. It is may be due to the fact that,
the binding energy of the [Cu (H2O)6]2+ complex have greater values
than that of the [Ni(H2O)6]2+ [85], which leads the crystals with
higher copper compositions to exhibit better degree of crystallinity.

5. Thermal analysis
Fig. 6. X-ray powder diffraction pattern of the sample crystals.
TG and DTG curves provide us important information regarding the
The inspection of the Fig. 7 shows that, there is a significant color thermal stability, physical and chemical changes in the sample due to
variation of the powder of our sample crystals when they were heated the temperature change and the estimation of dehydration temperature
at higher temperatures at 200 °C and 350 °C. The remarkable change of the samples. Fig. 9 shows the TG-DTG investigations of the crystals of
was observed when the diffractograms of the treated and non-thermally Tutton's salt with 100% Ni, 10% Cu, 30% Cu, 50% Cu, 70% Cu and 90%
treated samples were compared, such as the appearance or reduction of Cu compositions in the temperature range 30–900 °C, whereas Fig. 10
crystallographic plane intensities, as shown Fig. 8. After the heat shows the dehydration temperature with respect to the Cu compositions
treatment sample powders were exposed to the environment for few of the samples, and Table 5 provides quantities of mass loss throughout
the decomposition process and their comparison with theoretical

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S. Ghosh et al. Optical Materials 85 (2018) 425–437

Fig. 7. The image of the sample powder of the crystals after the heat treatment at 200 °C and 350 °C.

calculation. have reported more than 80% UV transmittance


From the TG-DTG curve in Fig. 9 we can observe that, our sample [2,38,40,42–44,49,59,87] of their sample crystals. Our mixed crystal
crystals show temperature stability in the range of 65–90 °C. The first with 50% Cu compositions exhibits a sharp narrow band in the wave-
stage of mass loss occurs in the temperature span ∼70–190 °C, where length range 230–385 nm with an outstanding 98% transmittance in the
maximum mass loss happens around 140 °C. This stage of decomposi- ultraviolet region, which indicates that ANCUSH crystals can be con-
tion results the elimination of six water molecules from the crystalline sidered as a promising candidate for the application as UV light filters
structure which is ∼26% of the observed mass of the crystal [58,86] and UV sensors for the solar-blind technology. It is necessary to mention
and the crystal becomes anhydrous salt [84]. The second step of mass that, the UV transmittance of the crystals not entirely depends on the
loss was observed in the temperature range ∼300–450 °C where the optical properties of the material, but the thickness of the sample
maximum mass loss occurs around 400 °C. In this stage of decomposi- crystals can play also an important role for the UV transmission.
tion process most of the crystals losses almost 32% of the crystal mass In the ANSH crystal, Ni+2 ion is at the center coordinated with six
which has very good agreement with theoretical calculation, shown in H2O molecules. According to the crystal field theory [88], due to the
the Table 5. This step can be attributed to the loss of two-mole am- certain orientation of d orbitals in space the bond-lengths of center
monium and 1-mol sulfate group. In the final stage, the decomposition Ni+2 ion to six neighbor H2O molecules situated at corners of octahe-
process continues from ∼660 to 900 °C and the maximum mass loss is dron are different, which results forming a distorted complex octahe-
observed around 750 °C, which is around 23% of the total mass of the dral [Ni (H2O)6]2+ unit. In ANSH crystal, the UV transmission bands
crystal and it can be assigned to the loss of remaining 1 mol sulfate. The (190–385 nm) appears caused by the light absorption due to the d8
final product available after the heat treatment at 900 °C is maybe some electronic transition of the of Ni+2 ion in the octahedral complex [Ni
oxides of nickel and copper. (H2O)6]2+ [38,52]. The electronic spectra of transition metal com-
From the Fig. 9 and Table 5 we can see that, for the crystal with 50% plexes [89,90] suggests that, due to the simultaneous effect of the re-
Cu composition, decomposition process starts very early (∼70 °C) and moval of the d-electron degeneracy and the effect of the electrostatic
it also exhibits unusual mass loss after 300 °C, which has not very good interaction between the d electrons, the crystal field splits the d2 energy
agreement with the theoretical calculation. Besides that, this crystal level into 3F of free metal ion Ni+2 [52,90–92], which is again splits to
also shows very low dehydration temperature (Td ∼ 84.46 °C) which is ground state 3A2g (3F) and spin allowed transition states 3T1g (3P), 3T1g
not very suitable for high temperature applications. On the other hand, (3F) and 3T2g (3F). The UV band in ANSH crystal appears due to the
the crystal with 10% Cu composition follows all the three steps of mass triplet-triplet 3A2g (3F) - 3T1g (3P) transition, whereas, the optical
loss with well agreement with the ideal calculation, and it also has transitions 3A2g (3F)- 3T1g (3F) and 3A2g (3F)- 3T2g (3F) gives rise to the
higher Td (∼108 °C), as a result this crystal can be considered as a visible band and IR band respectively [52]. The above transitions are
promising candidate for high temperature solar-blind UV light filter. governed by the following linear relations:
3
A2g (3F) → 3T1g (3P) = 15Dq+ 7.5 B+ 6B (1+μ)1/2
6. UV–Vis–NIR spectroscopy 3
A2g (3F) → 3T1g (3F) = 15Dq+ 7.5 B- 6B (1+μ)1/2

