"Electron Transfer in Chemistry" (Ed.: V. Balzani) Vol. 5, Part 3 Energy and the Environment (Ed.: I.

Gould) Wiley-VCH, Weiheim, 2001; pp. 589-644. _________________________________________________________

Solar Energy Conversion

Michael Grtzel and Jacques-E. Moser *

Laboratory for Photonics and Interfaces Institute of Physical Chemistry Ecole Polytechnique Fdrale de Lausanne CH-1015 Lausanne Switzerland

Table of Contents
1. 2. Introduction and Scope Thermodynamic Efficiency Limitations in Photochemical Conversion 2.1 2.2 2.3 2.4 3. 4. Maximum power extraction Limitations due to the entropy of light Further increase of entropy on absorption and scattering Efficiency of energy conversion under polychromatic radiation

Status of Photochemical Energy Conversion Systems Molecular Photovoltaics 4.1 4.2 Mimicking photosynthesis Mesoscopic oxide semiconductor films 4.2.1 Light harvesting by monomolecular layers 4.2.2 Preparation and morphology of mesoscopic semiconductor films 4.3 Photoinduced charge separation at the solid/electrolyte interface 4.3.1 Molecular engineering of sensitizers 4.3.2 Dynamics of charge injection in wide bandgap semiconductors 4.3.3 Recapture of the injected electron 4.4 Charge separation in molecular photovoltaic devices 4.4.1 Interception of dye cations by a redox mediator 4.4.2 Charge carrier percolation through mesoporous solid films 4.4.3 Charge separation across a solid-state heterojunction 4.5 4.6 Charge separation and recombination in nanocrystalline heterotriads Photovoltaic performances of dye-sensitized nanocrystalline solar cells

5.

Water Cleavage by Visible Light 5.1 5.2 5.3 Analogues of photosystem II of green plants Colloidal semiconductors systems Tandem systems for water cleavage by visible light

6.

Future Outlook and Concluding Remarks

Acknowledgements References

1. Introduction and Scope

There can be no question that the quality of human life is intimately associated with the ready availability of energy resources. At present, the worlds energy consumption rate exceeds already the stunning figure of 6000 Gigawatt. This is expected to grow rapidly in the next decades due to the increase in demand from the developing countries. The overwhelming part of our energy supply arises from the chemical energy stored in the fossil fuels. These reserves are being rapidly depleted and their combustion has led to unacceptable levels of pollution of our environment. Further acceleration of this process would lead to disastrous climatic consequences. It is evident that the well being of mankind is threatened unless renewable energy resources can be developed in the near future. Photochemistry is expected to make decisive contributions to identify environmentally friendly solutions to the energy problem. One attractive strategy discussed below is the development of systems that mimic natural photosynthesis in the conversion and storage of solar energy. Electron transfer reactions play a vital role in the light induced charge separation that forms the basis of this process. Our review will treat such redox processes that lead to the conversion of light to electric power and the storage of solar energy in the form of chemical fuels such as hydrogen. We shall focus our discussion on heterogeneous electron transfer reactions that occur on solidliquid interfaces that are of particular interest in this connection. To start with we shall briefly analyze the thermodynamic limitations of light energy conversion processes.

2. Efficiency Restrictions in Photochemical Conversion

The primary concern of photochemists and chemists when they run a reaction is the mass yield of product. In chemical reactions whose aim is to convert chemicals into fuels, in electrochemical reactions which convert electricity to chemical potential, or vice versa, and in photochemical reactions which convert light into chemical potential or work, the free energy yield is of equal importance. The laws of thermodynamics impose limitations on the efficiency of the conversion of light energy into chemical potential. Free energy losses in the sequence of steps during a photochemical process have several origins that will be considered in the following order [1]: (1) nonequilibrium conditions at maximum power, (2) entropy of the radiation source, (3) entropy increase on scattering or absorption of the original radiation, (4) inefficiency of polychromatic radiation. Further limitations associated to the storage of the chemical potential will not be discussed here.

2.1 Maximum power extraction

General to all reactions, whether photochemical or not, is the loss of free energy caused by non-equilibrium conditions due to finite power extraction. Consider a chemical reaction in which a reactant A at chemical potential A is converted into a product B at chemical potential B.

A
!A

jf jb

B
!B

i
(1)

The rate of storage of chemical potential in the product B per unit of volume is JB, where the flux J = d[A]/dt = d[B]/dt. If A and B are in equilibrium, the rates of the forward and back reactions are equal and the net flux to the product J = jf jb = 0. Under non-equilibrium conditions where the forward reaction takes place with J > 0, there is a net overall entropy increase and B < A. If K is the equilibrium constant for reaction A

B in ideal conditions, the change in chemical potential is given by

the vant Hoff isotherm :

= B A = RT ln K + RT ln ([B]/[A])

(2)

By putting K = kf / kb, where kf and kb are the rate constants of reactions AB and B , respectively, and by substituting the fluxes defined by jf = kf [A] and jb = kb [B], one obtains the expression of the free energy loss in a spontaneous reaction :

= RT ln ( 1 )

(3)

where = J / jf. The conversion power P of the reaction is given by the rate of production of chemical potential in the form of the product B at the potential B : P = JB = J(A + ). At maximum power, the reaction flux J is given by :

! A ln (1 !) = 1! RT
and the free energy transfer efficiency :

(4)

!p =

A + " A

(5)

The amount of chemical potential converted in a photochemical reaction is typically of the order of 12 eV. If A = 1 eV, one calculates from the latter equations = 0.972,

= 0.093 eV, and p = 0.91.

If the product B is involved in a leakage reaction to yield an undesired product C with a rate constant kl, Equation (4) can be re-written :

!" ln (1 !) = A 1! RT

(6)

with = kl / (kb + kl),, and the free energy conversion efficiency at maximum power :

k " (# 1) A + $ !p = [ 1 l ]" A kb

(7)

Assuming a leakage reaction with kl = kb, and A = 1 eV, one obtains = 0.5,

= 0.986, = 0.110 eV, and p = 0.89. If kl is increased by a factor of ten, the

efficiency decreases slightly to p = 0.85.

2.2 Limitations due to the entropy of light

The fact that radiation possess entropy imposes additional constraints on the possible changes in a material system interacting with light. These constraints determine, in particular, the efficiency of processes involving the utilization of radiant energy. Let consider a photochemical reaction without leakage, where the only fates of the product A* are reaction to give the final product (with flux i) and reverse reaction (with flux jb). The potential of the reactants is composed of the chemical potential A of A and the potential R of the radiation or, by analogy with chemical potentials, the partial molar free energy of the absorbed light quanta.

A + h!
!A !R

jf jb

A*
!A*

i
(8)

The change in potential during the light absorption process is given by:

! = A* - A - R = RT ln (1 ")

(9)

If the radiation is monochromatic at wavelength , its total energy is QR [JEinstein 1] = NAhc / , where NA is Avogadros number, and the entropy associated with it

SR = QR / TR. The effective temperature TR of the monochromatic radiation of

wavelength and of a given spectral irradiance I is expressed by the formula :
TR = hc " 1 kB ! ln ( 1 + 2 hc2 # ) ! 5 I!

(10)

where is the solid angle subtended by the source at the receiver (including any optical concentrator). The spectral irradiance I is the energy of the radiation incident on a unit area per unit time and unit wavelength interval at a given wavelength . Thus, we may write the dimension of I as, for example, [I] = W m2 nm1. Expression (10) for TR is the same as the Planck formula for a black-body giving the same spectral irradiance I at the same wavelength for unit wavelength interval and unit solid angle. Thus rays of light propagating in a specified direction and delivering at the receiver a spectral irradiance I possess a temperature equal to that of a black-body emitting radiation and giving rise to the same irradiance. The entropy of the radiation SR is lost when the light disappears in the absorption process. An equivalent amount of entropy must then be created in the absorber at

ambient temperature TA. Therefore, the maximum energy available to do work at temperature TA is given by: QR (TR - TA) TR

R =

(11)

The maximum possible conversion efficiency is then expressed by what appears to be simply the Carnot formula applied to radiation:

!r =

R = T R - TA QR TR

(12)

Figure 1. Spectral irradiance of the sun at mean earth-sun separation.

 10

The sun delivers a spectral irradiance at the earth surface at AM1.0 (air mass), without concentrator, of 1.16 Wm2nm1 at = 700 nm.[2] The solid angle represented by the sun seen from the earth is = 6.8105 steradian. From Equation (10), one calculates in this case TR = 5500 K, and from Equation (12) with TA = 298 K one obtains

r = 0.946. If the solar spectrum were that of a black-body, all wavelengths would lead
to the same values of TR and r. Figure 1 shows that this condition is fulfilled only if the receiver were outside the atmosphere. At the earth surface, absorption by atmospheric oxygen, ozone, water and carbon dioxide makes the structured solar irradiance spectrum deviate significantly from the ideal black-body spectrum and requires TR() is calculated for each wavelength.

2.3 Further increase of entropy on absorption or scattering

Apart from the entropy of the original radiation, a second source of entropy must be taken into account that causes losses of free energy in the course of the photochemical reaction. Upon absorption, the directionality of the radiation beam is indeed completely lost. The entropy thus increases, while the radiation temperature decreases. An equivalent effect is obtained when the original directional radiation concentrated in a small solid angle is scattered in all directions. The temperature of the scattered light is obtained by replacing in Equation (10) the solid angle by the value 4 corresponding to isotropic radiation at the receiver:
hc " 1 kB ! ln ( 1 + 8# hc2 ) ! 5 I!

TRs =

(13)

 11

With the same numerical figures as above for the irradiance of the sun at 700 nm, the scattering of the radiation over 4 or (what is strictly equivalent) its absorption in a photochemical reaction cause its effective temperature to decrease from TR = 5500 K to TRs = 1297 K. The maximum efficiency calculated from Equations (11) and (12) then drops from r = 0.95 to rs = 0.77. The solid angle does not appear anymore in Equation (13). It should be kept in memory, however, that if the solid angle of collection is increased at the absorber by use of an optical concentrator, the measured irradiance increases in proportion and hence the temperature, potential and efficiency. In the same conditions as in the example above, concentration of the incident radiation by a factor of 10, for instance, translates into a rise of the radiation temperature from 1297 K to 1517 K and an augmentation of the maximum conversion efficiency from 0.77 to 0.80. Under optimum conditions of maximum power, the extraction flux J = Jmax is given by Equation (4), or more generally, if there are leakage processes, by Equation (6). The global efficiency g of conversion of light into chemical potential at maximum power can be expressed by:

!g =

" # (A* A)
N A# hc

RT # " RTA# " = 1 TA A # ln (4$ / %) + # ln (1 &) TR N A# hc N A# hc

(14)

The last three terms represent the fractional losses due to (1) the entropy of the original radiation, (2) the entropy increase due to absorption or scattering of light, and (3) the minimum loss caused by non-equilibrium conditions at power extraction. For

= 700 nm and AM1.0 solar radiation, Rs = 1.36 eV. By substitution of /RT = 52.9
in Equation (4), one obtains = 0.97. The maximum global efficiency being finally estimated as g = 1 0.055 0.180 0.058 = 0.71. If there are leakages from the excited state due to radiationless deactivation processes, Equation (6) must be used with = 1 f, where f is the fluorescence quantum yield

 12

of A in the absence of reaction. These leakages will increase the last term of the summation in Equation (14) and hence lower the global conversion efficiency. In the above example, if f = 0.5 ( = 0.5), the flux ratio is increased from 0.98 to 0.99 and the global conversion efficiency at maximum power slightly reduced from 0.71 to 0.70.

2.4 Efficiency of energy conversion under polychromatic radiation

So far, calculations have assumed that the energy of the excited state is equal to that of the absorbed photon. This is not the case for polychromatic radiation when a single absorber is used. Losses due to non-absorption or the degradation of energy in excess of the excitation energy of A* are generally not avoidable. The simplest and most important case with which we are concerned is that of an absorber with a threshold excitation wavelength t. In a somewhat idealized form, the properties of a threshold converter are the following : (1) the absorptance of the system is 0 for light with wavelength superior to the threshold wavelength t ; (2) all absorbed quanta produce the same excited state with an excitation energy hc/t ; (3) the excess energy hc/ hc/t is transferred to the medium as radiation or heat.

Scheme 1

 13

Assuming that no reaction can take place from hot excited state levels, all absorbed photons, after degradation of excess energy, give rise to the same excitation energy hc/t. The fraction of the energy absorbed from a polychromatic source which is available in the photochemical conversion process is given by :

"t
0

! =

F" # " d" "t

$

F" d"
0

(15)

where F is the spectral radiation flux incident on the converter from an external source. For a threshold wavelength of 700 nm and AM1.0 solar radiation (Figure 1), the fraction = 0.38.[3] Obviously, the value of , and thus that of o, depends on the value of the threshold wavelength t. For a given spectral distribution of the incident radiation energy, an optimal threshold wavelength exists which yields a maximum . The optimal threshold wavelength for a given spectrum of the incident radiation may be determined from Equation (15). The calculation shows, for example, that for Planckian radiation (which spectral distribution matches that of a black-body at the same temperature) with a temperature TR = 5200 K (direct solar light at AM1.5) the optimal wavelength is

topt = 1273 nm, and accordingly opt = 0.44. This wavelength is near the absorption
threshold of silicon solar cells. Therefore, at = 700 nm, TA = 25 C, and for AM1.5 radiation, the maximum thermodynamic overall energy conversion efficiency of these photovoltaic cells is o = g = 0.70 0.44 = 0.31. For green plants, the threshold wavelength determined by the optical properties of chlorophyll is 700 nm. In this case, for AM1.5 irradiation = 0.34, giving an overall conversion efficiency o = 0.24. Molecular photovoltaic devices that will be discussed in section 4 are based on dye-

 14

sensitizers whose absorption threshold, for the most efficient ones, is typically

t = 800900 nm. The thermodynamic limiting energy conversion efficiency for these
photoconverters is thus somewhat lower than that of silicon cells and does not exceed 0.27 at any wavelength under AM1.5 solar irradiation.

 15

3. Status of Photochemical Energy Conversion Systems

Photovoltaic devices are based on the concept of charge separation at an interface of two materials of different conduction mechanism, normally between solid-state materials, either n- and p-type regions with electron and hole majority carriers in a single semiconductor material, heterojunctions between different semiconductors or semiconductor-metal (Schottky) junctions. In photo-electrochemical cells, the junctions are semiconductor-electrolyte interfaces. In recent years, despite prolonged effort, a disillusion has grown about the prospects of electrochemical photo-effects at these interfaces giving rise to competitive photovoltaic devices, since those semiconductors with band gaps sufficiently narrow for efficient optical absorption of visible-light photons are necessarily insufficiently stable against photo-corrosion. The width of the bandgap is a measure of the chemical bond strength. The semiconductors stable under illumination, typically the ceramic oxides of reactive metals such as titanium, therefore have a wide band gap, an absorption edge towards the ultraviolet and a consequent insensitivity to the visible spectrum. Hence the breakthrough represented by the separation of the optical absorption and the charge separation processes in photoelectrochemistry, realized by the association of a redox dye as light-absorbing material with the wide band gap semiconductor. These sensitized semiconductor systems will be discussed further below. The main thrust of the research in photoelectrochemistry during the three decades during the seventies and eighties has been to develop systems for the splitting of water into hydrogen and oxygen. The main obstacle to direct photoelectrolysis of water are the lack of efficient light absorption (for reasonable solar efficiencies, the band gap must be less than 2.0 eV), corrosion of the semiconductor (thermodynamically, most useful semiconductors are photochemically unstable in water), and energetics i.e. the

 16

difficulty of matching the semiconductor band-edge energies with the H2 and O2 evolution reactions). The most photochemically stable semiconductors in aqueous solution are oxides, but their band gaps are either too large for efficient light absorption or their semiconductor characteristics are poor. Semiconductors with better solid-state characteristics are typically thermodynamically unstable with respect to oxidation. However, p-type semiconductors generally offer some protection against

photocorrosion, because under illumination the surface is cathodically protected. p-type indium phosphide is stable in strong acid under illumination and H2 evolution but requires an external bias for water splitting. This earlier work on the photoelectrolyis of water has been reviewed.[4]

 17

4. Molecular Photovoltaics
In a conventional p-n junction photovoltaic cell made, for example, of silicon, the semiconductor assumes two roles simultaneously: It harvests the incident sunlight and conducts the charge carriers produced under light excitation. In order to function with a good efficiency, the photons have to be absorbed in the vicinity of the p-n interface. Electron-hole pairs produced away from the junction must diffuse to the p-n contact where the local electrical field separates the charges. To avoid charge carrier recombination during the diffusion, the concentration of defects in the solid must be small. This imposes severe requirements on the purity of the semiconductor material, rendering solid state devices of the conventional type quite expensive. Molecular photovoltaic systems separate the functions of light absorption and carrier transport. Light harvesting is carried out by a dye-sensitizer which initiates electron transfer events leading to charge separation. This renders unnecessary the use of expensive solid state components in the system. While being simple from the conceptual point of view, the practical implementation of such devices must overcome several serious obstacles if the aim is to develop molecular systems which convert sunlight to electricity at an efficiency comparable to that of silicon cells, and meet the stability criteria for practical applications.

4.1 Mimicking Natural Photosynthesis

Natural photosynthesis is the most important of the many interesting photochemical processes known in biology. Not only was the evolution of the Earths atmosphere dependent on it, but also it is the main route by which the free energy of the

 18

environment is made available to the living world. Green plants, algae and cyanobacteria make use of sunlight to drive a thermodynamically uphill reaction, the reduction of carbon dioxide to carbohydrates by water.

CO2 + H2O 1/6 C6H12O6 + O2

(16)

The input chemicals are carbon dioxide and water, while the output is oxygen and carbohydrates. The latter serve as a feed stock for other organic products such as wood, coal, oil and gas constituting the worlds fossil fuel reserves. It is estimated that about 1011 tons of carbon dioxide are assimilated annually by plants on Earth, whereby the amount of solar energy harvested by natural photosynthesis is 31018 kJ, corresponding to the continuous generation of 90 000 gigawatt of electrical power. Most of the key features of how photosynthetic energy conversion operates are known by now. Light induced charge separation is achieved through judicious spatial arrangement of the pigments and elements of the electron transport chain in the tylakoid membrane. Co-operative interaction between these components allows the electron transfer to proceed in a vectorial fashion. Although strategies to design artificial photoconversion devices should not attempt to blindly imitate all the intricate of natural photosynthesis, it is inconceivable to accomplish the challenging task of converting visible light into electrical work or chemical potential without suitable engineering on the molecular level. Efficient molecular photovoltaic devices described in section 4 and tandem systems for water cleavage by visible light presented in section 5 use similar concepts as green plants to harvest and convert solar energy. It is therefore useful to review the salient features of their natural analogue. The essence of natural photosynthesis is the use of photochemical energy to split water and reduce CO2. Molecular oxygen is evolved in the reaction, although it appears at an earlier stage in the sequence of reactions than the reduction of carbon dioxide.

 19

Photochemical processes produce compounds of high chemical potential, which can drive a multi-step synthetic sequence from CO2 to carbohydrate in a cyclic way. Reaction (16) is quite endoergic and thus thermodynamically very improbable in the dark (G = 522 kJ per mole of CO2 converted). Production of one molecule of oxygen and concomitant conversion of one molecule of carbon dioxide require the transfer of four electrons:

2H2O O2 + 4e + 4H+ 4e + 4H+ + CO2 1/6 C6H12O6 + H2O

(17)

(18)

Reaction (16) is the sum of reactions (17) and (18). Clearly, if each photon harvested by the system can lead to the transfer of one electron, then a minimum of four photons are required for the conversion of each CO2 molecule. Experimental measurements of the quantum yield indicate that eight photons are actually needed, suggesting that two photons are used for each electron transfer and that a two-step process is taking place with long-lived intermediates coupling the steps. Photosynthesis comprises a light-induced and a dark reaction. The first, called photophosphorylation, involves the two-electron reduction of nicotinamide adenine dinucleotide phosphate (NADP+) by water, to produce NADPH and oxygen. The redox reaction is coupled to the generation of adenosine triphosphate (ATP) from adenosine diphosphate (ADP):

2H2O + 2NADP+ + 3ADP + 3P 2NADPH + H+ + 3ATP + O2

(19)

where P stands for the phosphate PO43 anion. This light-driven reaction takes place in the tylakoid membranes located in the interior of the chloroplasts of plant cells.

 20

Figure 2. Functional organization of photosystem II in protein-complexes contained in the thylakoid membrane. Excitation energy is harvested by chlorophyll (Chl) and carotenoids (Car) molecules and transfered to the special pair (Chl2). Vectorial electron transfer across the membrane takes place from excited Chl2* to plastoquinone (pQ) via pheophitine (Ph) and quinone (Q) electron mediators.

The photosynthetic unit assembled in these membranes is composed of antenna pigments for light energy harvesting, i.e. chlorophyll and carotenoids, as well as a reaction center consisting of two photosystems. The photons absorbed by the antenna pigments are first transferred to a chlorophyll dimer that is part of the reaction center. The electronic excitation causes electrons to be ejected from the chlorophyll dimer and then passed on to various electron-transferring mediators. The judicious spatial arrangement of these components allows the electrons to be transferred in a vectorial fashion from the inner to the outer part of the membrane (Figure 3). The positive

 21

charges left behind produce oxygen and protons from water while the electrons reduce NADP+ to NADPH. The latter is nothing else but a hydride, i.e. a stored form of hydrogen. The pH gradient generated across the membrane is used to store additional energy via the phosphorylation of ADP to ATP. There are two light absorbing photosystems, PS I and PS II, each containing chlorophyll, that operate in series. Photoexcitation of PS II initiates a series of redox steps resulting in the transfer of electrons from water to plastoquinone (pQ). This product is the electron donor for PS I which under illumination performs the reduction of NADP+ to NADPH (Figure 3).

Figure 3. The Z-scheme of green plants photosynthesis: coupling of the two pigment systems, I and II. P680 and P700 = chlorophyll; pQ = plastoquinone; Cyt = cytochrome; pC = plastocyanine; Fd = ferrodoxine.

 22

The dark reaction, known as Calvin cycle, uses the reducing power of NADPH as well as the free energy stored in the ATP to assimilate carbon dioxide in the form of carbohydrates. The way by which Nature achieves carbon fixation is via the reaction of CO2 with ribulosebiphosphate (RuBP) to give two molecules of 3-phosphoglycerate, a process which is catalyzed by the enzyme RuBP-carboxylase. The phosphogylcerate is converted further to fructose 6-phosphate, the final product of the Calvin cycle. The overall reaction, despite its complex mechanism corresponds to the simple Equation (16) above. Most green plants operate with photosynthesis efficiencies of a few percent. Eucalyptus trees are particularly efficient in this respect and reach as high as 5 %, one fifth of the thermodynamic maximum energy conversion efficiency discussed in section 2. In plant leaves, sunlight is only weakly absorbed by chlorophyll and carotenoids molecules. These dyes, however, are contained in the membrane of stacked pancake-shaped vesicles, the thylakoids, that are grouped in the chloroplast cells. Efficient harvesting of sunlight is eventually achieved by absorption through numerous pigment layers. Furthermore, light harvesting and charge separation functions are carried out separately in the natural photosynthetic system, and end up in the transport of opposite charges on both sides of the thylakoid membrane. In molecular photovoltaic devices discussed hereafter, the incident photons excite a dye-sensitizer that injects an electron into the conduction band of a wide bandgap semiconductor. Positive holes left in the dye are then carried away by an electrolyte mediator or conducted through a hole-transporting medium (Figure 4). Mimicking the key features of natural photosynthesis, these devices rely on a mesoporous film structure to ensure efficient harvesting of sunlight using a molecular absorber. As well, light absorption and electron collection functions are separated in such systems. