You are on page 1of 8

International Journal of Mechanical Engineering and Technology (IJMET)

Volume 10, Issue 03, March 2019, pp. 1456–1463, Article ID: IJMET_10_03_147
Available online at
ISSN Print: 0976-6340 and ISSN Online: 0976-6359

© IAEME Publication Scopus Indexed


L.A. Butusov
RUDN University - Peoples’ Friendship University of Russia, Moscow, Russian Federation
Natural Science Center of General Physics Institute RAS, Russian Federation

V.V. Kurilkin
RUDN University - Peoples’ Friendship University of Russia, Moscow, Russian Federation

Jhonn Lenon Cueva Jimenez, Angel Daniel Peralta Umatambo

University of the armed forces – ESPE, Department of life sciences and agriculture, Ecuador

N.E.Temkina, V.A. Sinenko

RUDN University - Peoples’ Friendship University of Russia, Moscow, Russian Federation

This article reports photovoltaic and optical properties of composite films
5,10,15,20-tetraphenylporphyrin (TPP) with the addition of phosphor’s complex oxide
(Y0.9Eu0.05Bi0.05VO4) prepared by the spin-coating method on the surface of indium tin
oxide (ITO) plates. Studies of the photopotential of the films depending on the mass
ratio of phosphor and porphyrin are presented. The influence of complex oxide on
optical band gap of the semiconductor is shown and stability of the films calculated and
Key words: renewable energy, photovoltaics, composite materials, indium tin oxide,
rare earth complex oxide.
Cite this Article: L.A. Butusov, V.V. Kurilkin, Jhonn Lenon Cueva Jimenez, Angel
Daniel Peralta Umatambo, N.E. Temkina, V.A. Sinenko, Photovoltaic and Optical
Properties of Composite Films of Tetraphenyl Porphyrin and Yttrium Vanadate Doped
with Europium and Bismuth, International Journal of Mechanical Engineering and
Technology 10(4), 2019, pp. 1456–1463. 1456

L.A. Butusov, V.V. Kurilkin, Jhonn Lenon Cueva Jimenez, Angel Daniel Peralta Umatambo,
N.E. Temkina, V.A. Sinenko

The need for renewable energy sources stimulates fundamental researches to create new
photosensitive materials with improved characteristics. In particular, the creation of photoactive
supramolecular systems with an effective transfers of energy and an electron between donor
and acceptor components.
The two main pigments of photosynthesis, chlorophyll and carotene, are packed into a very
complex membrane structure, including pigment – protein complexes that differ in structure
and composition of both the protein and pigment components. The efficiency of energy
migration essentially depends both on the structural and functional properties of pigment-
protein complexes, and on the properties of the membrane system entirely [1].
The universality of physico-chemical acts occurring in the process of natural
photosynthesis, as well as natural progress in the areas of biochemistry, fine organic synthesis
and synthesis of nanoscale materials naturally leads to the fact that for modeling photosynthesis
and developing optoelectronic devices a variety of model systems [23], including both natural
pigments and their structural and functional analogues: from artificially formed membrane-like
systems of natural pigment-protein complexes [2] to supramolecular, covalently bound donor-
acceptor oligomers or composite systems in solutions or films, including carbon [3] or metallic
[4] nanostructures.
The fundamental sequence is as follows: the energy of the light causes an electron to go
from a low energy state to a higher energy state which must either appear at or migrate to an
interface or heterojunction where an electron transfer can take place, then the oxidized and
reduced species (holes and electrons) must be able to migrate to opposite sides of the cell where
they can be collected as electrical energy. So the solar cell needs a light-absorber which could
be a dye, a hole-transport agent, and an electron-transport agent [5].
Sometimes one component is forced into multiple duties, as in a typical silicon cell, where
silicon is the absorber and with different doping also serves as either a hole-transport (p-type)
or electron-transport (n-type) agent. Many organic solar cells apply a similar approach, using
the light-absorbing dyes as charge-transport agents, but other approaches separate all three
functions to different materials [6].
In a number of works, the use of yttrium vanadate has proven itself on the positive side to
improve the short-wavelength spectral response of materials used in solar cells [7]. Doping with
elements like neodymium contributes to an increase in the absorption band above 800nm what’s
useful in the development of laser resonators [8] but for solar cells the region of 300-800 nm is
most important so dopants like Europium are used [9]. Bismuth doping is the way to enhance
open-circuit voltage of dye-sensitized solar cells [10]. Some researchers report [11] that
addition of Bi at the surfaces of TiO2 could boost Voc from 0.633 V to 0.800 V but in most
cases it decrease’s voltage. Research [12] reports the use of Bi as a dopant for zinc oxide layer
as anti-reflection coating at the range of 400-1000nm.
The optical properties of yttrium – europium vanadates have been studied in detail, which
facilitates the interpretation of the results [13, 14]. The addition of vanadium REEs can lead to
an increase in the photostability of the film. The aim of the work is to study the energy
conversion efficiency in nanocomposite films from TPP and yttrium vanadate doped with
europium and bismuth, as well as a comparative study of the photo-response values on
substrates from ITO at various mass ratios of the dye and inorganic phosphor [15]. Although a
number of publications indicate whether the positive effect of adding bismuth to the
composition of photovoltaic layers, in most cases it reduces electrical conductivity. Therefore,
in this article the use of bismuth is considered solely from the standpoint of its biological 1457

