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International Research Journal of Engineering and Technology (IRJET) e-ISSN: 2395-0056
Volume: 05 Issue: 03 | Mar-2018 www.irjet.net p-ISSN: 2395-0072
© 2018, IRJET | Impact Factor value: 6.171 | ISO 9001:2008 Certified Journal | Page 3910
Lanthanum Doped Strontium Titanate as photoanode by Pechini
method for Dye Sensitized Solar Cell Application
Muthu Gomathy M1, Dr. Moorthy babu S2
1M.Tech scholar, Centre for Nanoscience and Technology, Anna University, Chennai, Tamil Nadu, India
2Director, Centre for Nanoscience and Technology, Anna University, Chennai, Tamil Nadu, India
---------------------------------------------------------------------***---------------------------------------------------------------------
Abstract - The high temperature synthesis results in
coarsening of the particles which ultimately quenches the
surface properties of a material. This will lead to poor
performance of the Dye sensitized solar cell. Therefore weaim
at synthesizing a single phase A-site deficient La doped SrTiO3
(LST) by Pechini method at lower temperatures. It is expected
to result in higher porosity and surface area which would aid
for better adsorption of the dye molecules onto the material
and the Lanthanum doping would contribute for more
vacancies which are really important for increasing the
conductivity. Thus, the LST powders synthesized by Pechini
method would save the energy needed for calcination process
and increase the porosity, active surface area, enhancing
physical and electrochemical properties of DSSC anode in
synergism with La doping.
Key Words: Pechini, adsorption, surface area, porosity,
doping, conductivity.
1.INTRODUCTION
The photovoltaic effect was discovered by Alexandre-
Edmond Becquerel, who was a French physicist, in 1839.
This was the beginning of the solar cell technology.
Becquerel’s experiment was done by illuminating two
electrodes with different typesof light. Dye-Sensitized Solar
Cells(DSSCs) have attracted widespread interest since their
first description by Grätzel and O’Regan [1] as an influential
and low cost solar energy harvester. In a DSSC, solar energy
is converted to electricity through light absorption by dye
molecules attached to a mesoporous semiconductor, green
leaves absorb the sunlight, in order to convertwaterandCO2
to oxygen and carbohydrates. After light absorption by the
dye molecule, the resulting excited dye injects an electron
into the conduction band (CB) of the semiconductor, andthe
oxidized dye is in turn regenerated by a redox mediator,
normally iodide/triiodide, in a surrounding electrolyte. The
cycle is closed by the reduction of the redox couple at a
platinized counter electrode [2, 3]. In a conventional DSSC,
the photoanode consists of a TiO2 layer (8-15 μm) deposited
on a Transparent Conducting Oxide (TCO) covered glass
substrate and sensitized with dye molecules (usually Ru
complexes).
Over the last 20 years, ruthenium complexes gifted with
thiocyanate ligands have achieved power conversion
efficiencies beyond 11%and showed good stability[4-6].An
electrolyte containing I-/I3- redox couple acts as hole
conductor and electrically regenerate the dye molecules.
Another TCO covered substrate with a thin Pt layer(fewnm)
serves as counter electrode, to promote the reduction of the
triiodide [7,8]. One of the crucial parts in DSSCs is the dye or
photosensitizer. Generally, metal complexes
photosensitizersconsist of a central metal ion with ancillary
ligandshaving at least one anchoringgroup.Lightabsorption
in the visible part of the solar spectrum is due to a metal to
ligand charge transfer (MLCT). The central metal ion is
therefore a crucial part of the overall properties of the
complexes. Ancillary ligands, typically bipyridines or
terpyridines, can be tuned by different substituents (alkyl,
aryl, heterocycle, etc.) to change the photophysical and
electrochemical properties and thus improve the
photovoltaic performance. In this study, LST(Lanthanum
doped Strontium Titanate) powders were synthesized by
Pechini method in order to increase surface area and reduce
the calcination temperature at which pure perovskite
structure can be obtained [9, 10].
2. EXPERIMENTAL PROCEDURE
(La0.3Sr0.7)0.93TiO3 powderswere synthesized by Pechini
method. Titanium iso propoxide (Ti(OCH(CH3)2)4) was
dissolved in ethanol (99.9 %) for stabilization, and then
distilled water wasadded to the solution. After stirring for 1
h, the stoichiometric amount of La(NO3)3.6H2O (Sigma
Aldrich, 99 %) and Sr(NO3)2 (Sigma Aldrich, 99 %) was
dissolved in the solution, and nitric acid (HNO3) was added
as a peptizing agent. The solution was stirred for 3 h, and
citric acid (C6H8O7) was added into the solution. Next,
ethylene glycol (C2H6O2) was added in the solution, and the
solution was strongly stirred at 70o C for 1 h. The
transparent solution was gradually changed to the LST gel.
With the gel formation, the temperature increased to 180o C
to obtain the LST powder. The LST powder was calcined at
600ºC temperature for 5 h in air [11].
International Research Journal of Engineering and Technology (IRJET) e-ISSN: 2395-0056
Volume: 05 Issue: 03 | Mar-2018 www.irjet.net p-ISSN: 2395-0072
© 2018, IRJET | Impact Factor value: 6.171 | ISO 9001:2008 Certified Journal | Page 3911
3. RESULTS & DISCUSSION
Fig -1: XRD patterns of SrTiO3 SrLaTiO3 powder calcined at
600˚C for 5h
The phase and crystallinity were examined by XRD over 2θ
angle from 25˚ to 75˚ shown in (fig.1). As the Lanthanum
percentage increases, the major peak at 32o corresponding
to (110) plane broadens and this is due to the reduction of
crystallite size on doping with Lanthanum. Crystallite sizeis
calculated using Scherrer equation, crystallite size of
SrLaTiO3 is 6nm [11].
Fig -2: SEM images of (a) TiO2; (b) SrTiO3; (c), (d) SrLaTiO3
SEM images of (a), (b) and (c) confirms the formation of
Spherical morphology of TiO2, SrTiO3 and SrLaTiO3
nanoparticles respectively and SEM image of (d) shows the
cross sectional SEM image of SrLaTiO3 respectively.
Fig -3: (a), (b) UV-Visible Spectroscopy for SrLaTiO3 at
254nm and Tauc plot for SrLaTiO3
It shows the Bandgap of SrTiO3 is 3.2eV. On doping the
Lanthanum nitrate hexahydrate to the strontium titanate
the bandgap of the material increased to 3.5eV, the wide
bandgap which is required for photo anode of dye sensitized
solar cell.
Fig -4: EDS result for SrLaTiO3
Element Weight % Atomic %
O 25.47 64.96
Ti 15.47 13.18
Sr 26.30 12.24
La 32.76 9.62
Table -1: EDS result for SrLaTiO3
The figure and table shows the quantitative analysis of
SrLaTiO3 which confirms the presence of Lanthanum,
Strontium, Titanium and Oxygen.
Parameters Value Obtained
Surface Area 35.0236m2/g
Pore Volume 0.002845cm2/g
Mean Pore Diameter 11.12nm
Table -2: BET-BJH results for SrLaTiO3
Table 2 shows the BET-BJH analysis, it was clear that the
Lanthanum doped Strontium titanate has the surface area
1 µm
1 µm 100 µm
(a) (b)
(c) (d)
1 µm
a
)
b
)
International Research Journal of Engineering and Technology (IRJET) e-ISSN: 2395-0056
Volume: 05 Issue: 03 | Mar-2018 www.irjet.net p-ISSN: 2395-0072
© 2018, IRJET | Impact Factor value: 6.171 | ISO 9001:2008 Certified Journal | Page 3912
(35.0236m2/g), the porevolume(0.002845cm3/g),andthe
mean pore diameter (11.12nm). It shows the prepared
anode material has sufficient surface area for Dye sensitized
solar cell application [11].
4. CONCLUSION
The narrow diffraction peaks are observed at 32º,
demonstrates the crystalline Lanthanum doped strontium
titanate and the SEM image confirms the spherical
morphology of SrLaTiO3. The UV-Vis Spectroscopy of
SrLaTiO3 shows 3.5eV wide bandgap which is necessary for
the photo anode material of the DSSC. EDS result showsthat
the quantitative analysis of the elements present in the
sample and confirms the presence of Lanthanum and BET-
BJH results shows high surface area, pore volume and pore
diameter of SrLaTiO3 which improves the adsorption of dye
and hence increases the efficiency due to theincreaseinlight
absorption.
