Optical Materials 85 (2018) 483–490

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

Photoluminescent electrospun europium complex Eu(TTA)3phen embedded T

polymer blends nanofibers
Manjusha P. Dandekara, Sangeeta G. Itankara, Subhash B. Kondawara,∗, Deoram V. Nandanwarb,
Pankaj Koinkarc,∗∗
a
Department of Physics, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur, 440033, India
b
Department of Physics, Shri Mathuradas Mohata College of Science, Nagpur, 440023, India
c
Department of Optical Science, Tokushima University, Tokushima, 7708506, Japan

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

Keywords: Europium complex Eu(TTA)3phen (TTA = 2-thenoyltrifluoroacetone, phen = 1,10-phenanthroline) was in-
Photoluminescence corporated into polymer blends made of polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(viny-
Europium complex lidene fluoride) (PVDF) to fabricate Eu(TTA)3phen/PVDF-PS, Eu(TTA)3phen/PVDF-PMMA and Eu(TTA)3phen/
Polymer blends PS-PMMA nanofibers by electrospinning for photoluminescent fabric designing. These nanofibers have been
Nanofibers
characterized by scanning electron microscopy with energy dispersive x-ray spectroscopy (SEM-EDX), Fourier
Electrospinning
transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD). Photoluminescence of Eu(TTA)3phen/
polymer blends nanofibers was systematically compared with pure Eu(TTA)3phen which showed typical Eu3+
ion red emission, assigned to the transitions between the first excited state (5D0) and the multiplet (7F0-3). The
presence of different polymer blends as matrix for Eu(TTA)3phen increases the fluorescent intensity of the
5
D0→7F2 hypersensitive transition of Eu3+ ions. Eu(TTA)3phen/PVDF-PS and Eu(TTA)3phen/PVDF-PMMA na-
nofibers showed better photoluminescence properties compared to that of Eu(TTA)3phen/PMMA-PS nanofibers
because of influence of polymers on the coordinative environment of europium ions and the dimensional effect
of polymer blend fibers. Eu(TTA)3phen/PVDF-PS and Eu(TTA)3phen/PVDF-PMMA nanofibers are found to be
potential materials for photoluminescent material designing.

1. Introduction
The photoactive lanthanide complexes such as europium with β-
diketones have great curiosity due to their intense emission peaks in the
visible and near infrared region under ultraviolet excitation. The tri-
valent europium ion (Eu3+) exhibits strong and intense emission bands
based on their f-f electronic transition and wide range of luminescent
lifetime suitable for various applications. But, trivalent europium ions
(Eu3+) have low absorption coefficient which limits the lighting output.
However, this can be enhanced by forming complexes of the rare-earth
ions with organic ligands. The absorption bands of the chromophores of
organic ligands are very strong, and hence ligand Eu(TTA)3phen can
absorb much more light than the Eu3+ ions. These ligands can proceed
as an antenna to absorb the excitation light and to transfer the excita-
tion energy to the higher energy levels of the Eu3+ ion, from which the
emitting excited levels can be populated. Phen is a synergic shielding
ligand which can reduce the rate of non-radiative decays and strongly
enhance the luminescence intensity of the complex [1–3]. The presence
of the ligand surrounding the ions acts as a physical buffer between the
rare-earth ions [4]. The increase of the absorptivity of the ligand may
improve the luminescent intensity of the complex. In these complexes,
the Eu(TTA)3phen has attracted a lot of attentions due to their high
fluorescence emission efficiency as the result of the high absorption
coefficient of the β-diketone ligand (TTA) and the synergistic effect of
1,10-phenanthroline (phen) [5–7]. Therefore, Eu(TTA)3phen as a suc-
cessful lanthanide organic complex has great concentration in high
merit of the intense emission peaks in the visible and near-infrared
region upon UV excitation. However, shortcoming of Eu(TTA)3phen
complexes with low processing ability, poor thermal stability and low
mechanical strength which bound its direct applications in the earlier
period. In order to overcome these limitations, europium complexes are
usually incorporated into organic, inorganic or organic/inorganic hy-
brid matrices [8,9]. The incorporation of europium complexes into
organic polymers presents an ideal and multipurpose approach to

∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: sbkondawar@yahoo.co.in (S.B. Kondawar), koinkar@tokushima-u.ac.jp (P. Koinkar).