Photovoltaic and Optical Properties of Composite Films of Tetraphenyl Porphyrin and Yttrium
Vanadate Doped with Europium and Bismuth

activity, which can increase the stability of photovoltaic and optical properties of film materials
for a long period of time.


Solution of 5,10,15,20-tetraphenylporphyrin (Sigma Aldrich) was prepared in chloroform
(Uvasol) at a concentration of 0.6 mg/ml. Complex oxide Y0.9Eu0.05Bi0.05VO4 obtained by solid
phase synthesis was mixed with TPP solution with different ratios - 4:1; 3:2; 2:3 and 1: 4.
Solutions were sonicated for 40 minutes (Branson 1510 frequency 42 kHz).
Spin coating method (2000 rpm) was used for an application of the films on indium tin
oxide plates. Films were deposited immediately to avoid sedimentation of phosphor in the
UV-VIS absorption and transition spectra were taken (Shimadzu UV-1800).
Photovoltaic measurements were made in real time with a load resistance of 105 Ohms at a
facility assembled at the laboratory, including a universal voltmeter connected to a computer.
The ITO electrode with a composite film and the silver-chloride reference electrode were
located in two cells containing 0.1 M KCl diluent and connected by a salt bridge. For
illumination, a white light source with a light intensity of 80 mW / cm2 was used. The
photopotential is the difference in the value of the potential recorded when the light is on (light
potential), and the value of the potential recorded when the light source is off (dark potential).
The uniformity of the surface topography was evaluated on a scanning microscope (NT-
MDT, Russia). Silicon cantilevers with a radius of curvature of the needle point of not more
than 10 nm were used in tapping mode of atomic force microscopy.
Origin lab 8.1 software was used for data processing. To unify the results in terms of
temporal photo stability of film-coated electrode integral absorption intensity (300-800 nm
range) was used.


In non-polar environments or dilute solutions of organic solvents porphyrin may exist in a
monomeric state. When a film is formed porphyrin molecules aggregation occurs, however a
common phenomenon is bathochromic shift of porphyrin absorption spectra in films compared
with spectra in solutions. In Langmuir films maximum shift of the Soret derivative band
tritolylporphyrin is 16–24 nm [16] or 10–25 nm [17] and depends on the structure of the
porphyrin film formation conditions and substrate nature: on quartz substrates for TPP films
the shift is 19 nm (λ max Soret = 437 nm).
With an increase in the number of aliphatic substituents n-C17H35 nitrophenyl-amidophenyl-
substituted porphyrin from 1–2 to 3–4, bathochromic shift decreases from 13 to 7 nm [18].
The maximum of the Soret DFT band on the surface of the ITO in a dilute solution of
chloroform is observed at 435 nm, which is consistent with the aggregation of porphyrin
molecules (the total batachromic shift of 24 nm) is apparently under the influence of the
substrate materials. 1458

