Optical Materials 109 (2020) 110407

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

Thermally evaporated of homogeneous nanostructured

gallium-phthalocyanine-chloride films: Optical spectroscopy
E.F.M. El-Zaidia a, b, Saleem I. Qashou c, A.A.A. Darwish b, d, e, *, I.S. Yahia f, g, h
a
Department of Physics, Faculty of Education, Ain Shams University, Roxy, 11757, Cairo, Egypt
b
Department of Physics, Faculty of Science University of Tabuk, Tabuk, 71491, Saudi Arabia
c
Department of Physics, Faculty of Science, Zarqa University, Zarqa, 13132, Jordan
d
Nanotechnology Research Unit, Faculty of Science, University of Tabuk, Tabuk, Saudi Arabia
e
Department of Physics, Faculty of Education at Al-Mahweet, Sana’a University, Al-Mahweet, Yemen
f
Research Center for Advanced Materials Science (RCAMS), King Khalid University, Abha, 61413, P.O. Box 9004, Saudi Arabia
g
Advanced Functional Materials & Optoelectronic Laboratory (AFMOL), Department of Physics, Faculty of Science, King Khalid University, P.O. Box 9004, Abha, Saudi
Arabia
h
Nanoscience Laboratory for Environmental and Biomedical Applications (NLEBA), Semiconductor Lab., Department of Physics, Faculty of Education, Ain Shams
University, Roxy, 11757, Cairo, Egypt

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

Keywords: Films of gallium-phthalocyanine-chloride (GaClPc) with various thicknesses were prepared by the vacuum
Organic material thermal evaporating technique. The films’ structural were studied by the X-ray diffraction pattern. It was found
Surface morphology that GaClPc films with a thickness beyond 45 nm showed a single sharp peak at 2θ = 26.6◦ . The atomic force
Nonlinear optical parameters
microscopy clarified that the grain size and the roughness increased as the film’s thickness increased. The ab­
Optical limiters
sorption exhibited a high linear transmittance in the region between 350 and 650 nm. Also, the values of the
band gap energies are unaffected by the film thickness. The dielectric constants of GaClPc films at different
thicknesses were evaluated. The first-order (χ(1)) and the third-order (χ(3)) nonlinear susceptibility of GaClPc
films were calculated. The values of (χ(3)) were increased as the film thickness was increased which may be due
to the possible orientation of the molecular chains in unfavorable direction with the induced electric field as the
film thickness increases. The optical limiter (OL) properties of GaClPc films have been discussed by the
normalized power of two laser beams (the He–Ne laser of 638.2 nm and green diode laser of 533 nm). It was
concluded that the GaClPc films can be used as a promised candidate OL material.

1. Introduction
Currently, the studies of optical and electronic properties of small
organic molecules have been effectively progressed due to the extensive
work of plentiful research groups. The intense works of these groups in
studying the characterizations of organic semiconductors materials
played an essential role in the evolution of designing optoelectronic
devices and in the applications of light-emitting diodes [1–3].
Phthalocyanine (Pc) and its derivatives are classified as one of the
attractive organic small molecules due to their broad potential appli­
cations such as solar cells [4] gas sensors [5] and switching devices [6].
Pc is a π-conjugated aromatic compound accompanied by electrons
delocalization in four isoindoline cycles with an available vacancy in the
center of the compound [7]. Numerous of metal phthalocyanine (MPcs)
have been fabricated by replacing the central vacancy of the compound
by a metallic atom. Indeed, MPcs are characterized by many vital
properties such as thermal and photochemical stability [8]. Moreover,
MPcs compounds that are familiar by their fast absorption of light in the
region of UV-VIS spectra could be considered as perfect organic dyes [9].
Further, the high thermal stability of MPcs without decomposition fa­
cilitates the preparation of Pc thin films by vacuum evaporation
technique.
On the other hand, the production of MPc derivatives can be ach­
ieved by the cross-linking of the terminal phthalocyanine compound
with peripheral groups or by introducing axial legends attached to the
central metallic atom. It was found that the central metal-axial ligand
bonds have a substantial effect in changing the π-electronic distribution
due to the variation of spin density and dipole moment of the central

* Corresponding author. Department of Physics, Faculty of Science University of Tabuk, Tabuk, 71491, Saudi Arabia
E-mail address: aaadarwish@gmail.com (A.A.A. Darwish).