https://doi.org/10.1016/j.optmat.2018.09.019
Received 7 April 2018; Received in revised form 1 September 2018; Accepted 10 September 2018
0925-3467/ © 2018 Elsevier B.V. All rights reserved.
M.P. Dandekar et al.
generate hybrid materials. It has been verified that the polymer-capped
complexes possess improved photoluminescence properties with
thermal stability and mechanical flexibility [10]. The presence of rare
earth (RE) complex in polymer has enhanced the luminescent effi-
ciencies due to uniform distribution of the complex along macro-
molecular chains of the polymer. The RE complexes incorporated in the
polymer matrices represents a class of new materials which shows the
characteristics of both the complexes and the matrix materials, making
them applicable in a broad range of new technologies. In recent years,
Eu(TTA)3phen/PS, Eu(TTA)3phen/PMMA, Eu(TTA)3phen/PVDF and
Eu(TTA)3phen/PVP have been carried out to improve the photo-
luminescence properties [11,12]. DBM (dibenzoylmethane) was also
used in RE complexes in place of TTA with PS, PMMA polymers
[13,14]. PMMA (polymethylmethacrylate) is well recognized for its
high transparency, flexible, excellent optical properties and simple
synthesis process, which make the material to be perfect host for rare-
earth ions [15]. PVDF (polyvinylidine fluoride) is a semicrystalline
polymer with very good resistance to chemicals, oxidation, and UV
radiation. It is also known for its polymorphism crystalline structure
and one of the most extensively studied polymers due to its non-line-
arity, piezo and pyro-electricity [16–19]. PS (polystyrene) is a long
chain hydrocarbon wherein alternating carbon centres are attached to
phenyl groups. The short-range van der Waals attractions between
polymer chains of polysterene confer flexibility and elasticity [20].
One-dimensional (1D) nanofibers have great attention due to their
outstanding properties and potential applications in many fields. The
polymer nanofibers synthesized by the electrospinning technique ac-
quired several advantages, such as exceedingly high surface-to-volume
ratio, tuneable porosity, malleability and the ability to control the na-
nofiber composition to accomplish the required performances from
their properties and functionalities. Electrospun nanofibers are good
candidates for protective clothing, filtration, electrode materials, op-
tical and chemical sensors, microarray optical ion sensors, defence and
security, optical communication and environmental engineering fields
[21–25]. The electrospinning is an exclusive approach and easiest way
using electrostatic force to fabricate the nanofibers from polymer so-
lutions or melts. The solution used in the electrospinning process has a
significant influence on its spinnability [26–28]. The presence of rare
earth complexes in polymers or polymer blends fabricated by electro-
spinning increases the fluorescent intensity of the 5D0→7F2 hy-
persensitive transition of ions [29–31].
We have reported the fabrication and photoluminescence properties
of electrospun Eu(TTA)3phen/PMMA, Eu(TTA)3phen/PS and Eu
(TTA)3phen/PVdF nanofibers [32]. The enhanced intensity ratios of
5
D0→7F2 to 5D0→7F1 in these composite nanofibers have indicated
more polarized chemical environment of Eu3+ ions and relatively
stronger hypersensitive behaviour of the 5D0→7F2 transition. This study
has influenced the researchers to use the different polymer blends na-
nofibers as matrices to improve the photoluminescence properties of Eu
(TTA)3phen for photoluminescent material designing. In this light of
improvement in fluorescent intensity of the 5D0→7F2 hypersensitive
transition of Eu3+ ions with the advantages of electrospinning, a series
of luminescent Eu(TTA)3phen nanofibers with the different combina-
tion of polymer blends as matrices have been fabricated. The photo-
luminescence properties of the Eu(TTA)3phen/PVDF-PS, Eu
(TTA)3phen/PVDF-PMMA and Eu(TTA)3phen/PS-PMMA nanofibers
were studied in comparison with that of the pure Eu(TTA)3phen. By
investigating the fluorescent spectral characteristics, the effect of
polymer blend matrix on the fiber diameter for improving photo-
luminescence properties for light emitting material designing is sys-
tematically explored in terms of luminescence parameters and CIE co-
ordinates.