L.A. Butusov, V.V. Kurilkin, Jhonn Lenon Cueva Jimenez, Angel Daniel Peralta Umatambo,
N.E. Temkina, V.A. Sinenko



80 2


transmittance %







300 350 400 450 500 550 600 650 700 750 800
wavelenght, nm

Figure 1. Optical transmission spectra of TPP (1) and TPP - Y0.9Eu0.05Bi0.05VO4 1:10 (2)
At the region 350-720 nm optical transmittance of the phosphor’s complex oxide is
significantly higher than of pure TPP on ITO substrate (Fig.1), a ratio of 1:10 was taken to show
the effect of introducing complex oxide on optical transmission. The absolute integral area of
transmittance for tetraphenylporphyrin is 21.792 units for TPP complex with
Y0.9Eu0.05Bi0.05VO4 - 26.693 what indicates that inorganic phosphors are able to suppress
reflection and enhance the transmission of light through the substrate materials.
A study of a new generation of photo catalyst suggests that doping different semiconductive
materials with rare-earth ions [19, 20] makes it possible to increase the conductive properties
due to hole conductivity in the valence band [21].


ITO plates
+ layer




3,0 3,2 3,4 3,6 3,8 4,0 4,2 4,4


Figure 2. First derivative (dT/dE) plot of the transmittance spectra 1459

Photovoltaic and Optical Properties of Composite Films of Tetraphenyl Porphyrin and Yttrium
Vanadate Doped with Europium and Bismuth

We used data obtained from optical spectra to study the effect of inorganic phosphor on the
optical band gap of the semiconductor indium tin oxide. (Fig.2)
The first derivative of the transmittance spectrum relative to energy proofs that there is no
significant effect of the layer on the band gap of semiconductor we used – the difference is
about 0.01 eV. It could be very important for the creation of new Gretzel cells using complex
oxides of inorganic phosphors.
The dependence of the photovoltage on the ratio of components in the film is nonlinear
(tab.1). For single-component film of TPP it’s about 0.6 mV with ratio of TPP-complex oxide
of 75% it increases by 0.4 mV and 0.1 mV for 1:1 and 1:4 ratios. Also we noticed that dark
potential of 25% TPP film declined more slowly over time.

Table 1. Open-circuit voltage under resistance of 105 Ohms of composite films consisting TPP and
С(TPP), % Voc,mV
100 0.6
75 1.0
50 0.7
25 0.7
The authors of [22] discussed the main mechanism of the formation of free charge carriers
is the surface deactivation of singlet excitons which generated under the action of light in the
volume of the film at the pigment – electrolyte phase boundary with the electron trapping by
the acceptor on the film surface.

Figure 3. AFM images of TPP- Y0.9Eu0.05Bi0.05VO4 layers 1:1 (left) and 1:4 (right) ratios 1460

L.A. Butusov, V.V. Kurilkin, Jhonn Lenon Cueva Jimenez, Angel Daniel Peralta Umatambo,
N.E. Temkina, V.A. Sinenko

Atomic-force microscopy was used to study film’s surfaces (Fig. 3). For TPP:
Y0.9Eu0.05Bi0.05VO4 we obtained a more sown film for 1:4 ration with an average roughness of
6.4 nm and grain size ranged from 13 to 26 nm, the same grain size parceling is true for 1:1
ratio with average roughness of 5.9nm
The use of layers in commercial photovoltaics always implies a certain stability, which can
vary not only by external factors, but also in cases where the organic component is used — for
example, dyes that have a tendency to photodegradation. In terms of chemistry, the dye and
electrolyte play the role of a double redox system so the degradation of films associated with
oxidative-reduction processes. Absorption measurements which were carried out for 2.5
months with a 1-day interval presented in fig 4.


integrated absorbtion



ITO plate

0 10 20 30 40 50 60 70 80


Figure 4. Time dependence of the integral absorption (350-800 nm range)

Integral abs was used for unification of results relatively to pure ITO plates. As shown in
the figure, the adsorption of active layers is “subsided” much more often in cases of excessive
amounts of dye, but still all of samples have better absorption than pure indium tin oxide plates.
The average value of the integral absorption of the samples relative to pure ITO plates for 71
days was 0.13 for 25% of TPP, 0.11 for 50% of TPP and 0.004 for 75% of TPP which in turn
means +13/11/0,4% to light absorption. At the same time, absorption is not the most important
parameter if the light conversion is minimal. Since the tests were carried out in identical
laboratory conditions, we associate changes in the absorption of light by samples exclusively
with the internal processes occurring in the films.