ACKNOWLEDGEMENT
I would like to express my sincere thanks and gratitude to
Dr.M.Mandhakini, Assistant Professor, Centre for
Nanoscience and Technology, Anna University, Chennai-25
for giving me an opportunity and guiding me in doing my
project. I would also like to thank Dr.M.Arivanandhan,
Associate Professor, Centre for NanoscienceandTechnology,
Anna University, Chennai-25 and Prof. Dr. P. Ramasamy,SSN
College of Engineering for taking great effortinprovidingI-V
characterization. Finally I thank DST Nano Mission 2015-
2020 for the financial support and all faculty and research
scholars of Centre for Nanoscience and Technology, Anna
University, Chennai-25 for their valuable support to carry
out this project.
REFERENCES
[1] O’Regan B and Grätzel M 1991Nature 353 737-740
[2] A. Hagfeldt and M. Grätzel, Chem. Rev. , 1995, 95, 49-68.
[3] A. Hagfeldt and M. Grätzel, Acc. Chem. Res. , 2000, 33,
269-277.
[4] Gratzel M 2009 Accounts of Chem. Res. 42 1788.
[5] Jang S R , Yum J H, Klein C, Kim K J, Wagner P, Officer D,
Gratzel M and Nazeeruddin M K 2009 J. Phys. Chem. C
113 1998-2003.
[6] Gao F, Wang Y, Shi D, Zhang J, Wang M, Jing X, Humphry-
Baker R, Wang P, Zakeeruddin S M, and GratzelM2008J.
Am. Chem. Soc. 130 10720-10728.
[7] Nazeeruddin M K, Kay A, Rodicio I, Humphry-Baker R,
Mueller E, Liska P, Vlachopoulos N and Graetzel M 1993
J. Am. Chem. Soc. 115 6382-6390.
[8] Nazeeruddin M K, Klein C, Liska P and Gratzel M 2005
Coord. Chem. Rev. 249 1460-1467.
[9] Leite ER, Sousa CMG, Longo E, Varela JA (1995)
Influence of polymerization on the synthesis of SrTiO3:
part I. Characteristics of the polymeric precursors and
their thermal decomposition. Ceram Int 21:143–152.
[10] Leite ER, Varela JA, Longo E, Paskocimas CA (1995)
Influence of polymerization on the synthesis of SrTiO3:
part II. Particle and agglomerate morphologies. Ceram
Int 21:153–158.
[11] Jin Goo Lee • Yong Gun Shul Sol-Gel Sci Technol(2014)
69:148–154.

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IRJET- Lanthanum Doped Strontium Titanate as photoanode by Pechini method for Dye Sensitized Solar Cell Application

  • 1. International Research Journal of Engineering and Technology (IRJET) e-ISSN: 2395-0056 Volume: 05 Issue: 03 | Mar-2018 www.irjet.net p-ISSN: 2395-0072 © 2018, IRJET | Impact Factor value: 6.171 | ISO 9001:2008 Certified Journal | Page 3910 Lanthanum Doped Strontium Titanate as photoanode by Pechini method for Dye Sensitized Solar Cell Application Muthu Gomathy M1, Dr. Moorthy babu S2 1M.Tech scholar, Centre for Nanoscience and Technology, Anna University, Chennai, Tamil Nadu, India 2Director, Centre for Nanoscience and Technology, Anna University, Chennai, Tamil Nadu, India ---------------------------------------------------------------------***--------------------------------------------------------------------- Abstract - The high temperature synthesis results in coarsening of the particles which ultimately quenches the surface properties of a material. This will lead to poor performance of the Dye sensitized solar cell. Therefore weaim at synthesizing a single phase A-site deficient La doped SrTiO3 (LST) by Pechini method at lower temperatures. It is expected to result in higher porosity and surface area which would aid for better adsorption of the dye molecules onto the material and the Lanthanum doping would contribute for more vacancies which are really important for increasing the conductivity. Thus, the LST powders synthesized by Pechini method would save the energy needed for calcination process and increase the porosity, active surface area, enhancing physical and electrochemical properties of DSSC anode in synergism with La doping. Key Words: Pechini, adsorption, surface area, porosity, doping, conductivity. 