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Optical Materials 85 (2018) 483–490
2. Experimental
2.1. Preparation of Eu(TTA)3phen and Eu(TTA)3phen/polymer blend
solutions
Europium complex Eu(TTA)3phen was synthesized by a simple so-
lution route as reported in our earlier work [32]. For the preparation of
Eu(TTA)3phen/PS-PMMA blend solution for electrospinning, 1g PS and
1g PMMA were dissolved in 10 ml tetrahydrofuran (THF) and magne-
tically stirred for 12 h till to get homogeneous solution. 20% Eu
(TTA)3phen powder was added to PS-PMMA blend solution and mag-
netically stirred for 12 h till to get homogeneous solution. Similarly, Eu
(TTA)3phen/PVDF-PS and Eu(TTA)3phen/PMMA-PVDF solutions were
prepared by using specific polymer for blends with the same processing
condition.
2.2. Fabrication of Eu(TTA)3phen/polymer blend nanofibers by
electrospinning
As-synthesized Eu(TTA)3phen/polymer blend solution was loaded
into a 5 ml disposable plastic syringe with the metallic needle of 0.5 mm
diameter for electrospinning. During the electrospinning process at
room temperature, the solution was fed to the tip using a computer
controlled syringe pump at a flow rate of 0.2 ml/h. A positive voltage of
20 kV was applied to the needle of the syringe containing solution and
the metallic plate wrapped with aluminium foil was grounded and kept
at a distance of 15 cm from the needle of the syringe. The electrospun
nanofibers were collected on the conducting foil (aluminium). After
electrospinning, the nonwoven membranes of the fibers were dried in a
vacuum oven at 60 °C for 12 h to remove the residual organic solvent.
Electrospinning process was carried out separately for the fabrication of
Eu(TTA)3phen/PMMA-PVDF, Eu(TTA)3phen/PS-PMMA and Eu
(TTA)3phen/PVDF-PS nanofibers.
2.3. Characterizations
The surface morphology and elemental composition of Eu
(TTA)3phen/PVDF-PS, Eu(TTA)3phen/PVDF-PMMA and Eu
(TTA)3phen/PS-PMMA nanofibers were investigated by scanning elec-
tron microscope (CARL ZEISS EVO-18) equipped with energy dispersive
X-ray spectroscopy. Fourier transform infrared (FTIR) spectra were
obtained on Thermo-Nicolet, Avatar 370 Infrared Spectrometer. X–ray
diffraction (XRD) patterns were recorded on Rigaku Miniflex II Desktop
X-ray diffractometer. Photoluminescence (PL) spectra were recorded on
Spectrofluorometer model FP8200 fluorescence spectrophotometer.
3. Results and discussion
3.1. Morphology
The morphology of the electrospun fibers is dependent upon the
solution conductivity, solution concentration, polymer molecular
weight, viscosity, surface tension, flow rate, applied voltage, and dis-
tance between syringe needle to collector [31]. With the same proces-
sing condition, (a) Eu(TTA)3phen/PVDF-PS, (b) Eu(TTA)3phen/PVDF-
PMMA, and (c) Eu(TTA)3phen/PMMA-PS blends nanofibers were fab-
ricated and their SEM images are respectively shown in Fig. 1 (a),
Fig. 1(b) and (c). The nanofibers are aligned in random orientation
caused by the bending instability associated with the spinning jet. The
diameter of the fibers is not same for all the composites due to the usage
of different electrospinning solvents and solution concentration.
