RESEARCH ARTICLE

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Synthesis, Characterization, and Optical Properties of New

Organic–Inorganic Hybrid Perovskites [(NH3)2(CH2)3]CuCl4
and [(NH3)2(CH2)4]CuCl2Br2
Seham K. Abdel-Aal,* Mohamed F. Kandeel, Ashraf F. El-Sherif,
and Ahmed S. Abdel-Rahman*

Organic–inorganic hybrid perovskites

Organic–inorganic hybrid perovskites (OIHs) are exceptionally promising sector (OIHPs) of the formula ABX4 where
of novel materials for optoelectronic applications. Herein, the OIHs of the for- A represents the organic diamine cation,
mula [(NH3)2(CH2)3]CuCl4 labeled by C3CuCl and [(NH3)2(CH2)4]CuCl2Br2 B represents the metal ion, and X is the hal-
ogen (I, Br, Cl, and so on) are class of new
labeled by C4CuClBr are prepared by slow evaporation method. The synthesis
materials that have very promising applica-
process is achieved by mixing equimolar ethanolic solutions ratios (1:1) of their tions[2–8] and tunable properties and struc-
basic components (organic/inorganic). Characterizations of these materials ture. Many scientists are attracted to work
using microchemical analysis, energy dispersion X-ray (EDX) and X-ray diffraction in OIHPs applications in photonics, other
(XRD) are discussed. The XRD is used to estimate the crystalline size for prepared fields and the preliminary speculation was
compounds and found in the range of 38.8 and 48.8 nm for C3CuCl and accompanied by work into the mechanical,
optical, and structural properties of perov-
C4CuClBr, respectively. The vibrational spectra are studied by Fourier transfor-
skites. Perovskites collect characteristics of
mation infrared spectroscopy (FTIR) and show the major diffraction peaks of both inorganic and organic: chemical
compounds and their assignment. UV-region strong absorption is clarified in the tuning of their optoelectronic properties,
optical properties studied for Cu hybrid, whereas the bandgap energy estimated minimal-temperature solution-based
via Kubelka–Munk equation and found 2.8 and 3.85 eV for C3CuCl and C4CuClBr, organic deposition remembrance.[7–9]
respectively. Bandgap is of crucial importance in
optoelectronic applications. It is the best-
known feature of hybrid perovskites where
their bandgap can be broadly modified
1. Introduction from blue-to-red spectral areas. It is possible to adjust the energy
gap in hybrid perovskites by adjusting the perovskites geometry.
In the Ural Mountains of Russia, Gustav Rose, in 1839, has dis- Geometry tuning can be accomplished by changing temperature
covered the perovskite and named afterward by L. A. Perovski and eliminating perovskite components.[4] This scope is accom-
(1792–1856), the Russian mineralogist, all materials of the crystal plished by adding the halide, increasing the width of the chain or
structure similar to CaTiO3.[1] Perovskites are one of the most both. The inorganic octahedron holds the valence and conduc-
important groups in material science due to their extraordinary tion bands. The valence band comprises hybridized metal and
physical and chemical properties. As it has properties appropriate halide p-orbitals, whereas the conductive band is mostly distin-
for many uses, the perovskite architecture has and continues to guished by small contributions from the orbital halides.[5,6]
attract interest.[2] These bands found to be independent on the organic cation
but modulate the bandgap by changing the bond length of
metal-halide,[10] which ensures that the shifts generated by
Dr. S. K. Abdel-Aal, Dr. A. S. Abdel-Rahman removing the organic cation are less noticeable than those cre-
Physics Department ated by halide replacement.
Faculty of Science The hybrid perovskites of the formula A2MX4, A: ammonium-
Cairo University
12613 Cairo, Egypt
substituted organic cation, M: a divalent metal ion, and X: a halo-
E-mail: [email protected]; [email protected] gen (Cl, Br, I) like the presently investigated hybrid perovskite of
M. F. Kandeel, Prof. A. F. El-Sherif [(NH3)2(CH2)3]CuCl4 and [(NH3)2(CH2)4]CuCl2Br2. The crystal
Laser and Photonics Center structure of these hybrid perovskites is stabilized by a series of
Engineering Physics Department hydrogen bonds and van der Waals interactions between anions
Military Technical College and cations. The ammonium ion at the end of organic chains
Cairo, Egypt
forms N–H···X hydrogen bonds with the halide ion of the metallic
The ORCID identification number(s) for the author(s) of this article layer. The structure of inorganic layer of Cu hybrid as reported
can be found under https://doi.org/10.1002/pssa.202100036. before[11–17] consists of corner-shared octahedral distorted [CuCl4]2