https://doi.org/10.1016/j.optmat.2020.110407
Received 10 April 2020; Received in revised form 25 August 2020; Accepted 2 September 2020
Available online 12 September 2020
0925-3467/© 2020 Elsevier B.V. All rights reserved.
E.F.M. El-Zaidia et al.
metallic atom [10]. Consequently, we expect many of electrical and
optical properties will be enhanced. The investigation of substitutional
groups’ effect on the optical properties of MPc compounds has been
devoted to many of the literature. For instance, the optical properties of
aluminum phthalocyanine chloride (AlPcCl) have been investigated, in
contrast, the optical and fundamental bandgap energies of this com­
pound were found to be 1.42 and 3.69 eV, respectively [11]. Also, the
optical constants of copper (II) 2,9,16,23-teter-tert-butyl-29H,
31H-phthalocyanine (CuTTBPc), under the effect of annealing temper­
atures, were calculated in our previous work [12].
Thereby, the low values of the optical bandgap energy and the
adequate optical constants of MPc compounds provide the engineers
with the necessary conditions for the designing of efficient solar cells
and performance photoelectronic devices. In the present work, we are
looking to introduce an innovation derivative material of MPc com­
pounds with desired optical parameters. Gallium-phthalocyanine-
chloride (GaClPc) is suggested to be one of the promised candidate
materials to be utilized as an excellent dye in the fabrication of long
series of organic dyes in the manufacturing of optoelectronic devices
[13]. In particular, GaClPc is epitomized by the linked-gallium atom
with the axially ligated halide over the isoindoline rings. Therefore, the
molecular structure of GaClPc (See Scheme 1) is characterized by a
non-planar configuration of atoms.
The investigation of the film thickness effect on the optical properties
and the film crystallography provides us an in-depth interior view of
several new conditions that occurred during the deposition of the ma­
terial on substrates. For example, the alteration of bandgap energy with
the variation of the film thickness could be used as a useful examination
tool to determine the possibility of creating oxides layers inside the film
structure. Further, the analysis of the X-ray diffraction (XRD) pattern
and the atomic forces microscopy (AFM) micrographs show us the in­
fluence of the film thickness in increasing the agglomeration of stacking
particles and thus the crystallization of the film will be boosted.
Consequently, the present work aims to study the effect of the film
thickness on the morphology and spectroscopy of GaClPc thin film.
Another purpose of the present literature is to determine the effect of the
film thickness on the bandgap energy and the optical parameters of
GaClPc thin film.
2. Experimental details
The powder of GaClPc, which has the empirical formula
(C32H16ClGaN8) and molecular weight of 617.7 g/mol, was purchased
from a well-known company (Sigma Aldrich Company). Different
Scheme 1. The chemical molecular structure of the GaClPc compound.
2
Optical Materials 109 (2020) 110407
thickness (45–151 nm) of GaClPc thin films was achieved by vacuum
thermal evaporating procedure [14,15]. The vacuum chamber was
firstly evacuated by applying the coating unit (HHV Auto 306) for 4 h
and the chamber pressure was lowered to 10− 5 Pa. The controllable of
the thin film thickness, with a deposition rate of 2 nms− 1, was accessible
by a thickness monitor of quartz crystal.
The analysis of the film crystallography was carried out by A Philips
X-ray diffractometer model Shimadzu XRD-6000 with the operation of
monochromatic CuKα radiation (1.5418 Å) at 40 kV and 25 mA. The
surface topography, grain size, and surface roughness were studied by
Atomic force microscopy model NT-MDT. The measurements of trans­
mittance (T) and the reflectance (R) in the UV-spectrum and the visible
spectra were obtained by a double beam spectrophotometer (JASCO
model V-570 UV–Vis–NIR). The attenuation of GaClPc thin film was
achieved by inserted the films between the lens (with a focal length of
10 cm) and the laser power meter (Lab-Master Ultima, COHERENT,
USA). The detector was calibrated at 632.8 nm for the He–Ne laser beam
and 533 nm for the green diode laser beam.
3. Results and discussions
3.1. Analysis of XRD and AFM studies
The XRD-pattern of GaClPc thin films with different values of
thickness was depicted in Fig. 1. Diffraction peaks for GaClPc thin film
were missing when the thickness of the films was approximately 45 nm,
which confirms that the amorphous structure was formed at the initial
implementation of the film growth. On the other hand, the rest of the
films with various thicknesses (75, 98, and 151 nm) exhibit a single
sharp peak observed at 2θ = 26.6◦ . This result indicates the increase of
the agglomeration stacking particles as the film thickness increases.
Meanwhile, this result implies that the π-π interaction between the two
molecules is strong enough to induce a templating structure [12].
Hence, we can conclude that the crystallization of GaClPc thin films has
been improved with the increasing of the deposited layer thickness.
Mainly, to check the nanostructure of as-deposited GaClPc thin films,
we usually calculate the mean crystallite size (D). Thus, according to
Scherrer’s equation, the values of D with different values of film thick­
ness can be evaluated as follows [14]:
Kλo
D= (1)
β cos θ
where K is the Scherrer’s constant, λ0 is the X-ray wavelength, β is the
broadness of peak in radians at the half-maximum. The values of D, as
were listed in Table 1, confirm the increase of D (from 16.58 to
18.23 nm) as the film thickness increases (from 75 to 151 nm). This
phenomenon reveals two remarkable results: (i) GaClPc thin films are
characterized by nanostructure property (ii) The crystallography of
Fig. 1. XRD of GaClPc films with different thickness.
E.F.M. El-Zaidia et al. Optical Materials 109 (2020) 110407

Table 1 of the GaClPc as it was deposited on a quartz substrate (with approxi­

Structure parameters for GaClPc films at a different film thickness. mately same film thickness ∼ 100 nm) , was reported to be 18.099 nm
X-ray analysis AFM analysis [16]. Therefore, it can be deduced that π-π interactions between the
− 3 GaClPc molecules and the glass substrate is larger than the relative
d (nm) L δ ( × 10 Nc Grain size Roughness
(nm) nm− 2) (nm− 2) (nm) (nm) interaction of GaClPc molecules with the quartz substrate. Hence, the
type of substrate has a significant effect on the structural and optical
45 – – – 90.3 65.2
75 16.58 3.64 0.016 94.4 68.2
properties.
98 16.65 3.60 0.021 103.8 71.2 Fig. 2 displayed the surface morphology of GaClPc thin films at
151 18.23 3.00 0.025 125.5 82.9 various thicknesses. The AFM images clarify that thin film is composed
of a uniform distribution of spherical nano-particles. The average grain
size and roughness were estimated and listed in Table 1. The grain size
GaClPc thin films increases as the layer thickness increases. For more
and the roughness increase as the film thickness increases. According to
elaboration in studying the structure of GaClPc thin films, the disloca­
the width and height-difference correlation function, the mean-square
tion density (δ), which introduces the length of dislocation lines per unit
surface roughness (Ro) is related to the film thickness (d) by the
volume, and the number of crystallites per unit surface area (Nc) was
power law of Ro ~ dγ, where γ is the growth exponent [17]. The
computed from the following equations [14]:
dependence of Ro on d was depicted in Fig. 3, and the value of γ was
1
δ= (2)
D2

d
Nc = (3)
D3

where d is the film thickness. The values of δ and Nc with different values
of film thickness were presented in Table 1. Accordingly, we can notice
the decrease of δ and the increase of Nc as the film thickness increases.
Hence, these results verify the enhancement of film crystallography as
the film thickness increases.
In common, the self-assembling nanostructure and the arrangement
of molecular orientations during the evaporation technique strongly
depends on growth conditions and the type of the substrate. It is well
known that the π-π* interactions between the GaClPc molecules are
effectively affected by another π-π* interaction with the substrate mol­
ecules. Hence, the strength of the π-π* interactions between the sample
molecules and the substrate molecules plays an essential role in the
orientation of the molecules and on the particle accumulation, which in
turn has its effect on the shape and the enhancement of crystallization.
For example, the grain size of GaClPc in the present work as it deposited Fig. 3. The mean-square surface roughness (Ro) versus the film thickness (d) of
GaClPc films.
on glass substrate was estimated to be 16.65 nm, whereas the grain size

