Accepted Manuscript

Performance of Caesalpinia Sappan heartwood extract as photo sensitizer for

dye sensitized solar cells

S. Ananth, P. Vivek, G. Saravana Kumar, P. Murugakoothan

PII: S1386-1425(14)01274-8
DOI: http://dx.doi.org/10.1016/j.saa.2014.08.083
Reference: SAA 12604

To appear in: Spectrochimica Acta Part A: Molecular and Biomo-

lecular Spectroscopy

Received Date: 13 May 2014

Revised Date: 18 August 2014
Accepted Date: 24 August 2014

Please cite this article as: S. Ananth, P. Vivek, G. Saravana Kumar, P. Murugakoothan, Performance of Caesalpinia
Sappan heartwood extract as photo sensitizer for dye sensitized solar cells, Spectrochimica Acta Part A: Molecular
and Biomolecular Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.08.083

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 Performance of Caesalpinia Sappan heartwood extract as
photo sensitizer for dye sensitized solar cells
S. Ananth, P. Vivek, G. Saravana Kumar, P. Murugakoothan*
MRDL, PG & Research Department of Physics, Pachaiyappa’s College, Chennai 600 030, India.
*Corresponding author mobile: +91 9444 447 586.
E-mail address: murugakoothan03@yahoo.co.in (P. Murugakoothan).
Abstract
A natural dye extracted from Caesalpinia Sappan heartwood was used as
photo sensitizer for the first time to fabricate titanium dioxide (TiO2) nanoparticles
based dye sensitized solar cells. Brazilin and brazilein are the major pigments
present in the natural dye and their optimized molecular structure were calculated
using Density functional theory (DFT) at 6 – 31G (d) level. The HOMO – LUMO
were performed to reveal the energy gap using optimized structure. Pure TiO2
nanoparticles in anatase phase were synthesized by sol – gel technique. The pure
and natural dye sensitized TiO2 nanoparticles were subjected to structural, optical,
spectral and morphological studies. Low cost and environment friendly dye
sensitized solar cells were fabricated using natural dye sensitized TiO2 based photo
anodes. The solar light to electron conversion efficiency of Caesalpinia Sappan
heartwood extract sensitized dye sensitized solar cell is 1.1%.