1.INTRODUCTION The photovoltaic effect was discovered by Alexandre- Edmond Becquerel, who was a French physicist, in 1839. This was the beginning of the solar cell technology. Becquerel’s experiment was done by illuminating two electrodes with different typesof light. Dye-Sensitized Solar Cells(DSSCs) have attracted widespread interest since their first description by Grätzel and O’Regan [1] as an influential and low cost solar energy harvester. In a DSSC, solar energy is converted to electricity through light absorption by dye molecules attached to a mesoporous semiconductor, green leaves absorb the sunlight, in order to convertwaterandCO2 to oxygen and carbohydrates. After light absorption by the dye molecule, the resulting excited dye injects an electron into the conduction band (CB) of the semiconductor, andthe oxidized dye is in turn regenerated by a redox mediator, normally iodide/triiodide, in a surrounding electrolyte. The cycle is closed by the reduction of the redox couple at a platinized counter electrode [2, 3]. In a conventional DSSC, the photoanode consists of a TiO2 layer (8-15 μm) deposited on a Transparent Conducting Oxide (TCO) covered glass substrate and sensitized with dye molecules (usually Ru complexes). Over the last 20 years, ruthenium complexes gifted with thiocyanate ligands have achieved power conversion efficiencies beyond 11%and showed good stability[4-6].An electrolyte containing I-/I3- redox couple acts as hole conductor and electrically regenerate the dye molecules. Another TCO covered substrate with a thin Pt layer(fewnm) serves as counter electrode, to promote the reduction of the triiodide [7,8]. One of the crucial parts in DSSCs is the dye or photosensitizer. Generally, metal complexes photosensitizersconsist of a central metal ion with ancillary ligandshaving at least one anchoringgroup.Lightabsorption in the visible part of the solar spectrum is due to a metal to ligand charge transfer (MLCT). The central metal ion is therefore a crucial part of the overall properties of the complexes. Ancillary ligands, typically bipyridines or terpyridines, can be tuned by different substituents (alkyl, aryl, heterocycle, etc.) to change the photophysical and electrochemical properties and thus improve the photovoltaic performance. In this study, LST(Lanthanum doped Strontium Titanate) powders were synthesized by Pechini method in order to increase surface area and reduce the calcination temperature at which pure perovskite structure can be obtained [9, 10]. 2. EXPERIMENTAL PROCEDURE (La0.3Sr0.7)0.93TiO3 powderswere synthesized by Pechini method. Titanium iso propoxide (Ti(OCH(CH3)2)4) was dissolved in ethanol (99.9 %) for stabilization, and then distilled water wasadded to the solution. After stirring for 1 h, the stoichiometric amount of La(NO3)3.6H2O (Sigma Aldrich, 99 %) and Sr(NO3)2 (Sigma Aldrich, 99 %) was dissolved in the solution, and nitric acid (HNO3) was added as a peptizing agent. The solution was stirred for 3 h, and citric acid (C6H8O7) was added into the solution. Next, ethylene glycol (C2H6O2) was added in the solution, and the solution was strongly stirred at 70o C for 1 h. The transparent solution was gradually changed to the LST gel. With the gel formation, the temperature increased to 180o C to obtain the LST powder. The LST powder was calcined at 600ºC temperature for 5 h in air [11].
  • 2. International Research Journal of Engineering and Technology (IRJET) e-ISSN: 2395-0056 Volume: 05 Issue: 03 | Mar-2018 www.irjet.net p-ISSN: 2395-0072 © 2018, IRJET | Impact Factor value: 6.171 | ISO 9001:2008 Certified Journal | Page 3911 3. RESULTS & DISCUSSION Fig -1: XRD patterns of SrTiO3 SrLaTiO3 powder calcined at 600˚C for 5h The phase and crystallinity were examined by XRD over 2θ angle from 25˚ to 75˚ shown in (fig.1). As the Lanthanum percentage increases, the major peak at 32o corresponding to (110) plane broadens and this is due to the reduction of crystallite size on doping with Lanthanum. Crystallite sizeis calculated using Scherrer equation, crystallite size of SrLaTiO3 is 6nm [11]. Fig -2: SEM images of (a) TiO2; (b) SrTiO3; (c), (d) SrLaTiO3 SEM images of (a), (b) and (c) confirms the formation of Spherical morphology of TiO2, SrTiO3 and SrLaTiO3 nanoparticles