Fig. 2. AFM of GaClPc films with different thickness (a) 45 nm (b) 75 nm (c) 98 nm and (d) 151 nm.

3
E.F.M. El-Zaidia et al.
estimated to be 0.19 ± 0.05. Due to the Kandar-Parish-Zhang growth
model, the small value of γ is mainly attributed to the amorphous
structure in the initial stage of the film growth [17]. This result is
verified by the absence of the diffraction peaks for (45 nm-film thick­
ness) of GaClPc film as was observed from the XRD-pattern.
Indeed, it is noticed that the grain size measured in AFM approxi­
mation can be greater than the crystallite size estimated from XRD. Here,
we speculate that the reason for getting bigger grain size as observed on
the surface morphology of the film is due to the agglomeration of smaller
crystals, while the XRD provides information about average crystallites
size that coherently scatters X-rays [18].
3.2. Linear optical characterizations
In the wavelength (λ) range of 200–2500 nm, the T and R of GaClPc
film, with various thicknesses, were depicted in Fig. 4. The trans­
mittance range is well observed in the visible light region (λ > 900 nm).
Meanwhile, the spectra of all films showed an optical transmittance edge
due to the most significant formation of excitons binding energy [19].
The transmittance in the visible range was significant, and the border of
the transparent domain was observed to be regular for all the films,
except the film of the lowest thickness (d = 45 nm). This result confirms
the homogeneity of the films with a thickness beyond 45 nm due to the
peak diffraction observed in the XRD analysis. Whilst, the wholly
amorphous structure of 45 nm film thickness unveils the existence of
various sublevels states occurred due to the production of disorder im­
perfections inside the structural film [20]. In the transmittance region,
the possibility of equality (T + R = 1) was satisfied, which means there is
a weak absorption of incident light that may be occurred in this region.
In contrast, in the short wavelength (i.e. UV-spectra), the absorption of
light is noticeable, and this region is known as the absorption domain of
light.
The way in which the extinction coefficient (k) relies on the wave­
length of the incident light, is a confidential physical method to un­
derstand the types of charges transport between the molecular orbits.
Hence, many familiar bands such as Q-band, B-band, C-band, and other
bands may be found due to the type of electron and holes transitions.
Utilizing the deliberate data of T and R, the absorption coefficient (α)
has been calculated using the following equation [14]:
⎛ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ ⎞
1 ⎝1 − R 2 1 − R2 ⎠
α = ln + R2 + (4)
d 2T 4T 2
Then, the values of k were calculated using k = αλ/4π. Fig. 5 dis­
played the variation of k values with λ values in the region of UV-VIS
spectra. In particular, the Q-band is related to the excitations between
Fig. 4. T and R as a function of λ for GaClPc films with different thickness.
4
Optical Materials 109 (2020) 110407
Fig. 5. The spectra of extinction coefficient (k) as a function of λ for GaClPc
films with different thickness.
the states of HOMO (π-state) and the LOMO (π*-state) [19]. According to
Fig. 5, it is clearly observed that Q-band splitting into two peaks (around
630–745 nm) for all the films with different film thicknesses. However,
the position of the peaks as a function of wavelength is shown to shift
towards the lower wavelength as the film thickness increases. As pointed
out by many of the literature, the metallo-phthalocyanine or
metallo-phthalocyanine chloride are classified into two forms (i,e dimer,
and monomer) [21]. Indeed, in the dimer form, the nearness of the two
rings can motivate the coupling between the transition moments for two
identical molecules. This interaction leads to two new levels of energy,
and the separation between them is attributed to the exciton splitting
energy. If there are two molecules in the unit cell, two exciton bands will
be presented in the spectrum and the corresponding Davydov splitting is
produced. Referring to many of the literature, it was reported that, the
allowed optical transition can be determined from the geometric
arrangement of dipoles. For instance, if the molecules oriented parallel
to one another and perpendicularly to the axis of the dimer, during the
film growth, then the only optical transition to higher (E− ) level of the
Davydov splitting is allowed and transition to lower (E+) level is
forbidden. This transition leads to a shift in absorbance spectra in the
direction of larger energy (shorter wavelength). And Vice versa, if the
molecules oriented parallel to one another and parallel to the axis of the
dimer, an only optical transition to lower (E+) level of the Davydov
splitting is allowed. This transition leads to a shift in absorbance spectra
in the direction of lower energy (longer wavelength).
Another aspect is also important to mention is the importance of
estimating the polymorphic phase of the layer obtained in the vacuum
sublimation process. In the case of the α-polymorphic phase, the changes
in the film layers unveil the changes in the film structure. This can be
verified by the relative changes in the intensity of the individual peaks in
the Q-bands. Otherwise, if there are negligible changes in the intensity of
the individual bands, then the β-polymorphic phase is dominant. On the
other hand, the position of the individual peak (E+(nm), E-(nm)), and
the energy separation due to Davydov splitting ΔQ in the Q-band for the
various film thickness of GaClPc films were listed in Table 2. It is
observed from this table the shifted of the position of the peaks to the
Table 2
The individual peaks position (E+), E- and the energy separation due to Davydov
splitting ΔQ in the Q-band for the various film thickness of GaClPc films.
d (nm) E+ (nm) E- (nm) E+ - E- (nm) ΔQ (eV)
45 735.3 633.8 101.5 0.27
75 738.9 637.5 101.4 0.26
98 742.5 670.2 72.3 0.18
151 738.5 668.3 72.2 0.17
E.F.M. El-Zaidia et al. Optical Materials 109 (2020) 110407