UV–Vis transmission spectroscopy of the pure and mixed crystals


3
A2g (3F) → 3T2g (3F) = 10 Dq
was performed in the wavelength range 190–1100 nm, shown in the Where Dq is the octahedral crystal field parameters or ligand field
Fig. 11. Due to their fragile nature, it was difficult to cut and polish all splitting energy, the parameter B is called Racah parameters which
the crystals to reduce the thickness to an extend suitable for UV–Vis measures the interelectronic repulsion among the electrons in the d-
experiment. For the pure crystal (ANSH) with 100% Ni composition, a orbitals, and the factor μ has the value order of 0.01 [93]. The values of
transmission band appears in the UV range (190–385 nm) with max- the parameters Dq, B and μ can be estimated from the references
imum transmittance of 72.4% with a peak at 300 nm, whereas for the [91,94,95].
mixed crystals (ANCUSH) with 10% Cu, 30% Cu and 50% Cu compo- In the mixed crystals ANCUSH, the transmission bands are char-
sitions, there is a sharp narrow band in the UV range (230–385 nm) acterized by the contribution of both [Ni (H2O)6]2+ and [Cu (H2O)6]2+
with a peak at 305 nm. In addition, for both pure and mixed crystals, octahedral complexes. The free Cu+2 ion in [Cu (H2O)6]2+ unit has
there is a transmission band in the visible range 400–640 nm with a electronic structure 3d9 or the hole structure 3d1, which are split by the
peak at 485 nm and another band in the IR range 710–1100 nm with a octahedral crystal field into 2T2g and 2Eg, and therefore only one single
peak at 858 nm. During the past two decades, there have many re- electron transition 2Eg - 2T2g is expected. The orbitals are further split in
searches been conducted on the UV transmittance of the crystals of the tetragonal field, where the ground state2Eg splits into 2B1g and 2A1g
Tutton's salt for the application of UV light filters, and many researchers

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S. Ghosh et al. Optical Materials 85 (2018) 425–437

Fig. 8. Comparison of the X-ray powder diffractograms of the sample at ambient temperature (TA), 200 °C and 300 °C.

432
S. Ghosh et al. Optical Materials 85 (2018) 425–437

Fig. 9. TG-DTG curve of the crystals with 100% Ni, 10% Cu, 30% Cu, 50% Cu, 70% Cu and 90% Cu compositions in the temperature range 30–900 °C. The downward
arrow indicates the dehydration temperature (Td) of the crystals.

and excited state 2T2g splits into 2B2g and 2Eg Ref. [96]. The transitions transition of the copper octahedral complex [95]. The visible band from
in tetragonal field are described by the following relations: 400 to 640 nm appears due to the overlapping of the vertical transi-
2 2 tions, 2B1g - 2B2g and 2B1g -2Eg of Cu+2 ion [97]. The UV transmission
B1g → A1g=4Ds + 5 Dt
band 230–385 nm for ANCUSH crystals can be assigned to the ligand to
2
B1g →
2
B2g=10 Dq metal charge transfer band in the octahedral field of [Cu(H2O)6]2+
2 2
complex [98]. There is another interesting fact deserved to be men-
B1g → Eg=10 Dq + 3Ds - 5 Dt tioned, for the ANSH crystals UV transmission starts at 190 nm, whereas
In the above expression, Dq is octahedral, and Ds and Dt are the for ANCUSH crystals UV transmission starts at 230 nm, it is may be due
tetrahedral crystal field parameters and their values can be found in the to the fact that the π-π* transition in metal-ligand bonding in [Cu
references [96,97]. (H2O)6]2+ complex shifts the transmission band into higher wave-
In the mixed crystals, a broad absorption band in the infrared region length. The electronic transitions of the corresponding band appear in
with maxima near to 858 nm can be attributed to the 2B1g - 2A1g the UV–Vis spectra for ANSH and ANCUSH crystals are listed in the

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S. Ghosh et al. Optical Materials 85 (2018) 425–437

Table 6
Sample crystal's thickness, maximum UV transmittance, direct and indirect
band gap obtained from Tauc's relation.
Sample Thickness Max. UV Transmittance Band Gap (Eg) from
(mm) (%) UV–Vis Spectra (eV)

100% Ni 2 72.4 Direct- 6.22


Indirect- 6.071
10% Cu 1.55 65.8 Direct – 5.02 Indirect-
4.87
30% Cu 1.17 86.5 Direct- 5.04
Indirect- 4.75
50% Cu 1 98 Direct- 5.145
Indirect- 4.875

Fig. 10. Dehydration temperature of the sample crystals with respect to the
copper compositions.

