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Ruthenium-based dyes for Dye-sensitized Solar Cells

By: Dr. Hans Desilvestro and Dr. Yanek Hebting,
Dyesol Ltd., 3 Dominion Place, Queanbeyan NSW 2620 AUSTRALIA

Working principle of dye-sensitized solar cells Related Links

Dye-sensitized Solar Cells (DSCs) are 3rd generation solar cells combining the promise of high efficiency with low production VIEW PRODUCT LIST
costs. While present-day DSCs provide light-to-electricity conversion of up to 11%,1-3 significant further improvement is  
envisaged through optimized materials and novel cell and module architectures. In addition, DSC devices can be
manufactured to be semi-transparent to harvest light from practically any angle and direction paving their way for use as
photovoltaic windows in buildings or small devices.
Related Products
The schematic shown in Figure 1 depicts the working principle of a DSC:
Dye Sensitized Solar Cell (DSSC)
Light is absorbed by a monomolecular layer of dye chemisorbed to a thin film
of nanocrystalline TiO2 promoting an electron from the Ru2+ based ground Materials
state to an excited state (Ru2*). Organic Photovoltaic (OPV)
The excited electron is then transferred within a very short time (pico to Materials
femtoseconds) into the conduction band (CB) of TiO2. This leads to an
effective charge separation, with a negative charge within the titania phase and
a positive charge on surface-adsorbed Ru3+.
The Ru3+ species is then reduced very rapidly (within nanoseconds) by an
iodide anion (I¯ ) present in the electrolyte system. The electron injected into Related Articles
TiO2 in the previous step diffuses through the nano-network of particles until it
reaches the electrically conductive surface for current collection, e.g. a thin
layer of conductive transparent oxide on glass, plastic or a metallic substrate. OPV Tutorial
The electric charge thus extracted from the photoanode as a current can be Efficient DSSC for Direct Conversion
utilised to provide useful electric power. of Sunlight to Electricity
In order to close the electric circuit, the negative charges are directed to the
Preparation of Photoactive Layers for
surface of a counter electrode (CE) where I3¯ is reduced to I¯. Thus no net
chemical reaction occurs within a DSC. OPV Applications
Synthesis of ZnO Aggregates and
DSC operation is much closer to photosynthetic processes than operation of their Application in DSSCs
standard solid-state photovoltaic devices such as silicon-based solar cells. As Plexcore® Photovoltaic Ink System
with photosynthesis, the effectiveness of the light conversion in DSCs depends
on the relative speed of reactions, i.e. kinetics. The electron injection into the Agfa OPV
titania conduction band is much faster than electronic relaxation processes back to the ground state or chemical side Materials for Flexible and Printed
reactions involving the excited state of the dye. Moreover, the reduction of the oxidized dye (Ru3+) by I¯ is significantly faster4 Electronics
than the direct recombination reaction between the injected electron and Ru3+. Innovative Materials for High-
Performance Optoelectronic Devices:

Ruthenium Dyes OPVs, OFETs, and OLEDs

Synthesis of ZnO Aggregates and
In dye-sensitized solar cells, the dye is one of the key components for high power conversion efficiencies. In recent years, Their Application in Dye-sensitized
considerable developments have been made in the engineering of novel dye structures in order to enhance the performance Solar Cells
of the system. In particular, amphiphilic homologues of the pioneering ruthenium based N-3 dye have been developed. These Photovoltaics, Ionic Liquids, and
amphiphilic dyes display several advantages compared to the N-3 dye such as: MOFs: Dye-sensitized Solar Cells
Organic & Printed Electronics
1. a higher ground state pKa of the binding moiety thus increasing electrostatic binding onto the TiO2 surface at lower pH values,
Technical Resources
2. the decreased charge on the dye attenuating the electrostatic repulsion in between adsorbed dye units and thereby increasing the
dye loading, OLED eFabricator
3. increasing the stability of solar cells towards water-induced dye desorption,
4. the oxidation potential of these complexes is cathodically shifted compared to that of the N-3 sensitizer, which increases the
reversibility of the ruthenium III/II couple, leading to enhanced stability.5

  Categories
Absorption
Calorimetry
Capillary electrophoresis
Ligands
Oxidations
Photosynthesis
Recombination
Reductions
Separation
Solar cells

N-3
C26H16N6O8RuS2 N-719
Mol Wt: 705.64 C58H86N8O8RuS2
Mol Wt: 1188.55

Z-907
C42H52N6O4RuS2
Mol Wt: 870.10
Figure 2. Ruthenium-based N-3, N-719 and Z-907 dyes.
 