higher energy as the film thickness. However, the experimental Davydov

peaks positions (E+(nm), E-(nm)) of the Q-bands, for GaClPc films with
approximately the same film thickness as extracted in the present work,
was found to be compatible with the numerical value of the same sample
as reported by the works of [22] Further, the experimental ΔQ values of
CoPc and ZnPc were evaluated to be 0.23 e V and 0.24 e V, respectively
[23,24]. Whereas the obtained value of ΔQ of GaClPc, in the present
work, with approximately the same film thickness was found to be 0.18 e
V, which means that the ΔQ of the present sample is also comparable
with the relative value of the most Pcs compounds.
In general, the B-band is corresponding to the transition of electrons
between the 4p1 state and the π* state [19]. As it is observed from this
figure, it was noticed that the absorption peaks are slightly shifted to the
higher energy of incident photons, which reveals the effect of the film
thickness on the location of the appearance bands. Hence, this result
suggests the slight increase of the bond length for both of π- π* bond and
4p1- π* as the film thickness increases. Also, this result is harmonized
with the analysis of the XRD-pattern and the AFM investigation which
Fig. 6. The spectral dependence of y/y’ for GaClPc films with
verifies that the boosting of the material crystallography may cause different thickness.
changes in the bonding length even these changes are of little impact.
Further, the increase in the peak intensity of the extinction coefficient,
as shown in Fig. 5, unveils the possibility of favorable high absorption of
incident light as the film thickness increases, which means that this
material possesses exclusive merit to be used in the fabrication of a solar
cell unit.
In particular, the values of the bandgap energies are usually evalu­
ated from the immensely sharp edges observed in the spectral of α. To
determine the type of the optical transition in the Q-band and the B-
band, the Tauc’s relation is mainly used [20]. Meanwhile, the values of
fundamental and optical band gap energy can be also calculated from
this equation. According to Tauc’s equation, the values of the band gap
energy can be estimated as follows [20].
( )
(αhv)r = A hv − Eg (5)

where A is constant, hν is photon energy, Eg is the energy gap and r is

constant which is applied to determine the real sort of the optical
transition. Accordingly, the type of transition can be determined as
follows: for r = 2, the transition is related to direct allowed transition. In
contrast at r = 1/2, the correlated transition is known as the indirect
allowed transition. The examination of the best fitting values of r has
been achieved by a simple estimation method which was described in
our previous work [12]. According to this method, the fitting value of r
can be estimated from the following relation:
/ ( )
1 ( ) relative phthalocyanine compounds was presented in Table 4. As shown
y y’ = hv − Eg (6)
r g and Eg values of
where y = αhν and y’ is the first derivative of y concerning hν. Hence,
Fig. 6 displayed the variation of y/y’ with respect to the photon energy
for GaClPc film with a thickness of 151 nm thin film. The slope of the
fitting line, as calculated from this figure, was found to be 0.50 ± 0.09
which indicates that the indirect allowed transition is the realistic model
to describe the optical transitions inside GaClPc thin films.
After that, the values of (αhv)1/2 versus hν were plotted in Fig. 7. This
figure unveils two kinds of energy bands. The lowest values of these
band energies are defined as the optical band gap energy (Eopt
g ), which is
attributed to many factors such as the formation of vacancies and dis­
locations inside the film microstructure [25]. The higher band gap en­
ergy is known as the fundamental band gap energy (Eg) and is usually
explained by the π-π* transition [25]. From the figure, the values of the
band gap energies for different thicknesses of GaClPc thin films are
unaffected by the film thickness were found to be 1.49 eV and 2.92 eV
for Eopt opt
g and Eg, respectively. We can conclude that Eg and Eg, unaffected
by the film thickness, which confirms the competence of the thermal
vacuum evaporation in avoiding the existence of oxidation layers during
the growth of the deposited the GaClPc compounds. Moreover, the vapor
Fig. 7. The relation between (αhν)1/2 and hν for GaClPc films with
different thickness.
of the GaClPc compound showed a weak tendency to react with the tiny
of the remaining of OH-groups during the evaporating process. How­
ever, the comparing of the band gap energies values with the other
from this table, we can deduce that the obtained Eopt
GaClPc thin films are compatible with the other phthalocyanine thin
films [11,26–30].
The refractive index (n) is considered the key parameter of the op­
toelectronic devices and the values of n for our synthesized thin film is
determined from [29].
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
(1 + R) + 4R − (1 − R)2 k2
(7)
n=
(1 − R)
Fig. 8 depicts the dependence of n values on λ values in the region of
UV-VIS spectra. The n values, as exhibited in this figure, are divided into
distinguishable domains. The normal dispersion refractive index which
is observed in the visible region (λ > 900 nm) and can be certainly
described by the single oscillator model. While the anomalous disper­
sion (λ < 900 nm) usually appears in the UV-spectra, and it is particu­
larly explained by the multi-oscillator model [31]. The increase of the
normal dispersion (n values) as the film thickness increases can be
explained due to the increase of the material crystallography which in
turn will reduce the optical film density.
The observed dispersion behavior can be explained if it is assumed to

5
E.F.M. El-Zaidia et al. Optical Materials 109 (2020) 110407

Table 3
Linear and nonlinear optical parameters for GaClPc films at a different film thickness.
d (nm) Eo (eV) Ed (eV) ε∞ εL N/m* ( × 1047g− 1cm− 3) no χ(3) n2 ( × 10− 11
esu)
12
( × 10− esu)