The preparation of porphyrin - Y0.9Eu0.05Bi0.05VO4 complex with the subsequent coating on the
surface of semiconductor is described. Optical studies have shown an increase in the absorbing
properties of the material due to the use of a composite film without significantly affecting the
band gap of a semiconductor. The photopotential values were measured and showed the most
effective conversion at a ratio of TPP - complex oxide 3: 1. Atomic force microscopy showed
a fairly uniform surface seeding with the size of aggregated particles up to 26nm. An 1461

Photovoltaic and Optical Properties of Composite Films of Tetraphenyl Porphyrin and Yttrium
Vanadate Doped with Europium and Bismuth

improvement in the absorption properties over time was observed for films with an excess of
complex phosphor oxide.

This publication was prepared with the support of the “RUDN University Program 5-100”.

[1] D. Von Wettstein, S. Gough, C.G. Kannangara, “Chlorophyll Biosynthesis”, The Plant Cell,
Vol. 7, pp. 1039-1057, July 1995, American Society of Plant Physiologists.
[2] G. LeBlanc, E. Gizzie, S. Yang, D.E. Cliffel, G.K. Jennings, “Photosystem I protein films
at electrode surfaces for solar energy conversion”, Langmuir. Vol. 30, No. 37, pp. 10990-
1001, February 2014.
[3] J.P. Giraldo, M.P. Landry, S.M. Faltermeier and etc., “Plant nanobionics approach to
augment photosynthesis and biochemical sensing”, Nat Mater., Vol. 13, No. 4, pp. 400-408,
April 2014.
[4] R. Tighe-Neira, E. Carmora, G. Recio, A. Nunes-Nesi and etc., “Metallic nanoparticles
influence the structure and function of the photosynthetic apparatus in plants”, Plant Physiol
Biochem., Vol. 130, pp. 408-417, September 2018.
[5] J. Teuscher, J.C. Brauer, A. Stepanov, A. Solano and etc., “Charge separation and carrier
dynamics in donor-acceptor heterojunction photovoltaic systems”, Struct Dynamics, Vol.
4, No. 6, pp. 061503, December 2017.
[6] M.G. Walter, A.B. Rudine and C.C. Wamser, “Porphyrins and phthalocyanines in solar
photovoltaic cells”, Journal of Porphyrins and Phthalocyanines, Vol. 14, No. 9, pp. 759-
792, 2010.
[7] N. Chander, S.K. Sardana, P.K. Parashar, A.F. Khan and etc., “Improving the Short-
Wavelength Spectral Response of Silicon Solar Cells by Spray Deposition of
YVO4:Eu3+Downshifting Phosphor Nanoparticles”, IEEE J. of Photovoltaics, Vol. 5, No.
5, pp. 1373-1379, June 2015.
[8] D.E. Zelmon, J.J. Lee, K.M. Currin, J.M. Northridge, D. Perlov, “Revisiting the optical
properties of Nd doped yttrium orthovanadate”, Appl Opt., Vol. 49, No. 4, pp. 644-647,
February 2010.
[9] J. Gong, K. Sumathy, Q. Qiao, Z. Zhou, “Review on dye-sensitized solar cells (DSSCs):
Advanced techniques and research trends”, Renewable and Sustainable Energy Reviews,
Vol. 68, Part 1, pp. 234-246, February 2017.
[10] C. Hsu, R.C. Powell, “Energy transfer in europium doped yttrium vanadate crystals”,
Journal of Luminescence Vol. 10, No. 5, pp. 273-293, June 1975.
[11] Ming-Chung Wu, Wei-Cheng Chen, Ting-Han Lin and etc., “Enhanced open-circuit voltage
of dye-sensitized solar cells using Bi-doped TiO2 nanofibers as working electrode and
scattering layer”, Solar Energy, Vol. 135, pp. 22-28, October 2016.
[12] T. Fangsuwannarak, P. Krongarrom, J. Kaewphoka, S.T. Rattanachan, “Bismuth doped
ZnO films as anti-reflection coatings for solar cells”, IEEE 10th International Conference
on Electrical Engineering/Electronics, Computer, Telecommunications and Information
Technology, Krabi, Thailand, 15-17 May 2013.
[13] A. Huignard, V. Buissette, A. Franville, T. Gacoin and J. Boilot, “Emission Processes in
YVO4:Eu Nanoparticles”, J. Phys. Chem. B, Vol. 107, No. 28, pp. 6754–6759, 2003. 1462