Keywords: Dye Sensitized Solar Cell, Titanium dioxide, Sol – gel, Natural dye,
density functional theory, Caesalpinia Sappan heartwood.
Introduction
The ever increasing demand for more energy requires our immediate action
for proper utilization of natural sources like solar energy wind energy, tidal energy
etc. Solar energy is an important renewable energy source to harvest clean energy.
Solar cells convert light photons from solar light energy into electrons by the
principle of photoelectric effect. Among the various solar cells available, dye
sensitized solar cell (DSSC) is an attempt to replicate nature’s photosynthesis
process which has merits, like less expensive, simple fabrication, choice of color,
design, environment friendly etc. [1, 2]. The DSSC consists of a metal oxide
semiconductor as photo anode, a dye sensitizer, an electrolyte and a counter
electrode [3]. In DSSC, the dye sensitizer adsorbed on semiconductor captures the
incident photon and generates electron / hole [4]. The excited electrons are injected
into the conduction band of the semiconductor and transported to counter
electrode. The dye molecule is regenerated by the redox system, which itself is
regenerated at the counter electrode by electrons passed through load [5]. This is in
contrast to conventional silicon based solar cells, where the semiconductor
performs both task of light absorption and charge separation. In addition, DSSC
does not need high purity and other advanced fabrication requirements unlike
silicon based solar cells. Hence, it can be fabricated at low cost to harvest green
energy from abundantly available sunlight. The efficiency of DSSC depends on its
major components, design and fabrication process [1]. Hence, optimizing each
component is essential to achieve maximum efficiency. Titanium dioxide (TiO2) is
the most successful photo anode material used in DSSC due to its low cost,
abundance, non – toxic, high stability, biocompatible and environment friendly
etc. [6]. The sol – gel, a versatile technique was used to synthesis pure TiO2
nanoparticles. Among photo sensitizers, the ruthenium polypyridyl complex
inorganic dyes are most successful and showing high efficiencies [7]. But,
alarming factors, like high cost, heavy metal presence and complicated synthesis
processes etc. have attracted the focus towards natural dyes as photo sensitizers
[8]. Natural dyes are environment friendly, very cheap, easily extractable using
cheap organic solvents and abundantly available in plant parts, like flowers, seeds,
barks, leaves, stem etc. [9]. So, natural dyes can be used as an effective alternative
to toxic and expensive inorganic dye sensitizers. Natural dye pigments, like
chlorophyll, betanins, carotenoids, anthocyanins and tannins are successfully used
as sensitizers in DSSC [10, 11]. The solar light to electron conversion efficiency of
DSSC prepared by chlorophyll dye from pomegranate leaf extract is 0.597% and
that of anthocyanin dye from mulberry extract is 0.548% [12]. The natural dye
extracts of red cabbage and blue pea sensitized DSSC showed the efficiencies of
0.73% and 0.67% respectively [13]. The anthocyanin dye extracted from Hibiscus
sabdariffa L. flower and the chlorophyll dye from Undaria pinnatifida showed the
efficiencies of 0.27% [14] and 0.178% [4] respectively. The natural dye extracted
from Kerria japoni (Caotenoid) and Rosa Chinensis (Anthocyanin) as photo
sensitizer to DSSC showed the efficiencies of 0.22% and 0.29% respectively [7].
The ivy gourd fruit extract and red frangipani flower extract showed the
efficiencies of 0.076% and 0.301% [11]. The DSSCs sensitized by the fruit extract
of Melastoma Malabathricum L. and Rose Bengal dye showed the efficiencies of
1.37% [9] and 2.09% [15] respectively. In general, the efficiency of the natural dye
sensitized DSSCs are lesser than that of synthetic dye sensitized DSSCs. Attempts
were made to improve the efficiency of natural dye sensitized DSSCs by using dye
mixtures, increased dye concentration and extraction in various solvents etc. To
achieve higher efficiency, the natural dyes must bind strongly to the TiO 2 surface
by means of their anchoring group to ensure efficient electron injection into the
conduction band of TiO2. In this work, a new natural dye extracted from
Caesalpinia Sappan heartwood was used as dye sensitizer for the fabrication of
TiO2 nanoparticles based DSSCs. The Caesalpinia Sappan heartwood extract
sensitized DSSC showed a promising solar light to electron conversion efficiency
of 1.1%.
Materials and methods
Materials
The titanium isopropoxide is purchased from Sigma – Aldrich and used as
titanium precursor. The isopropanol and nitric acid are purchased from Merck. The
Caesalpinia sappan heartwood was purchased from herbal shop,
Thiruvananthapuram, Kerala, India.
Apparatus
The powder X – ray diffraction (PXRD) study was carried out using ISO