45 1.09 5.62 5.46 9.87 10.3 2.34 2.70 4.35

75 1.12 8.39 7.32 12.55 12.0 2.71 10.88 15.16
98 1.15 11.17 8.74 14.65 11.9 2.95 24.46 31.21
151 1.16 12.13 9.38 14.78 11.5 3.06 33.62 41.40

Table 4
Comparison of optical parameters with other phthalocyanine compounds.
film Eg1 (eV) Eg2 (eV) E (eV) Ed (eV) ε∞ εL N/m* ( × 1047 g− 1cm− 3) Ref

GaClPc 1.49 2.92 1.09 5.62 5.46 9.87 10.3 Current work
GaClPc 1.52 3.23 [26]
AlPcCl 1.42 2.87 1.59 4.04 3.53 4.86 0.89 [11]
SnPcCl2 1.51 2.79 – – – – – [27]
NiPc 1.58 2.77 3.40 7.78 3.30 3.73 1.92 [28]
MgPc 1.34 2.47 3.59 8.48 3.36 3.58 0.25 [29]
CoPc 1.54 3.03 1.52 3.28 3.15 4.82 2 [30]

Fig. 8. The spectra of refractive index, n, a function of λ for GaClPc films with
different thickness. Fig. 9. The relation between 1/(n2 -1) and (hν)2 for GaClPc films with
different thickness.

be the response of a set of Lorentzian oscillators of adjustable strength

and position [32]. Using this postulation, the refractive index as a
function of photon energy can be analyzed based on the single oscillator
model, for photon energies below the interband absorption edge. Based
on this theory, Wemple and DiDomenico introduced two parameters: the
dispersion energy (Ed) and the single oscillator energy (Ea). For instance,
Ed is mainly used to determine the interband optical transitions [33],
whilst Ea represents the single oscillator energy which is affected by the
creation of excitons through the material [20]. These two parameters,
which were firstly discussed by Wemple and DiDomenico, are mainly
calculated by the following equation [14,33]:
( ) ( ) is the ratio of free carrier concentration to the free carrier effective mass.
( 2 )− 1 Ea 1
n − 1 = − (hv)2 (8)
Ed Ea Ed
Fig. 9 depicts the dependence of (n2 – 1)− 1 on (hν)2 in the region of
the low photon energy. In fact, in the low energy, the relationship be­
tween (n2 – 1)− 1 and (hν)2 is linear and consequently, the values of Ed
and Ea can be estimated from the slope and the extrapolation of the
fitting line until it intersects with the y-axis at hν equal to zero. Further,
the value of high-frequency dielectric constant (ε∞) can be obtained
from the intersection of the fitting line with the y-axis. Hence, the values
of Ea, Ed, and ε∞ for GaClPc thin films with different thicknesses were
given in Table 3. The increase of these parameters as the film thickness
increases can be explained due to the change of the ionicities which is
mainly occurred by the raising of the cations coordinating number to the
almost neighbor anions [19]. Also, the comparing of these constants
with the relative phthalocyanine compounds has been reported in
Table 4.
The lattice dielectric constant (εL) can be calculated according to the
following expression [14]:
e2 N
n2 = εL − λ2 (9)
4π2 ε0 m* c2
where e is the electron charge, εo is the free space permittivity and N/m*
Fig. 10 displays the dependence of n2 on λ2 in the transparent region. It is
observed that the dependence of n2 on λ2 is linear at longer wavelengths,
and thus the values of εL and N/m* can be easily calculated from the
extrapolation line towards λ2 → 0 and the slope of the fitting line
respectively.
These values were listed in Table 3. It was found from this table, the
remarkable increase of εL and N/m* as the film thickness increases
which may be attributed to the increase of the lattice vibration and the
decline of the bonded carrier in the visible region of light. Furthermore,
the comparison of εL and N/m* values with other phthalocyanine com­
pounds were given in Table 4.

