Dye-sensitized Solar Cells From Insect products Dactylopius coccus Costa

(Homoptera, Dactylopiidae) Pigments

(3) (1) (1) (1) (2) (1)
A.R. Hernández-Martínez , S. Vargas , M. Estevez , D. Rangel , F. Quintanilla , R. Rodríguez *

1) Centro de Física Aplicada y Tecnología Avanzada, Campus UNAM, Juriquilla, Apdo. Postal 1-1010, CP
76000, Querétaro, México.

karim_ag@comunidad.unam.mx, miries@fata.unam.mx, rogelior@servidor.unam.mx

2) Ciencias de la Salud, UVM, Campus Querétaro, Juriquilla, Qro. CP 76230, Mexico

3) Centro de Investigación y de Estudios Avanzados del IPN, Unidad Querétaro, Apartado Postal 1-798,
Querétaro, Querétaro, C.P. 76001, México

ABSTRACT

The performance of a new dye-sensitized solar cells (DSSCs) based in a natural dye extracted from Insect

products Dactylopius coccus Costa (Homoptera, Dactylopiidae) Pigments, is reported. The performance of this

solar cell was compared with cells prepared using a dye from Beta vulgaris extract. The solar cells were

electrically characterized and characterized using FTIR and UV–Vis. The obtained solar energy conversion
2 2
efficiency was of 0.1% with a current density Jsc of 0.16 mA/cm using an irradiation of 100 mW/cm at 25 ºC.

Keywords: dye-sensitized solar cell, natural dyes, solar energy, dip coating.

* Corresponding author: rogelior@servidor.unam.mx

INTRODUCTION

Dye-sensitized solar cells (DSSCs) are the third generation of photovoltaic devices for the conversion of

visible light in electric energy. These new types of solar cells are based on the photosensitization produced by

the dyes on wide band-gap mesoporous metal oxide semiconductors; this sensitization is produced by the dye

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absorption of part of the visible light spectrum. One aspect particularly attractive of these DSSCs photocells is

the low cost of the solar energy conversion into electricity; this is possible mainly due to the use of inexpensive

materials and the relative easiness in the fabrication processes [1-3].

The performance of DSSCs can be understood as a competition between two principal redox processes:
-15 -12
electrons injection with rate constants of the order of picoseconds (10 - 10 s) and the regeneration of the
-7 -9
oxidized dye with rate constants of the order of nanoseconds (10 to 10 s) [4]. The injected electrons are
- -
transported through the TiO2 film to a transparent electrode (ITO), while a redox-active electrolyte of I /I3 is used

to reduce the dye cation charge and transport the resulting positive charge to a counter-electrode; however,

before this, the photo-induced electron injection from the sensitizer dye to the TiO 2 film conduction band, initiates

the charge separation [5, 6]. In this sense, the sensitized dye acts as the photo-driven electron pump of the

device.

Figure 1. Kermessic acid Molecule

The use of natural pigments as sensitizing dye for the conversion of solar energy in electricity is very

interesting because, on one hand enhance the economical aspect and, on the other, produces significant

benefits from the environmental point of view [7, 8]. Coccus Costa Dactylopius Cochineal staying at the cactus

and is used to get the Kermessic acid or red carmine. Kermessic acid is a precipitate of cochineal made by

adding alum or potassium hydrogen oxalate to a solution of cochineal whit -OH and COO- groups can be

anchored to TiO2 film (Fig 1)

This natural dye is mainly used in the food industry because it is not dangerous to humans, does not

carcinogen agent and does not pollute the environment. Despite the renewed interest in natural dyes in Mexico

is still a sub-utilization while carmine, today there is a great interest for solar cells different from mono-crystalline

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silicon. Mexico is of interest to tie the need to exploit the production potential of lipstick with the need for

development of new photovoltaic devices trouble-free, cheap and environmentally friendly.