L.A. Butusov, V.V. Kurilkin, Jhonn Lenon Cueva Jimenez, Angel Daniel Peralta Umatambo,
N.E. Temkina, V.A. Sinenko

[14] H.J. Rajendra, C. Pandurangappa, “Optical Properties of Pure and Europium-doped YVO4
Phosphor”, Nanoscience and Nanotechnology Research, Vol. 4, No. 2, pp. 43-48, 2017.
[15] I.A. Nagovitsyn, G.K. Chudinova, A.I. Zubov, L.A. Butusov and etc., “Light conversion in
thin films of a mixture of mesotetraphenylporphyrin and erbium-doped yttrium vanadate
crystallites: 2. Optical properties”, Russian Journal of Physical Chemistry B, Vol. 10, No.
4, pp. 566–569, July 2016.
[16] J. Bardwell, J.R. Bolton, “Monolayer studies of 5‐ (4‐ carboxyphenyl)‐ 10,15,20‐
tritolyl‐ porphyrin–i. optical studies of films at the air‐ water interface and of films
transferred onto solid substrates”, Photochem. Photobiol., Vol. 39, No. 6, pp. 735, May
[17] Z. Zhang, A.L. Verma, K. Nakashima, et al., “Molecular Orientation and Aggregation in
Langmuir−Blodgett Films of 5-(4-N-Octadecylpyridyl)-10,15,20-tri-p-tolylporphyrin
Studied by Ultraviolet−Visible and Infrared Spectroscopies”, Langmuir, Vol. 13, No. 21,
pp. 4422–4427, August 1997.
[18] H. Chou, C. -T. Chen, K.F. Stork, et al., "Langmuir-Blodgett Films of Amphiphilic Push-
Pull Porphyrins," J. Phys. Chem., Vol. 98, pp. 383-385, 1994.
[19] L.P. Kharel, P.M. Cuillier, K. Fernando, et al., “Effect of Rare-Earth Metal Oxide
Nanoparticles on the Conductivity of Nanocrystalline Titanium Dioxide: An Electrical and
Electrochemical”, J. Phys. Chem. C, Vol. 122, No. 27, pp. 15090–15096, June 2018.
[20] J. Reszczynska, T. Grzyb, J.W. Sobczak, et al., “Visible light activity of rare earth metal
doped (Er3+, Yb3+ or Er3+/Yb3+) titania photocatalysts”, Appl. Catal. B: Environmental,
Vol. 163, pp. 40–49, 2015.
[21] C. Gioncoa, M.C. Paganinia, E. Giamello, et al., “Rare earth oxides in zirconium dioxide:
How to turn a wide band gap metal oxide into a visible light active photocatalyst”, J. of
Energy Chemistry, Vol. 26, No. 2, pp. 270–276, March 2017.
[22] J. Teuscher, J.C. Brauer, A. Stepanov, et al., “Charge separation and carrier dynamics in
donor-acceptor heterojunction photovoltaic systems”, J. Structural Dynamics, Vol. 4, No.
6, 2017.
[23] R.R. Gurina, A.A. Rozhkova, N.G. Khomenets, A.A. Poddubsky, V.V. Plyushchikov,
Prospects for the Elimination of Toxic Waste at the Polygon of "Krasny Bor".
International Journal of Civil Engineering and Technology,9(7), 2018, pp. 1419-1424. 1463