6
E.F.M. El-Zaidia et al.
Fig. 10. The relation between n2 and λ2 for GaClPc films with
different thickness.
3.3. Calculated nonlinear optical characterizations
The investigation of nonlinear optics parameters is essential to
explain the aspects that appear in the optical properties of the material
when it is exposed to incident light. The nonlinear optical properties of
the material reflect the response of the material with the strength of the
applied electromagnetic field of incident photons. The nonlinear optical
of the material is mainly given by a series expansion of the polarization
as follows [34]:
(( ) ( ) ( ) )
(10)
2 3
p̃ = ε0 χ (1) Ẽ + χ (2) Ẽ + χ (3) Ẽ + .....
where p̃ denotes the complex polarization, χ (n) represents the nth-order
susceptibility. The dealing with all terms of χ (n) is considered as one of
the difficult problems; meanwhile, the first three terms could provide us
with enough view of the natural interaction of the material with incident
light. The first term (χ (1)) represents the linear proportionality of
induced polarization with the applied electro-optical field. While χ (2),
which represents the second-order susceptibility, is usually ignored
since this parameter is attributed only to the noncentrosymmetric
crystals (having non-inversion symmetry). In contrast, χ (3), which is
related to the third harmonic oscillator photons (w1, w2, and w3) in
space, is mainly correlated with the centrosymmetric organic materials
and could be calculated.
The values of χ (1) can be calculated from the following equation [35]:
n2 − 1
χ (1) = (11)
4π
Fig. 11 illustrates the dependence of χ (1) on λ of incident light for
various film thicknesses. This figure clarifies the increase of χ (1) as the
film thickness increases which reveals the increase of the induced linear
polarization of the present material as the film thickness increases.
The induced polarizability of GaClPc molecular dipoles are produced
as a result of the electromagnetic field of the emerged photons. After
that, the existence of the generating polarized molecules in the region of
the electric field, which was produced originally from the emerged
photons, will induce a new polarization of GaClPc molecules to radiate
new photons with different frequencies. This phenomenon is known as
light control by light [36], and it is mainly understood by studying the
third-nonlinear susceptibility. Indeed, the studying of χ (3) is essentially
needed to optimize the different functionality for the enhancements of
the device application such as optical logic, photonics, and optical
switching [37]. The values of χ (3) at hν→ 0, can be evaluated from
Miller’s generalized rule as follows [34]:
7
Optical Materials 109 (2020) 110407
Fig. 11. The linear optical susceptibility as a function of wavelength for GaClPc
films with different thickness.
( 2 )4
( )4 n0 − 1
χ (3) = A χ (1) = A (12)
4π
where A is frequency-independent constant (A = 1.7 × 10− 10 esu [34]).
Further, the nonlinear refractive index (n2) can be evaluated from
Miller’s rule as follows [35]:
12πχ (3)
n2 = (13)
n0
The estimated values of no, χ (3) and n2 for various film thicknesses
were displayed in Table 3. It is clear from this table the raise of χ (3)
values as the film thickness increased. Indeed, the optical nonlinearity
χ (3) was found to be strongly affected by the extent of π-electron delo­
calization between the attached chains in the polymer (or oligomer)
structure and it was deduced that the expanded π-conjugation is also
often related with the enhanced conductivity in organic systems [38,
39]. Further, it was found the aligned chains of the organic molecules in
the direction of the induced electric field lead to a high value of the
third-nonlinear susceptibility [38,39]. Hence, we believe that the in­
crease of the film thickness may cause a possible orientation of the
molecular chains of GaClPc in unfavorable direction with the induced
electric field. Thus, the values of χ (3) raise. The comparing of χ (3) values
with the other phthalocyanine compounds, which were achieved by the
Millers generalized method, it found in the same order [11]. However,
many of the literature have adopted another method, such as Z-scan, to
study the nonlinear (NLO) optical properties of the materials. For
instant, the χ (3) value of alkoxy Phthalocyanines, as was estimated by the
Z-scan, was found to be 2.91 × 10− 12 esu [40]. Hence, the obtained
value of χ (3) estimated by the Z-scan is the same order with the value
getting from Millers generalized method for Pcs compounds.
3.4. Optical limiting characterizations
Nonlinear optical materials are predominantly used to enhance the
functions of the optical limiting (OL) devices due to its excellent atten­
uation of the intensive incident light. The dense incident light has a
considerable modification of the absorption and refractive character­
izations of the OL material. The superior OL materials are generally
characterized by their high transmittance of weak intense incident light
and filtering the intensive incident light to a reasonable transmittance
value [41].
The position of B-band and Q-band, as observed from the linear
absorption spectrum (See Fig. 5), was found to be in the region of 358
and 738 nm, respectively. Thus, GaClPc thin films have a window of
E.F.M. El-Zaidia et al. Optical Materials 109 (2020) 110407

high linear transmittance between these two bands which suggests the
possible utilizing of this material as a good limiter of visible light. Hence,
the OL properties of GaClPc films have been discussed by the normalized
power (I/Io) of two laser beams in the transmittance window of this
material. In this case, the red He–Ne laser of 638.2 nm and green diode
laser of 533 nm were used to test the validity of GaClPc films to atten­
uate the highly intensive light. The obtained values of the normalized
power for the He–Ne laser of 638.2 nm and green diode laser of 533 nm
were shown in Fig. 12 and Fig. 13. It can be displayed from the figure,
the significant attenuation of the incident He–Ne laser beam, as well as,
the incident 533 nm lasers light. This result verifies the possible use of
GaClPc films as a promised candidate OL material. Further, we deduced
that the increase of the film thickness has a slight effect in decreasing the
normalized power of GaClPc films. One the other hand, the compatible
attenuation of the present sample with the other organic films verifies
the high performance of GaClPc to attenuate the highly intensive inci­ Fig. 12. The output power and the normalized power after the transmission of
dent light. For instance, it was observed that the normalized power (I/Io) the incident light of the Red He–Ne Laser inside the GaClPc films. (For inter­
for the interaction of the incident light of He–Ne laser of 638.2 nm and pretation of the references to colour in this figure legend, the reader is referred
green diode laser of 533 nm with Methyl violet-10 B (MV-10 B to the Web version of this article.)
∼ nm180 film thickness) was found to be 0.285 and 0.381 respectively
[19]. Whereas, the normalized power of He–Ne laser of 638.2 nm and
green diode laser of 533 nm with the interaction of 151 nm film thick­
ness of GaClPc were measured to be 0.01 and 0.433, respectively.