DOI: 10.1002/pssa.202100036 anion alternative with organic layer [(NH3)2(CH2)n]2 cations.

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To save the environment and solve the energy crisis, it is The [(NH3)2(CH2)3]CuCl4 was prepared by mixing the
important to use environmental friendly, low-cost, and lead-free ethanolic solution of organic cation and CuCl2 in 1:1 ratio
materials in perovskite solar cell applications, all these require- with constant stirring, heat (60 ºC for 30 min) and then slow
ments are involved in the Cu hybrid perovskite that are previ- cooling to room temperature. The steps of preparation are indi-
ously reported.[11–18] As the optical properties of lower organic cated in Figure 1. Green powder of [(NH3)2(CH2)3]CuCl4 denoted
chain length of Cu hybrid perovskite is not reported as well as C3CuCl precipitate out, as shown in Figure 2. The reaction
introducing of both Cl and Br ion in lower chain lengths. It is equation is
of our interest to prepare and study some of the properties of
Δ
C3CuCl and C4CuClBr to add to global knowledge about these ½ðNH3 Þ2 ðCH2 Þ3 Cl2 þ CuCl2 !½ðNH3 Þ2 ðCH2 Þ3 CuCl4 (1)
promising materials.

2.1.2. Synthesis of [(NH3)2(CH2)4]CuCl2Br2 Hybrid Perovskites

2. Experimental Section
2.1. Synthesis The organic cation 1,4 diamine butane bromide [(NH3)2(CH2)4]
Br2 synthesized by the same method of [(NH3)2(CH2)3]Cl2 using
All used chemicals in the preparations are used as-received HBr. The salt was filtered, washed with alcohol, and used.[20,22,23]
and purchased from Sigma-Aldrich with purity exceeds 97%. The perovskite hybrid of [(NH3)2(CH2)4]CuCl2Br2 was pre-
All solvents were of reagent grade. pared according to Equation (2).[11,20,24] The steps of preparation
are shown in Figure 3. Brown cubic crystals of [(NH3)2(CH2)4]
2.1.1. Synthesis of [(NH3)2(CH2)3]CuCl4 Hybrid Perovskites CuCl2Br2 denoted C4CuClBr precipitate out, as shown in
Figure 4.
The organic cation [(NH3)2(CH2)3]Cl2 1,2 diamine propane- Δ
chlorate was prepared according to the previous works.[18–21] ½ðNH3 Þ2 ðCH2 Þ4 Br2 þ CuCl2 !½ðNH3 Þ2 ðCH2 Þ4 CuCl2 Br2 (2)

Figure 1. OIHPs procedure of C3CuCl.

Figure 2. C3CuCl perovskite before and after the deposition.

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Figure 3. OIHPs procedure of C4CuClBr.

Figure 4. Indicate the C4CuClBr perovskite before and after the precipitation.

2.2. Characterizations 2.2.3. Infrared Spectroscopy (IR)

2.2.1. Elemental Analysis The Fourier transformation infrared (FTIR) spectroscopy

measurements were achieved on FTIR 4100 spectrometer
Carbon, hydrogen, and nitrogen microchemical analysis using pure KBr pellets and the measuring spectra in the range
carried out in a Perkin Elmer C,H,N analyzer and energy- 4000–400 cm
1.
dispersive X-ray (EDX) spectroscopy was carried out on samples
by scanning electron microscope (SEM) equipped with an EDX
detector type SUTW-Sapphire, resolution:132.14 and was operat-
ing at 25 kV. Table 1. The chemical analysis of synthesized perovskites.