Table 1: Dyesol® dyes offered in our catalog.

Product
Synonym Product Description No.

N-3 cis-Bis(isothiocyanato) bis(2,2’-bipyridyl-4,4’- • Pioneering dye for use in DSSCs. 703206

dicarboxylato ruthenium(II) • Sensitizes wide band gap semi-conductors
such as titanium oxide up to wavelengths of
700 nm.
N- Di-tetrabutylammonium cis- • Modified dye to increase device voltage. 703214
719 bis(isothiocyanato)bis(2,2’-bipyridyl-4,4’- • Highly studied, high performance dye.
dicarboxylato)ruthenium(II)
Z-907 cis-Bis(isothiocyanato)(2,2’-bipyridyl-4,4’- • Hydrophobic dye. 703168
dicarboxylato)(4,4’-di-nonyl-2’- • Very efficiently sensitizes wide band-gap
bipyridyl)ruthenium(II) titanium oxide up to 750 nm.

Ruthenium-based dyes exhibit ligand-centered charge transfer (LCCT) transitions (π - π*) as well as metal-to-ligand charge
transfer (MLCT) transitions (4d - π*) that can be observed in the UV/Vis spectra of N-719 and Z-907 dyes (Figure 3). The
absorption bands at lower energies represent the MLCT transitions (λ1 and λ2) whereas the more energetically demanding
transitions (λ3 and λ4) correspond to LCCT transitions.6

Figure 3. UV/Vis spectra of N-719 (Product No. 703214) and Z-907 (Product No. 703168) dyes.

DSC Cell
A translucent DSC with an active area of 0.88 cm2 (8 mm x 11 mm) based on
Dyesol test cell hardware7,8 prepared with N-719 dye is illustrated in Figure 4. The
orange area is a result of the dye-modified titania; the yellow color is given by the
electrolyte of the system.

JV Curves
Standard test cells are characterised by typical JV plots as shown in Figure 5 when tested at three different sun levels (1 sun
corresponds to 100 mW cm-2). The voltage,V, and the current density, J (mA cm-2), at the maximum power point are
represented by Vmax and Jmax. Therefore the efficiencies can be calculated by:
η (%) = (Vmax x Jmax) / (sun level)

With commercially relevant low volatility electrolyte systems, typical short circuit currents are 15.5 mA cm-2 and 13.7 mA cm-2
at full sun for an efficiency of 5.7% and 4.8% for N-719 and Z-907 respectively. The efficiencies characteristically increase at
lower sun levels in DSC systems, when compared to full sun level efficiencies, to 7.8% (5.2 mA cm-2) and 7.6% (1.5 mA cm-2)
for N-719 and to 6.9% (4.8 mA cm-2) and 6.9% (1.4 mA cm-2) for Z-907 at 1/3 sun and 1/10 sun respectively.
Materials
     

Product # Image Description Add to Cart

1,3-Bis[4-(dimethylamino)phenyl]-2,4-dihydroxycyclobutenediylium dihydroxide, bis(inner
149063 pricing
salt) Dye content 90 %

cis-Bis(isothiocyanato)(2,2′-bipyridyl-4,4′-dicarboxylato)(4,4′-di-nonyl-2′-
703168 pricing
bipyridyl)ruthenium(II) 95% (NMR)

703206 cis-Bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)ruthenium(II) 95% (NMR) pricing