4. Conclusions

The well-known vacuum thermal evaporating technique was used to

get homogenous thin films of GaClPc with different thicknesses (45, 75,
98, and 151 nm). The AFM images confirmed that the grain size and the
roughness were increased as the film thickness increases. The funda­
mental and the optical band gap energies of GaClPc with different values
of thickness were calculated, and they were found to be compatible with
the other phthalocyanine compounds. Also, it was found that the elec­
tron transition was followed by the indirect allowed transition. The
dielectric constants (Ed, Ea, and ε∞) and the lattice dielectric constant
(εL) of GaClPc thin films with different thicknesses were evaluated. Also,
the first-order susceptibility (χ (1)) and the third-nonlinear susceptibility
(χ (3)) of GaClPc with different values of thickness were calculated. χ (3)
has a value of 2.70 × 10− 12 esu for the film with 45 nm thickens, where
this value increased by increasing film thickens. Further, the investiga­
tion of the two laser beams (the He–Ne laser of 638.2 nm and green
diode laser of 533 nm) showed that the film of 45 nm has a normalized
power of 0.092 and 0.456, respectively. These values decreased as film
thickness increases to reach 0.01 and 0.433, respectively for the film of
151 nm. The investigation of the normalized power of the two laser
beams (the He–Ne laser of 638.2 nm and green diode laser of 533 nm)
suggests the possible utilizing of this material as a powerful candidate
material in the field of optical limiting. Further, our experimental results
calculation confirms that the value of the third-order optical suscepti­
bility makes this material interesting for future nonlinear optical ap­
plications. Moreover, the low optical band gap energy of GaClPc confers
this material the opportunity to be used in the application of solar cell
units.
5. Ethical statement letter
“I, the Corresponding Author, declare that this manuscript is orig­
inal, has not been published before and is not currently being considered
for publication elsewhere.
Author contributions section
This article was produced with the participation of all authors.
Fig. 13. The output power and the normalized power after the transmission of
the incident light of the Green Laser diode inside the GaClPc films. (For inter­
pretation of the references to colour in this figure legend, the reader is referred
to the Web version of this article.)
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
One of the authors (I.S. Yahia) expresses his appreciation to the
Deanship of Scientific Research at King Khalid University for funding
this work through research groups program under grant number R.G.
P.2/65/40.
References
[1] J.A.A. Krasnovsky, M. Bashtanov, N. Drazdova, O. Yuzhakova, M. Lukyanets, Laser
induced singlet-oxygen-sensitised delayed fluorescence of dyes in aqueous
solutions, Quant. Electron. 32 (2002) 83–86.
[2] S.E. Al Garni, A.A.A. Darwish, Photovoltaic performance of TCVA-InSe hybrid solar
cells based on nanostructured films, Sol. Energy Mater. Sol. Cell. 160 (2017)
335–339.
[3] J. Rogers, K. Nguyen, D. Hufnagle, D. Mc Lean, W. Su, K. Gossett, A. Burke,
S. Vinogradov, R. Pachter, P. Fleitz, Observation and interpretation of annulated
Porphyrins: studies on the photophysical properties of meso
tetraphenylmetalloporphyrins, J. Phys. Chem. 107 (2003) 11331.