Average diameter of Eu(TTA)3phen/PVDF-PS, Eu(TTA)3phen/PVDF-
PMMA and Eu(TTA)3phen PS-PMMA was found to be 690 nm, 324 nm
and 2400 nm respectively, as obtained from their histograms shown in
Fig. 1(a–c). Nanofibers with smaller diameter has high surface area due
to which more emission centres Eu3+ can be excited and may show
M.P. Dandekar et al. Optical Materials 85 (2018) 483–490

Fig. 1. (a): SEM image and histogram of Eu(TTA)3phen/PVDF-PS nanofibers.

(b): SEM image and histogram of Eu(TTA)3phen/PVDF-PMMA nanofibers.
(c): SEM image and histogram of Eu(TTA)3phen/PMMA-PS nanofibers.

Fig. 2. EDX spectra of (a) Eu(TTA)3phen complex and (b) Eu(TTA)3phen/PVDF-PMMA nanofibers.

485
M.P. Dandekar et al.
Fig. 3. (a): FTIR spectrum of Eu(TTA)3phen.
(b): FTIR spectra of Eu(TTA)3phen/PVDF-PMMA, Eu(TTA)3phen/PVDF-PS, and
Eu(TTA)3phen/PMMA-PS nanofibers.
better photoluminescence properties.
3.2. Energy dispersive x-ray spectroscopy
An energy-dispersive x-ray spectroscopy (EDX) was used to examine
the elemental composition of Eu(TTA)3phen. Fig. 2(a) shows EDX
spectrum of europium complex. It shows the presence of C, O, Eu, S and
F, elements in europium complex due to TTA and phen. This confirmed
that the europium complex Eu(TTA)3phen was successfully synthesized
and used for Eu(TTA)3phen/polymer blends nanofibers. Fig. 2(b) shows
EDX spectrum of Eu(TTA)3phen/PVDF-PMMA nanofibers. It also shows
the presence of C, O, Eu, S and F, elements in Eu(TTA)3phen/PVDF-
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Optical Materials 85 (2018) 483–490
PMMA with more percent of F and C due to PVDF–PMMA matrix in-
dicating that europium complex was successfully electrospun using
polymer PVDF-PMMA blend.
3.3. Fourier transform infrared spectroscopy
Fig. 3(a) shows FTIR spectra of europium complex Eu(TTA)3phen.
C]O stretching vibration of TTA in the complex is shifted to lower
frequency from 1645 cm−1 of free TTA to 1624 cm−1 of coordinated
TTA, as the intensity of C]O weakens after it coordinates with Eu3+
ions. C]C stretching vibration of TTA in the complex is also shifted to
lower frequency from 1585 cm−1 to 1535 cm−1. The stretching vibrant
peak of the C]N bond in phen shifted from 1614 to 1601 cm−1 and the
peak of CeH bond shifted to 724 and 843 cm−1 shows that phen par-
ticipated in the coordination with Eu3+ [11,33]. Fig. 3(b) shows FTIR
spectra of Eu(TTA)3phen/PVDF-PMMA, Eu(TTA)3phen/PVDF-PS and
Eu(TTA)3phen/PMMA-PS composites nanofibers. In spectra of Eu(TTA)
3Phen/PVDF-PS and Eu(TTA)3Phen/PMMA-PS, there are the presence
of bands of PS which are shifted at 756, 1450, 1492, and 1602 cm−1
can be assigned to the vibrations of the benzenoid ring. Spectra also
shows the band at 1185 cm−1 which is due to the stretching vibration
of the C]O group in PVDF shift to the higher frequency as compared
with pure PVDF spectra. This shifting of bands occurs due to co-
ordination of europium complex with PS and PVDF polymer matrix.