Table 7.
The band gaps of the above crystals from UV–Vis spectra was de-
termined by using the Tauc's equation as follows:

αhν = B (hν − Eg )m (1)

The absorption coefficient α is an important physical parameter


which describes the intensity changes of the incident light when pro-
pagating through a material. The absorption coefficient (α) can be
written as:

1 1
α= ln ⎛ ⎞ Fig. 11. UV–Vis transmission spectroscopy of the sample crystals with 100% Ni,
d ⎝ T% ⎠ (2)
10% Cu, 30% Cu and 50% Cu compositions in the wavelength range
Where d is the thickness of the sample crystals. The parameter m in the 190–1100 nm.
equation (1) characterizes the types of optical transition, and it can
have four values, m = 2 for an indirect allowed transition, m = 3 for an dopant copper, it can also be dependent on the crystallite size, struc-
indirect forbidden transition, m = 1/2 for direct allowed transition and tural parameter, and presence of impurities. The inspection of the
m = 3/2 for direct forbidden transition [99]. The parameter B in Table 6 also shows that the mixed crystals have lower values of optical
equation (1) has value depends on the category of transmission decided band gap than ANSH crystal, which facilitates electronic transitions
through the parameter m. To estimate the band gap (Eg), we have between the highest occupied molecular orbital (HOMO) and lowest
plotted (αhν )2 vs hν for direct allowed transitions and (αhν )1/2 vs hν for unoccupied molecular orbital (LUMO) energy levels. The smaller value
indirect allowed transitions, as shown in the Fig. 12 and the extra- of Eg for ANCUSH crystals makes the material more electroconductive,
polation of the straight line portion of the curves to zero absorption which is very significant in applications for optoelectronic devices
coefficient value α = 0 [100] gives the energy band gap value Eg. The [101].
maximum UV-transmittance, thickness of the sample crystals and band NIR absorption spectroscopy of our sample crystals with 100% Ni,
gap obtained from UV-VIS spectra by using Tauc's relation is shown in 30% Cu, 50% Cu, 70% Cu, 90% Cu and 100% Cu compositions per-
the Table 6. From the Fig. 12 we can observe that, the plot of (αhν )2 vs formed in the wavelength range 830–2500 nm is shown in the Fig. 13.
hν has stepper increase than the (αhν )1/2 vs hν plot near to the ab- In NIR spectroscopy the most prominent absorption bands occurring in
sorption edge of the optical spectra, which causes to have greater value the NIR region are related to the overtones and combinations of fun-
of the direct band gap compared to indirect one. From the Table 6, we damental vibrations of the functional groups. From the Fig. 13 we can
can see that there is a small variation of the values of band gaps be- see, for pure crystals with 100% Cu compositions (ACUSH), there is an
tween ANCUSH crystals, this differences not only depends on the

Table 5
Quantities of mass loss and dehydration temperature (Td) of the samples during thermogravimetric analysis.
Sample 1st Mass Loss 2nd Mass Loss Final Mass Loss Dehydration Temp. (Td) (°C)

Temp (°C) Ideal (%) Exp. (%) Temp (°C) Ideal (%) Exp. (%) Temp (°C) Ideal (%) Exp. (%)

100% Ni 97–193 27.34 25.83 320–451 33.41 31.35 715–811 24.50 23.30 105.76
10% Cu 98–184 27.31 25.71 317–451 33.38 31.29 673–900 24.29 23.14 107.76
30% Cu 97–184 27.24 26.49 308–456 33.29 31.87 660–766 24.22 23.02 101.50
50% Cu 70–186 27.17 26.79 316–453 33.21 25.62 677–781 24.15 16.59 84.46
70%Cu 82–184 27.11 25.94 312–454 33.14 33.06 660–778 24.10 22.35 96.24
90% Cu 97–182 27.04 25.71 316–453 33.05 32.5 680–781 24.03 21.82 103.5

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S. Ghosh et al. Optical Materials 85 (2018) 425–437

Table 7
Electronic transitions corresponding to the optical bands appears in the UV–Vis transmission spectra.
Transmission Band Electronic Transitions for Transmission Band Electronic Transmission of Mixed ANCUSH Crystals
ANSH Crystal