8
E.F.M. El-Zaidia et al.
[4] Maxence Urbani, Maria-Eleni Ragoussi, Mohammad Khaja Nazeeruddin,
Tomás Torres, Phthalocyanines for dye-sensitized solar cells, Coord. Chem. Rev.
381 (2019) 1–64.
[5] Inta Muzikante, Vicente Parra, Rorijs Dobulans, Egils Fonavs, Janis Latvels,
Marcel Bouvet, A novel gas sensor transducer based on phthalocyanine
heterojunction Devices, Sensors 7 (2007) 2984–2996.
[6] Seungchel Choi, Sang-Hyun Hong, Hyo Cho Shin, Samdae Park, Su-Moon Park,
Ohyun Kim, Moonhor Ree, High-performance programmable memory devices
based on hyperbranched copper phthalocyanine polymer thin films, Adv. Mater. 20
(2008) 1766–1771.
[7] M. Hanack, M.M. Lang, Conducting stacked metallophthalocyanines and related
compounds, Adv. Mater. 6 (1994) 819–833.
[8] N. d’ Alessandro, L. Tonucci, A. Morvillo, L.K. Dragani, M. Di Deo, M. Bressan,
Thermal stability and photostability of water solutions of sulfophthalocyanines of
Ru(II), Cu(II), Ni(II), Fe(III) and Co(II), J. Organomet. Chem. 690 (2005)
2133–2141.
[9] Z.T. Liu, H.S. Kwok, A.B. Djurišić, The optical functions of metal phthalocyanines,
J. Phys. D Appl. Phys. 37 (2004) 678.
[10] E. V Tikhonov, D. R Khokhlov, Y.A. Uspenski, E.T. Kulatov, I.A. Belogorokhov,
Electronic and spin structure of metal phthalocyanines, Solid State Phenom. 190
(2012) 141–144.
[11] M.M. El-Nahass, H.S. Soliman, B.A. Khalifa, I.M. Soliman, Structural and optical
properties of nanocrystalline aluminum phthalocyanine chloride thin films, Mater.
Sci. Semicond. Process. 38 (2015) 177–183.
[12] A.A.A. Darwish, Saleem I. Qashou, M. Rashad, Structural, surface topography and
optical investigations of nanostructure films of copper (II) 2,9,16,23-teter-tert-
butyl-29H,31H-phthalocyanine controlled at thermal effect, Appl. Phys. A 125
(2019) 271.
[13] V. Tamara, V.G. Kieslver, F. Latteyer, H. Peisert, T. Chase, Molecular organization
in thin films of gallium(Ш) phthalocyanine chloride and its μ − oxodimer: optical
and spectroscopy and XPS study, Appl. Surf. Sci. 322 (2014) 242–248.
[14] Saleem I. Qashou, M. Rashad, A.Z. Mahmoud, A.A.A. Darwish, The promotion of
Indeno [1, 2-b] flourene-6, 12 dione thin film to be changed into stable aromatic
compound under the effect of annealing treatment, Vacuum 162 (2019) 199–207.
[15] Saleem I. Qashou, A.A.A. Darwish, S.E. Al Garni, Enhancement of microstructure
and electrical conductivity of N, N′ -dimethyl-3,4,9,10-perylenedicarboximide
nanostructured films by thermal annealing for photoelectronic applications, Synth.
Met. 242 (2018) 67–72.
[16] A. Zawadzka, A. Karakas, P. Pł_ociennik, J. Szatkowski, Z. Łukasiak, A. Kapceoglu,
Y. Ceylan, B. Sahraoui, Optical and structural characterization of thin films
containing metallophthalocyanine chlorides, Dyes Pigments 112 (2015) 116–126.
[17] Joachim Krug, Origins of scale invariance in growth processes, Adv. Phys. 46
(1997) 139–282.
[18] F.A. Akgul, G. Akgul, N. Yildirim, H.E. Unalan, R. Turan, Influence of thermal
annealing on microstructural, morphological, optical properties and surface
electronic structure of copper oxide thin films, Mater. Chem. Phys. 147 (2014)
987.
[19] E.F.M. El-Zaidia, M.S. Al-Kotb, I.S. Yahia, Deposition of nanostructured methyl
violet-10B films/FTO: optical limiting and optical linearity/nonlinearity, Mater.
Chem. Phys. 240 (2020) 122074.
[20] A.Z. Mahmoud, A.A.A. Darwish, Saleem I. Qashou, Film thickness effects on
nanorods organic films of azo quinoline derivatives for optical applications, Prog.
Nat. Sci.: Materials International 29 (2019) 402–409.
[21] A. Zawadzka, P. Płóciennik, J. Strzelecki, M. Pranaitis, S. Dabos-Seignon,
B. Sahraou, Structural and nonlinear optical properties of as-grown and annealed
metallophthalocyanine thin films, Thin Solid Films 545 (2013) 429–437.
Optical Materials 109 (2020) 110407
[22] A. Zawadzka, P. Płociennik, I. Czarnecka, J. Sztupecka, Z. Łukasiak, The effects of
annealing process influence on optical properties and the molecular orientation of
selected organometallic compounds thin films, Opt. Mater. 34 (2012) 1686–1691.
[23] M.M. El-Nahass, Z. El-Gohary, H.S. Soliman, Structural and optical studies of
thermally evaporated CoPc thin films, Optic Laser. Technol. 35 (2003) 523–531.
[24] M.M. El-Nahass a, H.M. Zeyada, M.S. Aziz, N.A. El-Ghamaz, Structural and optical
properties of thermally evaporated zinc phthalocyanine thin films, Opt. Mater. 27
(2004) 491–498.
[25] A.A.A. Darwish, Saleem I. Qashou, Z. Khattari, Mustafa M. Hawamdeh,
Allayth Aldrabee, S.E. Al Garni, Effect of gamma radiation induced on structural,
electrical, and optical properties of N, N′ -Dimethyl-3,4,9,10 perylenedicarboximide
nanostructure films, J. Electron. Mater. 47 (2018) 7196–7203.
[26] A. Zawadzkaa, K. Waszkowskaa, A. Karakas, P. Płóciennik, A. Korcala,
K. Wisniewski, M. Karakaya, B. Sahraoui, Diagnostic and control of linear and
nonlinear optical effects in selected self assembled metallophthalocyanine
chlorides nanostructures, Dyes Pigments 157 (2018) 151–162.
[27] M.M. El-Nahass, K.F. Abd-El-Rahman, A.A. Al-Ghamdi, A.M. Asiri, Optical
properties of thermally evaporated tin-phthalocyanine dichloride thin films,
SnPcCl2, Physica B 344 (2004) 398–406.
[28] A.A.A. Darwish, Shams A.M. Issa, M.M. El -Nahass, Effect of gamma irradiation on
structural, electrical and optical properties of nanostructure thin films of nickel
phthalocyanine, Synth. Met. 215 (2016) 200–206.
[29] M.M. El-Nahass, A.A. Atta, H.E.A. El-Sayed, E.F.M. El-Zaidia, Structural and optical
properties of thermal evaporated magnesium phthalocyanine (MgPc) thin films,
Appl. Surf. Sci. 254 (2008) 2458–2465.
[30] M.M. El-Nahass, A.A.M. Farag, A.A. Atta, Influence of heat treatment and gamma-
rays irradiation on the structural and optical characterizations of nano-crystalline
cobalt phthalocyanine thin films, Synth. Met. 159 (2009) 589–594.
[31] O. Stenzel, S. Wilbrandt, A. Stendal, U. Beckers, K. Voigtsberger, C. Von
Borczyskowski, The incorporation of metal clusters into thin organic dye layers as a
method for producing strongly absorbing composite layers: an oscillator model
approach to resonant metal cluster absorption, J. Phys. Appl. Phys. 28 (1995)
2154.
[32] M. Ghanashyam Krishna, J.S. Pillier, A.K. Bhattacharya, Variable Optical
Absorption Edge in Ion Beam Sputtered Thin Ytterbium Oxide Films Thin Solid
Films vol. 357, 1999, pp. 218–222.
[33] S.H. Wemple, M.D. DiDomenico, Behavior of the electronic dielectric constant in
covalent and ionic materials, Phys. Rev. B 3 (1970) 1338.
[34] R.W. Boyd, G.L. Fischer, Nonlinear Optical Materials, Encyclopedia of Materials:
Science and Technology, second ed., 2001, pp. 6237–6244.
[35] L. Tichý, H. Ticha, P. Nagels, R. Callaerts, R. Mertens, M. Vlcek, Optical properties
of amorphous As-Se and Ge-As-Se thin films, Mater. Lett. 39 (1999) 122–128.
[36] P.N. Prasad, Third-order nonlinear optical effects in molecular and polymeric
materials, ACS (Am. Chem. Soc.) Symp. Ser. 455 (1991) 50–66.
[37] M. Frumar, J. Jedelský, B. Frumarová, T. Wágner, M. Hrdlička, Optically and
thermally induced changes of structure, linear and non-linear optical properties of
chalcogenides thin films, J. Non-Cryst. Solids 326–327 (2003) 399–404.
[38] D.S. Chemla, J.E. Zyss, Nonlinear Optical Properties of Organic Molecules and
Crystals, vols. I and 2, Academic Press, Orlando, 1987.
[39] Nonlinear optical properties of polymers, in: A. J Heeger, J. Orenstein, D.R. Ulrich
(Eds.), Mater. Res. Soc. Symp. Proc.: Pittsburgh 109 (1987).
[40] P.T. Anush, P. Silviya Reet, L. Giribabu, Surya P. Tewari, S. Venugopal Rao,
Picosecond nonlinear optical studies of unsymmetrical alkyl and alkoxy
phthalocyanines, Mater. Lett. 64 (2010) 1915–1917.
[41] M. Hanack, Th Schneider, M. Barthel, J.S. Shirk, S.R. Flom, R.G.S. Pong, Indium
phthalocyanines and naphthalocyanines for optical limiting, Coord. Chem. Rev.
219–221 (2001) 235–258.