DEBYEFLEX 2000 diffractometer employing CuKα (λ = 1.5418 Å) radiation. The
UV–vis absorption spectrum was recorded in the wavelength range from 300 to
800 nm using Shimadzu Model 1601 spectrophotometer. The Perkin Elmer
Spectrum1 FT – IR instrument with a resolution of 1.0 cm-1 was used to identify
the functional groups present in the samples. F E I Quanta FEG 200 – High
Resolution Scanning Electron Microscope with a resolution of 1.2 nm was used to
study the morphological properties. The I – V response of the fabricated solar cells
were studied using Keithley 2400 sourcemeter with a Xenon lamp of 100 mWcm-2
as solar simulator at standard AM 1.5 illumination.
Preparation of Pure TiO2
The pure TiO2 nanoparticles were synthesized using sol – gel method by
taking titanium isopropoxide as titanium precursor and an alcohol with distilled
water as hydrolysis medium. The 15 mL isopropyl alcohol was mixed thoroughly
with 250 mL of distilled water and the initial pH was noted as 8.75. The pH has
strong influence on the formation and size distribution of TiO2 nanoparticles. When
the pH is higher than 2, a white suspension of rough precipitants was formed
immediately. On the other hand, when the pH is 2, a homogeneous suspension of
fine particles was formed. Hence, the pH value was adjusted to 2 by adding nitric
acid drop wise. This solution was stirred vigorously and 5 mL of titanium
isopropoxide solution was added drop wise to result a white precipitation. After
hydrolysis process, the turbid solution containing TiO2 precipitation was heated up
to 80°C for 3 hours. Then, the mixture was kept at room temperature for an hour
for aging. This yields a white suspension which is washed in distilled water first
and then in ethanol to remove byproduct impurities. The prepared white precipitate
was dried at 150 °C for 15 hours to obtain fine particles of pure TiO2.
Extraction of Natural Dye
Caesalpinia Sappan Linn is a species of flowering tree in legume family,
namely fabaceae. It is native to south India, Southeast Asia and the Malay
Archipelago. Caesalpinia Sappan, a small thorny tree shown in fig. 1(a) grows 6 to
9 meter height. The aqueous extract was prepared the simple procedure [16] by
soaking 150 gram of cleaned and dried Caesalpinia sappan heartwood in fig. 1(b)
to 100 mL of distilled water and kept for 12 hours. The mixture was filtered and
dark orange red extract was collected. The extract was concentrated and used as
photo sensitizer to TiO2 nanoparticles for the fabrication of DSSCs. Brazilin, a
reddish dye, is the major pigment present in the extract which is used for dyeing
fabric, making red paints and inks. Brazilin on oxidation results more strong red
pigment called brazilein. Both pigments are tetra cyclic with two aromatic rings,
one pyrone and one five membered ring [17]. The structures of brazilin and
brazilein pigment are shown in fig. 1(c) and 1(d).
Computational Studies on Natural Dye
The optimized molecular geometry of brazilin and brazilein was computed
by employing the DFT methods using Gaussian 03 program package [18]. The
Becke’s three parameter (local, non – local, HF) with Lee – Yang – Parr hybrid
correlation functional (B3LYP) has been used with split valence basis set 6 – 31G
augmented by ‘d’ polarization functions added [19, 20]. The optimized geometry
of brazilin and brazilein using B3LYP methods are shown in fig. 1(c) and 1(d)
gives the minimum energy values as –992.99 a.u. and –992.86 a.u. respectively.
The optimized structure was used to calculate HOMO-LUMO energy gap.
The electronic transition from ground state to first excited state is mainly
explained by one electron excitation from highest occupied molecular orbital
(HOMO) to lowest unoccupied molecular orbital (LUMO). The HOMO represents
the ability to donate an electron, LUMO as an electron acceptor, represents the
ability to obtain an electron. The energy of HOMO is directly related to ionization
potential and LUMO energy is directly related to electron affinity. These orbitals
determine the way in which the molecule interacts with other species. The frontier
molecular orbital energy gap helps to characterize the chemical reactivity and
kinetic stability of the molecule. A molecule with a smaller energy gap between
HOMO – LUMO is more polarizable, with high chemical reactivity and low
kinetic stability. The 3D frontier molecular orbital (FMOs) plots of brazilin and
brazilein pigments in fig. 2 and 3 are localized on almost the whole molecule in
which the positive and negative phases are represented by red and green color
respectively. The energy gap for both pigments is similar. Hence, even if brazilin
pigment gets oxidized to brazilein, it doesn’t alter the reactivity with TiO2
nanoparticles.
Fabrication of DSSC
The pure TiO2 obtained by conventional sol – gel technique was made into a
paste using titanium isopropoxide. A thin film was coated using doctor blade