The vibration peaks of Eu(TTA)3Phen complex also get shifted may be
due to the surrounding polymer matrix. The band at 1720 cm−1 which
is due to the stretching vibration of the C]O group in PMMA as a
characteristic peak of PMMA [34]. This band shows a little shift to the
higher frequency at 1724 cm−1 due to coordination with europium
complex. The band appeared at 1173 cm−1 is assigned to the symme-
trical stretching of eCF2 group as characteristic peak of PVDF [35] shift
to the higher frequency at 1185 cm−1. In FTIR spectra of Eu
(TTA)3Phen/PMMA-PVDF, characteristics bands of PMMA and PVDF
obtained at 1724 cm−1 and 1185 cm−1 respectively at higher frequency
region with some bands of Eu(TTA)3Phen complex. Same for spectra of
Eu(TTA)3Phen/PS-PMMA, it shows all bands of PS and PMMA moves
towards at high frequency region as coordinates with europium com-
plex. These results shows that the europium complexes are successfully
incorporate into polymer blend matrix.
3.4. X-ray diffraction (XRD)
Fig. 4 shows XRD pattern of Eu(TTA)3phen, Eu(TTA)3phen/PVDF-
PS, Eu(TTA)3phen/PVDF-PMMA and Eu(TTA)3phen PMMA-PS. The
crystalline behaviour of Eu(TTA)3phen was confirmed from well re-
solved peaks at 20.26, 21.64, 21.66, 27.80, 28.20°. Various peaks of Eu
(TTA)3phen/polymer blends are characteristic diffuse scattering peaks
of pure amorphous polymers. The crystallinity Eu(TTA)3phen has been
dominated by polymer matrices. It can be seen from XRD of Eu
(TTA)3phen/polymer blends that the diffraction peaks of PMMA, PVDF
and PS coexist after their blending and it is clear that the maximum
sharp peak intensity for polymer blends which leads to exhibit a max-
imum degree of crystallinity due to increasing the degree of ordering of
atoms at polymer blends, means that the crystal structure remained
constant. It shows a sharp peak of europium complex, in Eu
(TTA)3phen/polymer blends and it is indicated that chemical bonding
exist between polymers and europium complex. This result indicates
the formation of a solid solution of Eu(TTA)3phen in polymer blends
matrices.
3.5. Photoluminescence (PL)
Photoluminescence (PL) properties of the Eu(TTA)3phen/polymer
blends nanofibers was studied and compared with that of the pure Eu
(TTA)3phen complex. Fig. 5(a) shows PL excitation spectrum of Eu
(TTA)3phen complex obtained by monitoring at 615 nm, exhibits a
M.P. Dandekar et al.
Fig. 4. XRD patterns of Eu(TTA)3phen, Eu(TTA)3phen/PVDF-PMMA, Eu
(TTA)3phen/PVDF-PS, and Eu(TTA)3phen/PMMA-PS nanofibers.
broad band between 250 and 400 nm which is attributable to π → π*
electron transition of the coordinated ligands demonstrating that en-
ergy transfer occurs from the ligands to the Eu(III) ion. The PL emission
spectrum of the Eu(TTA)3phen complex as shown in Fig. 5(b) obtained
upon excitation at 354 nm shows the bands characteristics of the metal
ion emissions in the 550–700 nm range. The well-resolved peaks ob-
served are due to the transitions from the metal-centered 5D0 excited
state to the7FJ ground state multiplet [5,36]. Maximum peak intensities
at 580, 593, and 613 were attributed to the J = 0, 1 and 2 transitions,
respectively. The emission band at 580 nm is very weak since its cor-
responding transition 5D0→7F0 is forbidden by the selection rules of
forced dipole transitions [37]. The intensity of the emission band at
593 nm is relatively weak and independent of the coordination en-
vironment because the corresponding transition 5D0→7F1 is a magnetic
transition. On the contrary, the 5D0→7F2 hypersensitive transition at
613 nm is the strongest emission (electric dipole) and it is the re-
sponsible for the red luminescence colour of the complex. Moreover, its
intensity is very sensitive to the coordination environment of the Eu(III)
ions [28]. Once the Eu(TTA)3phen complex has been extensively
characterized, its incorporation into different host polymers will be
performed. The interest lies on the expected influence that the polymers
may exert on the photoluminescence properties and how the local en-
vironment of the complex into the hybrid material may be affected. The
excitation spectra of Eu(TTA)3phen/PVDF-PS, Eu(TTA)3phen/PVDF-
PMMA and Eu(TTA)3phen/PMMA-PS monitored at 615 nm are shown
in Fig. 6(a). The excitation bands shows blue shift and all split into two
components, with peaks at around 270 and 345 nm. In the composite
nanofibers, the site symmetry of the Eu3+ ion may become lower and
distorted by the surrounding polymer media [38]. The 7F0→5D2 and
487
Optical Materials 85 (2018) 483–490
Fig. 5. (a): Excitation spectrum of Eu(TTA)3phen.