UV Region:190–385 nm, Peak: 300 nm [Ni (H2O)6]2+: 3A2g (3F) → UV Region: 230–385 nm, Peak: [Ni (H2O)6]2+: 3A2g (3F) → 3T1g (3P) [Cu (H2O)6]2+:
3
T1g (3P) 305 nm Ligand to metal charge transfer
Visible Region: 400–640 nm, Peak: 485 nm [Ni (H2O)6]2+: 3A2g (3F)→ 3T1g Visible Region: 400–640 nm, Peak: [Ni (H2O)6]2+: 3A2g (3F)→ 3T1g (3F) [Cu (H2O)6]2+:2B1g
(3F) 485 nm →2B2g 2B1g →2Eg
IR Region: 710–1100 nm, Peak: 858 nm [Ni (H2O)6]2+: 3A2g (3F)→ 3T2g IR Region: 710–1100 nm, Peak: [Ni (H2O)6]2+: 3A2g (3F)→ 3T2g (3F) [Cu (H2O)6]2+:2B1g
(3F) 858 nm →2A1g

absorption band near to 860 nm, and it is attributed to the 2B1g - 2A1g
transitions [102,103]. There is another broad band appears from 1432
to 1614 nm with a peak at 1558 nm, can be assigned to the overtones of
OH stretches and the combinations of the H-O-H bend with the OH
stretches of water molecules [104]. There is another broad band from
1880 to 2283 nm is observed, with peaks at 1968 nm, 2053 nm and
2154 nm, this band occurs due to the combinations of the OH vibrations
of water molecules and the water bending modes [105]. There is an-
other prominent absorption band which appears with a peak at
2410 nm, can be assigned to the combinational modes of SO4−2 ion
[105]. From the Fig. 13 we can observe that, the mixed crystal (AN-
CUSH) with higher (90%) Cu composition shows the same type of NIR
characteristics as that of pure crystal with 100% Cu composition.
For the ANSH crystal with 100% Ni composition, there is a broad
absorption band from 890 to 1424 nm with a peak at 1130 nm, this
band can be attributed to the 3A2g (3F)- 3T2g (3F) transition of Ni+2 ion
in the octahedral complex of nickel. There is another band appears
1425–1858 nm with two peaks at 1503 nm and 1627 nm, and it can be Fig. 13. Near-infrared (NIR) absorption spectra of the sample crystals in the
wavelength range 830–2500 nm.
considered as the overtones of water molecules. An overlapping of
bands observed in the wavelength range 1860–2280 nm, with three
peaks at 2035 nm, 2158 nm and 2223 nm and this band can be assigned (NH4)2Cu(SO4)2.6H2O indicates that the octahedral complex [Cu
to the combinations of the OH vibrations of water molecules and water (H2O)6]2+ unit is slightly distorted. The three-dimensional Hirshfield
bending bonding modes. The peak at 2410 nm is similar to that of the surface analysis and the two-dimensional fingerprint plot of HS surface
ACUSH crystal and can be attributed to the combinational modes of demonstrates that, O⋯H/H⋯O intermolecular contacts are pre-
(SO4)−2 ion. The crystals with lower percentage of Cu concentration, dominant which is 69% contribution of the entire crystal. The sharp
for example 10% Cu, 30% Cu, 50% Cu have the same type of NIR peak in X-ray diffraction pattern represents the good crystalline per-
spectra as that of ANSH crystals. fection of the samples and the small displacement of the peaks is ob-
served caused by the change of Cu compositions in the composition
range. The comparison of the X-ray diffractograms of the samples at
7. Conclusions ambient temperature, 200 °C and 350 °C indicates that, there is a re-
arrangement of the structure and occurrence of new phase happened
We have obtained the mixed crystal of ammonium nickel-copper when the samples were subjected to the higher temperature.
sulfate Tutton's salt by employing growth from slow evaporation of The TG-DTG analysis shows that, for the crystal with 50% Cu
aqueous solution technique. The metal-ligand bond distances and bond compositions, decomposition process starts around 70 °C and it shows
angles estimated from the single-crystal X-ray diffraction of the sample

Fig. 12. Direct and indirect band gap of the sample crystal with 50% Cu composition obtained from Tauc's equation. (a) The direct band gap was obtained from
extrapolation of the straight-line portion of the (αhν )2 vs hν curve to zero absorption coefficient value α = 0 (b) The indirect band gap was obtained from extra-
polation of the straight-line portion of the (αhν )1/2 vs hν curve to zero absorption coefficient value α = 0.

435
S. Ghosh et al. Optical Materials 85 (2018) 425–437

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