technique on the FTO glass plate. This coating process was repeated twice to form
a thick layer of TiO2 on the FTO glass plate. The dried TiO2 coated glass plate was
sintered at 450ºC for 30 minutes to improve the electronic contact between the
TiO2 nanoparticles and to eliminate internal gas and voids. The photo anode was
soaked in Caesalpinia Sappan heartwood extract for 10 hours to adsorb dye onto
the TiO2 surface. A platinum coated FTO glass plate was used as the counter
electrode. The two electrodes were joined together with dye sensitized TiO 2 at the
middle without creating air bubbles. The liquid electrolyte (I - / I3-) was placed
through the fine holes in the two electrodes carefully and sealed to prepare TiO2
DSSC.
Results and Discussion
POWDER XRD analysis
The pure TiO2 nanoparticles synthesized by sol – gel method are
calcined at 250º C for 2 hours. The Powder X – ray diffraction pattern of TiO2
nanoparticles after calcination, shown in fig. 4, gives the structural, crystalline
quality and crystalline size information. The nano crystalline anatase structure of
natural dyed TiO2 is confirmed by the presence of (101), (0 0 4), (2 0 0), (2 1 1), (2
0 4), (1 1 6) and (2 1 5) diffraction peaks. The diffraction peaks belonging to other
polymorphs of TiO2 namely, rutile and brookite are not present. The broadened
characteristic diffraction peaks indicates the smaller size of the natural dyed TiO2
nanoparticles. The grain size was obtained by Scherrer’s equation,
D = Kλ / (β cosθ), where, ‘D’ is grain size, ‘λ’ is wavelength of the CuKα X – ray
radiation (λ = 1.5418 Å),‘K’ is shape factor – a dimensionless constant (0.9 in
case of spherical shaped particles) and ‘β’ is the full width at half – maximum
height (FWHM) of the respective diffraction peaks [21]. The average grain size of
TiO2 nanoparticles in anatase phase is approximately 23 nm.
UV–vis absorption spectral analysis
The UV – vis absorption spectrum of pure TiO2 nanoparticles is shown in
fig. 5(a) shows that the TiO2 nanoparticles absorb light photons in UV and nearby
regions only. Hence, we need a separate dye sensitizer attached with TiO2 for
making it suitable for solar cell applications. From the absorption spectrum of pure
TiO2 nanoparticles, the cutoff wavelength (λ) found to occur at 356 nm. The band
gap energy can be calculated by the relation Eg = 1239.8 / λ eV (λ in nm) [22]. The
band gap of TiO2 nanoparticles was found to be 3.48 eV. The band gap of normal
or bulk TiO2 is 3.2 eV and this variation is due to the change in particle size [23].
The absorption spectrum of natural dye sensitized TiO2 in fig. 5 (b) shows
enhanced light photon absorption and extension of absorption region than in pure
TiO2. In addition, it shows a sharp absorption peak at 349 nm and a broad
absorption peak at 658 nm. This improvement in absorbance is due to more
natural dye molecules adsorbed on TiO2 surface which leads to increase in photo
current and in total conversion efficiency [24]. And, the charge injected into the
conduction band of the TiO2 is also affected by the type of attraction between
sensitizer and its anchoring group with TiO2 [14]. The dye structure of brazilein
dye possesses several C = O and – OH groups which are capable of anchoring to
the Ti sites on the TiO2 surface. The cutoff wavelength of natural dye sensitized
TiO2 is 426 nm and the band gap is found to be 2.91 eV. The band gap of TiO2 is
related to the wavelength range absorbed and the band gap decreases with
increasing absorption wavelength [22]. The absorption study reveals that decrease
in band gap results in enhancement of photo sensitization behavior of TiO2
nanoparticles.
FTIR Spectral Analysis
The Fourier transform infra red (FTIR) spectra of pure and natural dye
sensitized TiO2 nanoparticles are shown in fig. 6(a) and 6(b) respectively. Both
spectra has the characteristic vibration of Ti – O bond at 646 cm-1 (in pure) and
644 cm-1, 747 cm-1 (in natural dye sensitized) which normally occur in between the
standard range of 450 – 1000 cm-1[25]. The peaks present at 1029 cm-1 and
1054 cm-1 in colored TiO2 are due to ring stretching. The peaks present at
1170 cm-1, 1254 cm-1 and 1289 cm-1 in natural dye sensitized TiO2 are assigned to
C – C – H bending, C – C stretching and C – O stretching vibrations respectively
[17]. The peak present at 1318 cm-1 in colored TiO2 is assigned to bending mode of
O – C – C stretching vibration. The peaks present at 1046 cm-1 in pure TiO2 are
assigned to O – H plane bending vibration mode [9]. The absorption peaks at
1623 cm-1 in pure and 1622 cm-1 in natural dye sensitized TiO2 is assigned to
O – H bending modes [25]. The absorption peak at 1384 cm-1 in both TiO2 is due
to nitrate ions from the nitric acid which is added to adjust the pH during synthesis
[26]. The absorption peaks at 3234 cm-1 in pure and 3185 cm-1 in natural dye
sensitized TiO2 is assigned to O – H stretching vibration mode of water molecules.