(b): Emission spectrum of Eu(TTA)3phen.
7
F1→ 5D1 excitation lines in the excitation spectra of composites na-
nofibers have been disappeared. This suggested that the f–f inner-shell
transitions in the composite fibers might be quenched through the non-
radiative energy transfer from the higher excited states to some un-
certain defect levels, which substituted the non-radiative relaxation
from higher excited states to 5D0. By comparing the emission spectra of
Eu(TTA)3phen/PVDF-PS, Eu(TTA)3phen/PVDF-PMMA and Eu
(TTA)3phen/PMMA-PS excited at the same excitation wavelength
354 nm as shown in Fig. 6(b) with that of Eu(TTA)3phen complex, the
characteristic narrow emission bands of the Eu(III) ion corresponding to
the 5D0→7FJ (J = 0–2) transitions indicating that the energy transfer
from ligands to central Eu(III)ions seems very effective. Presence of RE
complex in polymers generally enhances the luminescent intensity as
compared to pure complex due to uniform distribution of the complex
along macromolecular chains of the polymers. As fibers of Eu
(TTA)3phen/polymer blends are electrospun nanofibers the lumines-
cent complex get similarly distributed to macromolecular chain of
polymers and increased luminescent intensity of materials as compared
to bulk material [39]. Therefore, the above results indicate that the
presence of polymers like PS, PMMA and PVDF generally increases the
fluorescent intensity of the 5D0→7F2 hypersensitive transition of Eu3+
ions. When the europium complex is incorporated into the micro-
cavities of the polymer matrix, the complex exhibit more disordered
M.P. Dandekar et al.
Fig. 6. (a): Excitation spectra of Eu(TTA)3phen/PVDF-PMMA, Eu(TTA)3phen/
PVDF-PS, and Eu(TTA)3phen/PMMA-PS nanofibers.
(b): Emission spectra of Eu(TTA)3phen/PVDF-PMMA, Eu(TTA)3phen/PVDF-PS,
and Eu(TTA)3phen/PMMA-PS nanofibers.
local environments due to the influence of the surrounding polymer
[40]. The symmetry of the coordination sphere for the Eu(III) ions
changes moderately in the PS and PMMA based hybrids as compared to
the pure precursor complex [32]. Different polymer matrix when used
for Eu3+ ions to be embedded represents the enhancement in emission
intensity as excited nearly at same wavelength. Due to smaller fiber
diameter of Eu(TTA)3phen/PVDF-PS and Eu(TTA)3phen/PVDF-PMMA
as compared to that of Eu(TTA)3phen/PMMA-PS, the incorporation of
Eu(TTA)3phen into PVDF based blends showed better photo-
luminescence properties. Under the influences of the electric field of the
surrounding ligands, the distortion of the symmetry around the lan-
thanide ions by the capping polymer results in the polarization of the
Eu3+ ions, which increases the possibility for electronic dipole, allowed
transitions. According to these results, the different polymers clearly
influence the coordinative environment of the Eu(III) ions which in turn
will have an impact on the energy-transfer probabilities and hence on
the photoluminescent properties.
One of the feature for photoluminescence properties of europium
complex is that the intensity ratios of 5D0→7F2 to 5D0→7F1 (I02/I01).
This ratio of electric dipole transition to the magnetic dipole transition
in the europium complex measures the symmetry and mono-
chromaticity of the surrounding coordination sphere [11,30]. The ratio
between the emission intensities of these two peaks is an asymmetry
parameter for the Eu3+ surroundings, higher values indicating lower
symmetry configurations. Intensity ratio is related to the presence or
absence of an inversion centre in the coordination sphere. Very high
value of this ratio suggests that a very low symmetric coordination
488
Optical Materials 85 (2018) 483–490
environment exists around the Eu3+ ion in the complex. As could be
noted, complex through embedding in the PVDF matrix the intensity
ratio (I02/I01) is found to be 8.26 and 8.38 respectively for Eu
(TTA)3phen/PVDF-PS and Eu(TTA)3phen/PVDF-PMMA while for the
case of the pure complex the intensity ratio (I02/I01) is 7.11 indicating
more disordered configuration of the Eu3+ surroundings.
3.6. Judd-Ofelt analysis and CIE chromaticity coordinates
Judd-Ofelt theory is a useful method for analyzing f–f inner shell
electronic transitions and its intensity parameters [41]. Judd-Ofelt in-
tensity parameters for transitions are denoted by Ωλ (λ = 2, 4 and 6)
which are obtained from emission data of electronic transitions
5
D0→7F2, 5D0→7F4 and 5D0→7F6 respectively. However, in case of
Eu3+ the pure magnetic dipolar transition display by the 5D0→7F1
transition makes possible the determination of the intensity parameters
from emission spectra since, this transition does not depend on the local
ligand field seen by Eu3+ ions. Therefore this transition used as re-
ference for the whole spectrum. In particular, the electric dipole tran-
sition 5D0→7F2 so called hypersensitive transition, is more sensitive to
the symmetry and sequence of ligand fields, hence used to find intensity
parameters Ω2. From the emission spectra of the Eu(TTA)3Phen com-
plex and Eu(TTA)3Phen/Polymer blends, the experimental intensity
parameters Ω2 was determined by using the 5D0→7F2 transition by
expressing the emission intensity I0J in terms of the surface ‘S’ under the
emission curve. The radiative transition rate emitting level 5D0 was
determined from intensity I0J and used it for the determination of in-
tensity parameters Ω2 [11]. Intensity parameters Ω2 for Eu(TTA)3phen,
Eu(TTA)3phen/PVDF-PMMA, Eu(TTA)3phen/PVDF-PS, and Eu
(TTA)3phen/PS-PMMA nanofibers are reported in Table 1. It is ob-
served that Eu(TTA)3phen/PVDF-PMMA and Eu(TTA)3phen/PVDF-PS
nanofibers have values of Ω2 higher than that of Eu(TTA)3phen sug-
gesting an increase in the co-valency degree in the europium first co-
ordination shell interaction in the sense of the dynamic coupling con-
tribution to the total intensity results relatively stronger hypersensitive
behaviour of the 5D0→7F2 transition under the influence of polymer
blend matrix [42]. This may be due to the ligand effect of TTA in Eu
(TTA)3phen disturbed by the surrounding polymer blend matrix, con-
ferring a more polarized chemical environment of the Eu3+ ion. Moura
Jr et al. reported the experimental values of Ω2 = 33.0 for Eu
(TTA)3(H2O)2, 29.0 for Eu(TTA)3DBSO and 41.5 for Eu(TTA)3(TPPO)2
[43]. The theoretical intensity parameters as obtained with the new
dynamic coupling mechanism introduced in their work were matched
with the experimental values. When the europium complex is in-
corporated into the PVDF matrix, it increases the probability for elec-
tronic dipole allowed transition due to increase in the covalency degree
and hence the value of Ω2 intensity is lesser for Eu(TTA)3phen/PS-
PMMA nanofibers.
The International Commission on Illumination (CIE) chromaticity
coordinates Eu(TTA)3Phen complex, Eu(TTA)3Phen/PVDF-PS, Eu
(TTA)3Phen/PVDF-PMMA and Eu(TTA)3Phen/PMMA-PS nanofibers
are calculated based on the corresponding PL spectra and are re-
presented in Fig. 7. Consequently, the CIE values for PVDF/Eu3+ (1:2)
and PS/Eu3+ (1:2) nanofibers are calculated to an average (0.68, 0.32),
which is close to the standard red chromaticity of Nation Television
Table 1
Judd-Ofelt intensity parameter Ω2 and radiative transition rate ARAD of Eu
(TTA)3phen, Eu(TTA)3phen/PVDF-PMMA, Eu(TTA)3phen/PVDF-PS, and Eu
(TTA)3phen/PMMA-PS nanofibers.
Materials Intensity (a. u.) Ω2 (10−20 cm2) ARAD (s−1)
Eu(TTA)3Phen 573.32 6.025 203.54
Eu(TTA)3Phen/PMMA-PS 539.03 5.664 191.37
Eu(TTA)3Phen/PVDF-PS 2464.62 26.95 910.51
Eu(TTA)3Phen/PVDF-PMMA 2497.25 26.24 886.59
M.P. Dandekar et al.
Fig. 7. Chromaticity diagram of Eu(TTA)3phen, Eu(TTA)3phen/PVDF-PMMA,
Eu(TTA)3phen/PVDF-PS, and Eu(TTA)3phen/PMMA-PS nanofibers.
Standard Committee (NTSC) (x = 0.68, y = 0.32). The CIE chromati-
city coordinates for these PVDF/Eu3+ and PS/Eu3+ nanofibers are lo-
cated in the red region. Thus, PVDF/Eu3+ and PS/Eu3+ nanofibers can
be used for white light emitting fabric designing.
The CIE results of Eu(TTA)3Phen complex showed red emission with
appropriate CIE values with coordinates are x = 0.61, y = 0.32. These
are near to the National Television System Committee (NTSC) co-
ordinates for pure red emission. CIE coordinates of Eu(TTA)3Phen
complex deviated from its original position when incorporated into
polymer blends matrices shows good colour saturation. The calculated
CIE coordinates for Eu(TTA)3Phen/PMMA-PS are x = 0.60, y = 0.31,
for Eu(TTA)3Phen/PVDF-PS are x = 0.64, y = 0.33 and for Eu
(TTA)3Phen/PVDF-PMMA for x = 0.64, y = 0.34. It is also observed
that as europium complex incorporated into polymer blend matrix, the
emission intensity increased and the CIE colour coordinates moves to-
wards pure or saturated red emission. The CIE colour coordinates of the
complex showed red colour and the complex incorporated polymer
matrix shows saturated red emission.
4. Conclusion
Eu(TTA)3phen/PVDF-PS, Eu(TTA)3phen/PVDF-PMMA and Eu
(TTA)3phen/PMMA-PS nanofibers were successfully prepared by elec-
trospinning. The fluorescent intensity of Eu3+ ions in Eu(TTA)3phen
complex increased with the effect of high surface area of PVDF-PMMA,
PVDF-PS and PMMA-PS blends in composites nanofibers. Presence of
PVDF has an effect on the fluorescent intensity of the 5D0→7F2 hy-
persensitive transition of Eu3+ ions in the complex which is due to its
large surface area as confirmed from its SEM images. Also under the
influences of the electric field of the surrounding ligands, the distortion
of the symmetry around the lanthanide ions by the capping of PVDF
polymer results in the polarization of the Eu3+ ions, which increases
the possibility for electronic dipole, allowed transitions. Due to the
good morphology and outstanding fluorescent property, Eu
(TTA)3phen/polymer blends nanofibers show potential applications in
light emitting material designing.
489
Optical Materials 85 (2018) 483–490
Acknowledgements
This work is supported by the Department of Science and
Technology (DST, New Delhi, India) Support under DST-FIST Program,
Grant No. SR/FST/PSI-178/2012(C) and RTM Nagpur University, India
Research Project Support Grant No. Dev./RTMNURP/AH/1672(II).
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