EXPERIMENTAL

The conductive glass plates were ITO-coated glass slides (In2O3:SnO2) with a sheet resistance of 30-60
2
Ω/cm , 84% transmittance nominal at 550 nm, dimensions (L,W,D) of 25 x 25 x 1.1 mm. Titanium oxide (TiO2)

nanopowder (mesh 320) (Aldrich) and the solvents, ethanol and acetonitrile (Aldrich), were analytic grade; they

were used as received. ITO substrates were ultrasonically cleaned in an ethanol-water mixture for 30 min and

then heated at 450 ºC during 30 min prior to film deposition. The photo-anodes were prepared by sliding a glass

rod along the tape spacer; ITO glass plate were covered with adhesive tape (Scotch 3M) to control the thickness

of the film; finally a TiO2 paste was spread uniformly on the substrate. The TiO2 paste was prepared by mixing

3.0 g of TiO2 nano-powder, 10 mL of nitric acid 0.1 N and 4 mL of polyethylene glycol; this suspension was

stirred in a closed glass container for 24 hours to obtain a smooth paste with the appropriate viscosity. The film

was heated at 450 ºC for 60 minutes resulting in a mesoporous film with a thickness of around 8–10 μm and

opaque. The TiO2 photo-anodes were first soaked for 12 h in HCl and then immersed in the natural dye solutions

for one night at room temperature, according to published procedures [8]; the natural dye solution was prepared

by the incorporation of 20 mg Kermessic acid in 100 ml volumetric of water. Later, the photo-anodes were rinsed

with distilled water and ethanol and dried. Carbon coated counter electrodes were prepared following a

procedure reported elsewhere [9].

DSSC Assembling

An electrolyte solution was prepared as reported elsewhere [8]: 0.1 M of I2 was mixed with 0.05 M of LiI

and 0.05 M of 3-methoxypropionitrile in 50 mL of acetonitrile (C2H3N) and stirring for 60 minutes. This electrolyte

3
solution was poured in the mesoporous TiO2 film which was previously prepared using paraffin-film as framework

to seal the cells again an acid attack. The counter electrode was pressed against the impregnated anode and

clamped firmly in a sandwich configuration. No leaks (solvent evaporation) were detected.

RESULTS AND DISCUSSION

Both, kermessic acid and Beta vulgaris extract were used as dyes for solar cells. The short-circuit

photocurrent density JSC, the current density at maximum power JMP, the open-circuit voltage VOC, the

maximum power voltage VMP, the maximum power PM, the theoretical power PT, the fill factor FF, and the

energy conversion efficiency η, were and are reported in Table 1.

Table 1. Electrical characterization of all prepared solar cells.

Jsc JMP VOC VMP PM PT FF η

2 2
(mA/cm ) (mA/cm ) (V) (V) (mW) (mW) (%)
2.71 ± 1.98 ± 0.576 ± 0.451 ± 0.89 ± 1.561 ± 0.572 ± 0.89 ±
BVE
0.003 0.003 0.0002 0.0002 0.006 0.007 0.003 0.006
kermessic 0.21± 0.16 ± 0.322 ± 0.05 ± 0.104 ± 0.499 ±
0.5 ± 0.0002 0.1 ± 0.005
acid 0.003 0.003 0.0002 0.005 0.006 0.003

It is important to conduct error analysis showing the errors in the experimental values and the

propagated errors in calculated values based on experimental data. In this way, to validate the experimental data

of current density and voltage, the statistical experimental errors and their propagation were determined for JSC,

JMP, VOC, VMP, PM, FF, and the energy conversion efficiency.

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 Photocurrent-Photovoltage Curves
Current Density (mA/cm2) 3

2.5

1.5

0.5

0
0 0.1 0.2 0.3 0.4 0.5 0.6
Photovoltage (V)
Natural Beta vulgaris kermessic acid

Figure 2. Photocurrent-photovoltage curves for BVE and BVE/TEOS solar cells.

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It was found that the JSC using kermessic acid was 2.5 mA/cm lower than the corresponding value of

Beta vulgaris extract, as shown in Figure 2 and figure 3 shows the power curves obtained as a function of

voltage. It is possible to observe here that the PM of kermessic acid solar cell was 0.84 mW lower than the

corresponding value for Beta vulgaris extract.

Photopower-Photovoltage Curves
1.00
Photopower (mW)

0.75

0.50

0.25

0.00
0 0.1 0.2 0.3 0.4 0.5 0.6
Photovoltage (V)
Natural Beta vulgaris kermessic acid

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CONCLUSIONS

Beta vulgaris extract and using kermessic acid were studied as dyes for DSSCs. The results obtained for

Beta vulgaris extract dye are consistent with results previously reported. Significant low energy conversion

efficiency was found using using kermessic acid dye compared to the Beta vulgaris extract dye. This energy

conversion efficiency may possibly be improved by forming a complex of kermessic acid with aluminum or some

other metal. The using kermessic acid dye presented a disadvantage and their use as dye-sensitized for solar

cells is not recommended under the conditions in which it was used in this research.

ACKNOWLEDGMENTS

One of the authors (AHM) is in debt for the economical support from CONACyT.

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