Scanning Electron Microscope studies
The scanning electron microscope (SEM) image of pure TiO2 nanoparticles
synthesized by sol – gel method is shown in fig. 7 (a). The pure TiO2 nanoparticles
have agglomerated together to form nano clusters. These nano clusters will affect
the photo electric behavior of TiO2. Hence, to minimize this agglomeration,
capping agent is needed. The SEM image of natural dye sensitized TiO2
nanoparticles in fig.7(b) shows improvement in morphology as nearly spherical
particles. The dye aggregation on nano crystalline film produces absorptivity that
may block the physical contact between the electrolyte and TiO 2. Hence, the
reduction in efficiency will occur [27]. And, the uniform adsorption of natural dye
on TiO2 surface reduces the possibility of dye aggregation also.
Energy Dispersive X – Ray spectrum analysis
The energy dispersive X – ray (E – DAX) spectrum of TiO2 nanoparticles is
given in fig. 7 (c). The spectrum has prominent peaks of Ti and O. From the peaks,
it is confirmed that the nanoparticles synthesized by sol – gel technique belongs to
pure TiO2. The weight contributions are 33.83 and 61.45 percentage for Oxygen
and Titanium respectively which is in agreement with 2:1 stoichiometry of TiO2.
Both the elements together contribute 95.28 percentage of the total weight. This
indicates the purity of TiO2 as there is no impurity material presence. The E – DAX
spectrum of natural dye sensitized TiO2 nanoparticles is shown in fig. 7 (d). The
weight contributions are 36.01, 33.13 and 30.85 percentages for Oxygen, Titanium
and Carbon respectively. The change in weight contributions of natural dye
sensitized TiO2 is attributed to O – Ti – O bond changed into O – Ti – OOC due to
adsorption of natural dye on TiO2 surface.
Efficiency Studies
The current – voltage (I – V) characteristics of Caesalpinia Sappan
heartwood extract sensitized photo anodes prepared by TiO2 nanoparticles based
DSSC under the AM 1.5 G illumination at 100 mW/cm2 is shown in fig. 8. The
light photon to electron conversion efficiency was studied. The fill factor (FF) was
found using the relation as given below,
FF = (Imax × Vmax) / (Isc × Voc)
Where, Imax and Vmax denote the maximum output value of current and voltage
respectively, and Isc and Voc denote the short – circuit current and open – circuit
voltage respectively. The natural dye sensitized TiO2 based DSSC exhibits the
observed values of Isc = 3.3 mA cm-2, Voc = 0.49 V and the calculated value of
FF is 67.26%. The total energy conversion efficiency was calculated using the
relation as given below,
η = (Jsc × Voc × FF) / Pin
where, Pin denotes the energy of incident photon.
The efficiency of Caesalpinia Sappan heartwood extract sensitized TiO2
based DSSC was found as 1.1%.
Conclusion
The natural dye extracted from Caesalpinia Sappan heartwood was
successfully used as dye sensitizer for first time to pure nanoparticles synthesized
using sol – gel techniques. The optimized molecular structure of brazilin and
brazilein pigments was performed and their HOMO, LUMO were studied. The
PXRD analysis confirms the anatase phase of TiO2 nanoparticles calcined at 250ºC.
The UV – vis absorption studies confirm the more dye absorbance in natural dye
sensitized TiO2 and FTIR spectra confirms the formation of TiO2 in sol – gel
process. The SEM images confirm the improved morphology and reduced
agglomeration in natural dye sensitized TiO2. DSSCs were fabricated using TiO2
sensitized by brazilein pigment rich natural dye. The light to electron conversion
efficiency of natural dye sensitized TiO2 based DSSC is 1.1%. The natural dye
extracts of Caesalpinia Sappan heartwood can be used as an effective photo
sensitizer for making natural dye based DSSCs with good efficiency.
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Figure Captions
Fig. 1(a) Caesalpinia Sappan Linn. Tree
Fig. 1(b) Caesalpinia Sappan heartwood
Fig. 1(c) Optimized molecular structure of brazilin pigment
Fig. 1(d) Optimized molecular structure of brazilein pigment
Fig.2 HOMO – LUMO of brazilin pigment
Fig.3 HOMO – LUMO of brazilein pigment
Fig. 4 PXRD pattern of TiO2 after calcination at 250°C.
Fig.5 (a) Absorption spectrum of pure TiO2
Fig.5 (b) Absorption spectrum of natural dye sensitized TiO2
Fig.6 (a) FTIR spectrum of pure TiO2
Fig.6 (b) FTIR spectrum of natural dye sensitized TiO2
Fig.7 (a) SEM Image of pure TiO2
Fig.7 (b) SEM Image of natural dye sensitized TiO2
Fig.7 (c) E – DAX spectrum of pure TiO2
Fig.7 (d) E – DAX spectrum of natural dye sensitized TiO2
Fig.8 I – V characteristics of natural dye sensitized TiO2 based DSSC
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
 Caesalpinia Sappan heartwood extract as new dye sensitizer for DSSC.
 Brazilin and brazilein are the major pigments.
 Optimized molecular structure was calculated.
 HOMO – LUMO were studied.
 Efficiency is 1.1% for natural dye sensitized DSSC.