Compound Elements
2.2.2. X-Ray Powder Diffraction Measurement
Measured Calculated
The X-ray powder diffractometer Siemens D-500 computer C% H% N% C% H% N%
controlled with Cu Kα radiation λ ¼ 1.54056 Å were used to col- C3CuCl 13.46 5.52 10.96 12.79 4.26 9.95
lect XRD powder diffraction data with the measuring range (2θ)
C4CuClBr 12.36 3.76 7.85 12.49 3.71 7.29
from 5 to 70 , step 0.04.

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Figure 5. Crystal image and EDX spectrum of C3CuCl.

Figure 6. Crystal image and EDX spectrum of C4CuClBr.

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2.2.4. Optical Properties 3. Result and Discussion

Jenway 7205 UV–vis Scanning Spectrometer was used in meas- 3.1. Elemental Analysis
urements of optical properties of the samples and collects data
from 200 to 2000 nm wavelength range. Microchemical analysis and SEM–EDX have been used to inves-
tigate the presence of each element in the synthesized perov-
skites after preparation. The carbon, nitrogen, and hydrogen
percentages have been determined by microchemical analyses
Table 2. The average bond length of [(NH3)(CH2)n(NH3)]CuX4, center in Cairo University. The calculated values according to
n ¼ 2, 3, 4., X ¼ Cl, Br. the elemental molecular weight for (C, H, and N) divided by
the total molecular weight for the compound. The calculated
Chemical formula Average metal–halogen References and measured results of all synthesized perovskites analysis
bond length
are shown in Table 1.
[(NH3)(CH2)2(NH3)]CuCl4 C2CuCl Cu─Cl ¼ 2.312 Å [30] The EDX spectra for C3CuCl and C4CuClBr (apart
[(NH3)(CH2)2(NH3)]CuBr4 C2CuBr Cu─Br ¼ 2.436 Å [31] from crystal images taken by computerized OPTIKA
[(NH3)(CH2)3(NH3)]CuCl4 C3CuCl Cu─Cl No available Microscopes B-190) are shown in Figure 5 and 6, respectively.
data The atomic percentage of metal and halide for all synthesized
[(NH3)(CH2)3(NH3)]CuBr4 C3CuBr Cu─Br ¼ 2.441 Å [31] materials is tabulated in inset of each figure, which
confirms the elemental composition of different metals and
[(NH3)(CH2)4(NH3)]CuCl4 C4CuCl Cu─Cl ¼ 2.294 Å [20]
halides.
[(NH3)(CH2)4(NH3)]CuBr4 C4CuBr Cu─Br ¼ 2.436 Å [20]
The results obtained by EDX may be due to instrumental
limitations that make quantification of light elements such
as C and N difficult. So, the main focus of the spectrum
was the compositional analysis of the inorganic component
of the perovskite, we investigated the variations of Cu, Cl,
and Br. The O signal also be seen in the spectra may be attri-
bute to water molecule. The shown data in microchemical anal-
ysis and EDX confirm the presence of all used elements in the
preparation and the hybrids are in the correct chemical
formula.

3.2. X-Ray Diffraction

The structure of Cu hybrid consists of corner shared octahedral

structure anion followed by organic cations that form cations–
anions–cations cohesions as discussed in detail in our previous
work and other reported Cu hybrid perovskites.[7,12–14,25–29]
Table 2 shows the Cu─X, X ¼ Cl, Br average bond length of short
organic chain length of the formula [(NH3)(CH2)n(NH3)]CuX4,
Figure 7. XRD diffraction patterns of C3CuCl and C4CuClBr. n ¼ 2, 3, 4.

6
1.2
x10 -5 (dhkl W hkl CosθD)2

4
0.8

2 0.4

C3CuCl (d hkl W hkl CosθD)2 = 5.29x10 -3 (dhkl 2 W hkl CosθD) + 6.25x10 -8

C4CuClBr (dhkl W hkl Cosθ D)2 = 4.21x10 -3 (d hkl 2 W hkl CosθD) + 4.33x10 -7
0 0
0 2 4 6 8 10 12
x10-3 (dhkl 2 W hkl CosθD)

Figure 8. Linear fit of SSP of C3CuCl and C4CuClBr.