respectively and SEM image of (d) shows the cross sectional SEM image of SrLaTiO3 respectively. Fig -3: (a), (b) UV-Visible Spectroscopy for SrLaTiO3 at 254nm and Tauc plot for SrLaTiO3 It shows the Bandgap of SrTiO3 is 3.2eV. On doping the Lanthanum nitrate hexahydrate to the strontium titanate the bandgap of the material increased to 3.5eV, the wide bandgap which is required for photo anode of dye sensitized solar cell. Fig -4: EDS result for SrLaTiO3 Element Weight % Atomic % O 25.47 64.96 Ti 15.47 13.18 Sr 26.30 12.24 La 32.76 9.62 Table -1: EDS result for SrLaTiO3 The figure and table shows the quantitative analysis of SrLaTiO3 which confirms the presence of Lanthanum, Strontium, Titanium and Oxygen. Parameters Value Obtained Surface Area 35.0236m2/g Pore Volume 0.002845cm2/g Mean Pore Diameter 11.12nm Table -2: BET-BJH results for SrLaTiO3 Table 2 shows the BET-BJH analysis, it was clear that the Lanthanum doped Strontium titanate has the surface area 1 µm 1 µm 100 µm (a) (b) (c) (d) 1 µm a ) b )
  • 3. International Research Journal of Engineering and Technology (IRJET) e-ISSN: 2395-0056 Volume: 05 Issue: 03 | Mar-2018 www.irjet.net p-ISSN: 2395-0072 © 2018, IRJET | Impact Factor value: 6.171 | ISO 9001:2008 Certified Journal | Page 3912 (35.0236m2/g), the porevolume(0.002845cm3/g),andthe mean pore diameter (11.12nm). It shows the prepared anode material has sufficient surface area for Dye sensitized solar cell application [11]. 4. CONCLUSION The narrow diffraction peaks are observed at 32º, demonstrates the crystalline Lanthanum doped strontium titanate and the SEM image confirms the spherical morphology of SrLaTiO3. The UV-Vis Spectroscopy of SrLaTiO3 shows 3.5eV wide bandgap which is necessary for the photo anode material of the DSSC. EDS result showsthat the quantitative analysis of the elements present in the sample and confirms the presence of Lanthanum and BET- BJH results shows high surface area, pore volume and pore diameter of SrLaTiO3 which improves the adsorption of dye and hence increases the efficiency due to theincreaseinlight absorption. ACKNOWLEDGEMENT I would like to express my sincere thanks and gratitude to Dr.M.Mandhakini, Assistant Professor, Centre for Nanoscience and Technology, Anna University, Chennai-25 for giving me an opportunity and guiding me in doing my project. I would also like to thank Dr.M.Arivanandhan, Associate Professor, Centre for NanoscienceandTechnology, Anna University, Chennai-25 and Prof. Dr. P. Ramasamy,SSN College of Engineering for taking great effortinprovidingI-V characterization. Finally I thank DST Nano Mission 2015- 2020 for the financial support and all faculty and research scholars of Centre for Nanoscience and Technology, Anna University, Chennai-25 for their valuable support to carry out this project. REFERENCES [1] O’Regan B and Grätzel M 1991Nature 353 737-740 [2] A. Hagfeldt and M. Grätzel, Chem. Rev. , 1995, 95, 49-68. [3] A. Hagfeldt and M. Grätzel, Acc. Chem. Res. , 2000, 33, 269-277. [4] Gratzel M 2009 Accounts of Chem. Res. 42 1788. [5] Jang S R , Yum J H, Klein C, Kim K J, Wagner P, Officer D, Gratzel M and Nazeeruddin M K 2009 J. Phys. Chem. C 113 1998-2003. [6] Gao F, Wang Y, Shi D, Zhang J, Wang M, Jing X, Humphry- Baker R, Wang P, Zakeeruddin S M, and GratzelM2008J. Am. Chem. Soc. 130 10720-10728. [7] Nazeeruddin M K, Kay A, Rodicio I, Humphry-Baker R, Mueller E, Liska P, Vlachopoulos N and Graetzel M 1993 J. Am. Chem. Soc. 115 6382-6390. [8] Nazeeruddin M K, Klein C, Liska P and Gratzel M 2005 Coord. Chem. Rev. 249 1460-1467. [9] Leite ER, Sousa CMG, Longo E, Varela JA (1995) Influence of polymerization on the synthesis of SrTiO3: part I. Characteristics of the polymeric precursors and their thermal decomposition. Ceram Int 21:143–152. [10] Leite ER, Varela JA, Longo E, Paskocimas CA (1995) Influence of polymerization on the synthesis of SrTiO3: part II. Particle and agglomerate morphologies. Ceram Int 21:153–158. [11] Jin Goo Lee • Yong Gun Shul Sol-Gel Sci Technol(2014) 69:148–154.