791423 C101 Dye pricing

791393 C106 Dye ≥85% (HPLC) pricing

791873   Conductive silver printing ink, resistivity 5-6 μΩ cm pricing

791881   Conductive silver printing ink, resistivity 9 - 10 μΩ-cm pricing

791903   Conductive silver printing ink, resistivity 30 - 35 μΩ-cm pricing

546283 Coumarin 6 ≥99% pricing

546127 Coumarin 30 Dye content 99 % pricing

546151 Coumarin 102 Dye content 98 % pricing

546186 Coumarin 153 Dye content 99 % pricing

745944 D102 Dye 95% (HPLC) pricing

797391 D131 dye >95% (HPLC) pricing

736015 D149 Dye 98% (HPLC) pricing

745618 D205 Dye 97% (HPLC) pricing

746606 D358 Dye 95% pricing

Di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-
703214 pricing
dicarboxylato)ruthenium(II) 95% (NMR)

791482   EL-HPE high performance electrolyte pricing

791466   EL-HSE high stability electrolyte pricing

791458   EL-HTE high temperature electrolyte pricing

 Product # Image Description Add to Cart

805238 FK 102 Co(II) PF6 salt pricing

805246 FK 102 Co(II) TFSI salt pricing

805386 FK 209 Co(II) TFSI salt pricing

805394 FK 209 Co(III) TFSI salt pricing

805807 FK 269 Co(III) TFSI salt pricing

791415 K19 Dye 85% (HPLC) pricing

323756 Merocyanine 540 Dye content 90 % pricing

791245 N749 Black Dye pricing

791512 Platinum paste, screen printable pricing

791555 Titania paste, active opaque pricing

791539 Titania paste, reflector pricing

791547 Titania paste, transparent pricing

774529 Titanium(IV) oxide nanowires, diam. × L ~10 nm × 10 μm pricing

774510 Titanium(IV) oxide nanowires, diam. × L ~100 nm × 10 μm pricing

637254 Titanium(IV) oxide, anatase nanopowder, <25 nm particle size, 99.7% trace metals basis pricing

Titanium(IV) oxide, mixture of rutile and anatase nanopowder, <100 nm particle size (BET),
634662 pricing
99.5% trace metals basis

Titanium(IV) oxide, mixture of rutile and anatase nanoparticles, <150 nm particle size
700347 pricing
(volume distribution, DLS), dispersion, 40 wt. % in H2O, 99.5% trace metals basis

Titanium(IV) oxide, mixture of rutile and anatase nanoparticle, <250 nm particle size (DLS),
700355 paste, 53-57 wt. % in diethylene glycol monobutyl ether/ethylene glycol, 99.9% trace metals pricing
basis

637262 Titanium(IV) oxide, rutile nanopowder, <100 nm particle size, 99.5% trace metals basis pricing

544906 Zinc oxide nanopowder, <100 nm particle size pricing

677450 Zinc oxide nanopowder, <50 nm particle size (BET), >97% pricing

773999 Zinc oxide nanowires, size × L × 1 μm pricing

773980 Zinc oxide nanowires, size × L × 300 nm pricing

774006 Zinc oxide nanowires, size × L × 4-5 μm pricing

 References
1. Chiba, Y.; Islam, A. ; Watanabe, Y. ; Komiya, R.; Koide, N. ; Han, L. Jpn. J. Appl. Phys. 2006, 45, L638.
 2. Grätzel, M. J. Photochem. Photobiol., A 2004, 164, 3.
3. Chiba, Y.; Islam, A.; Kakutani, K. ; Komiya, R.; Koide, N.; Han, L. 15th International Photovoltaic Science & Engineering Conference (PVSEC-15),
Shanghai, China, 2005, Technical Digest, p.665.
4. Grätzel M. Inorg. Chem. 2005, 44, 6841.
5. Klein, C.; Nazeeruddin, Md. K.; Di Censo, D.; Liska, P.; Grätzel, M. Inorg. Chem. 2004, 43, 4216.
. Hirata, N.; Lagref, J. J.; Palomares, E. J.; Durrant, J. R.; Nazeeruddin, Md. K. ; Grätzel, M.; Di Censo, D. Chem. Eur. J. 2004, 10, 595.
7. Dyesol Research, Development and Prototyping Solutions Page. http://www.dyesol.com/index.php?page=Equipment (accessed April 17th
2009)
. Dyesol Glass Test Plates Page. https://secure.dyesol.com/index.php?template=TestCell (accessed April 17th 2009)

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