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Table 3. The calculated values of crystallite size (nm) and microstrain by Table 4. The assignment of the observed bands of IR for the compound
four methods of C3CuCl and C4CuClBr. [(NH3)2(CH2)3]CuCl4 and [(NH3)2(CH2)4]CuCl2Br2.

Compound Debye–Scherrer Williamson–Hall Halder–Wagner SSP Attributed toa) C3CuCl C4CuClBr

4
3
3
D [nm] D [nm] ε [10 ] D [nm] ε [10 ] D [nm] ε [10 ] νas(NH3) 3429 3682, 3435
C3CuCl 29.01 42.33 0.99 38.66 0.58 38.82 0.5 νs(NH3) 3032 3066, 3024
C4CuClBr 29.86 45.04 3.44 48.8 2.14 48.8 1.32 νas (CH3)/The N–H···Cl bond 2942, 2712 2872, 2624
δas(NH3) 1574 1584
δs(NH3)/δ(CH2) 1495 1469
From this table, one can see that the Cu─Cl bond length is δw(CH2)/δt(CH2) 1395, 1146 1402, 1342
shorter than Cu─Br bond length by 0.14 Å regardless the ν(C─C)/r(NH3) 1050 1109, 1025
organic chain length.
νsy(C─N) 875 915, 869
X-ray diffraction was used to evaluate the crystalline size of the
C─H2 (δS) 808 757, 726
obtained perovskite. The Debye–Scherrer’s Equation (3) was
used to determine the average crystalline size. Tortional C─N 541, 496 496, 423
References [16,23,24,51] [16,17,51,52]
kλ
D¼ (3)
W cos θ sy, symmetric; asy, asymmetric; ν, stretching; δ, bending; δw, wagging; r, rocking.
a)

where k is the shape factor which usually takes a value of 0.94, W

is the full width half maximum intensity (FWHM) in radians, than that obtained of Debye–Scherrer equation where these
λ is the used wavelength of the X-ray radiation (λCu ¼ 1.54056 Å), methods take into effect of all diffraction peaks and consider
D is the average crystalline size, and θ is the Bragg diffraction the lattice strain, which is missed in Scherrer’s equation.[37–39]
angle. The XRD diffraction patterns of C3CuCl and C4CuClBr
shown in Figure 7, at T ¼ 298 K. 3.3. IR Spectroscopy
In addition to Debye–Scherrer’s method to determine the
crystalline size, there are another methods to estimate D and The infrared spectra of hybrid perovskites C3CuCl, C4CuClBr
the average lattice microstrain ε[32–36] can be also estimated are recorded at room temperature and shown in Figure 9.
from the Williamson–Hall’s equation,[37–43] Halder–Wagner’s It is difficult to assign all bands to their source bonds, but the
method,[44–46] and size–strain plot (SSP) (linear fit is shown in most important peaks are analyzed by comparison with similar
Figure 8).[47,48] Table 3 shows the calculated value of crystalline compounds.
size and microstrain for synthesized perovskites at room temper- Also the vibrational study of infrared absorption has been
ature. The tunable crystal size, depending on the change in the carried out to get more information on the crystal structure.
length of the organic chain or the replacement of the halide, will Figure 9 shows the infrared spectra of [(NH3)2(CH2)3]CuCl4
have an effect on the optical properties (the next section). and [(NH3)2(CH2)4]CuCl2Br2.
It is clear that, all D value that calculated using Williamson– The absorption peak of 3000–3500 cm
1 is assigned to
Hall, Halder–Wagner’s method, and SSP techniques are higher N─H stretching. The νas(NH3) asymmetric stretching modes
Transmittance (a.u.)

C4CuClBr
C3CuCl

400 800 1200 1600 2000 2400 2800 3200 3600 4000
-1
Wavenumber (cm )

Figure 9. The infrared spectrum of the compounds [(NH3)2(CH2)3]CuCl4 and [(NH3)2(CH2)4]CuCl2Br2 at room temperature.

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Reflection (a.u.)

2.85eV 3.9eV

C3CuCl
C4CuClBr

200 300 400 500 600 700 800

Wavelength (nm)

Figure 10. Optical properties of C3CuCl and C4CuClBr, the bandgap energy for C3CuCl and C4CuClBr in the inset figure.

3500–3200 cm
1 and νs(NH3) symmetric modes are assigned to where υ is the vibration frequency, A is a constant, h is the Planck
peaks in range 3200–3500 cm
1.[24] The νas(CH2) asymmetric constant, and Eg is bandgap. The type of transition is associated
stretching mode appeared at 2900–2950 cm
1. The hydrogen with the exponent n which takes values 1/2 or 3/2 for indirect
bonds are expected at 2950–2850 cm
1 band. The bands transitions, and 2 or 3 for direct allowed.[50,53–57]
associated with CH stretching are in range 2780–2790 cm
1 Figure 10 shows the optical properties of [(NH3)2(CH2)3]CuCl4
and the nonfundamental NH and CH modes in the range and [(NH3)2(CH2)4]CuCl2Br2. Due to the strong absorption at the
2600–1800 cm
1.[49] Weak intensities peaks occurred at 2400– UV region of [(NH3)2(CH2)4]CuCl2Br2 sample it may find attrac-
2600 cm
1 region, which are attributed to combination and tive applications as UV light photocatalysis. The estimated energy
overtone bands of N─H deformation modes and C─NH3 torsion gap plot is shown in the inset figure of the [(NH3)2(CH2)3]CuCl4
modes.[24] The CH2 bending modes are associated with bands at and [(NH3)2(CH2)4]CuCl2Br2 sample which equals to 2.85 and
1490–1470 cm
1. The asymmetric δas(NH3) and symmetric 3.9 eV, respectively.
δs(NH3) bending modes are bands observed in the range The bandgap energy rises when mixed halide Cl2Br2 with a
1450–1600 cm
1. The C─N stretching modes are occurred small chain length is used. The OIHPs’ dielectric activities are
around 860–1200 cm
1, whereas 600–2100 cm
1 is assigned to related to their mechanical properties and demonstrate the
C─C symmetric stretching.[50] The C─N torsional mode impact of microstructure on the polarons.[58]
observed at the range of 550–400 cm
1.[13]
The assignment of the bands in IR absorption is shown in
Table 4 for [(NH3)2(CH3)2]CuCl4 and [(NH3)2(CH2)4]CuCl2Br2. 4. Conclusion
Figure 9 shows the region bounded by brown rectangle
is the fingerprint of the each molecule and lies from 1300 Cu hybrid perovskites diammonium series [(NH3)2(CH2)3]CuCl4
to 400 cm
1. and [(NH3)2(CH2)4]CuCl2Br2 are successfully prepared by the
evaporation method. Microchemical analysis, EDX, XRD, and
FTIR have been used to confirm the formation of the novel
3.4. Optical Measurements hybrid perovskites. The X-ray diffraction for [(NH3)2(CH2)3]
CuCl4 and [(NH3)2(CH2)4]CuCl2Br2 are carried out, and the aver-
The relation between the absorption of the sample (K ), reflec- age crystallite size calculated are 38.8 and 48.8 nm, respectively.
tance (R∞), and scattering (S) are correlated in Schuster– These Cu-based hybrid perovskites show strong absorption in
Kubelka–Munk (SKM) remission function. UV region according to the optical absorption study. The energy
gap of C3CuCl and C4CuClBr are equal to 2.85 and 3.9 eV,
F SKM ðR∞ Þ ¼ ð1
R∞ Þ2 =2R∞ ¼ K=S (4)
respectively.
In the plot of (F(R∞) hυ)n versus (hυ), the extrapolation of the
drawn straight line estimate the energy gap Eg according to the
Kubelka–Munk equation. Acknowledgements
The authors thank Academy of Scientific Research and Technology ASRT-
ðFðR∞ ÞhυÞn ¼ Aðhυ–E g Þ (5) NSFC cooperation project ID.3233 for fund.

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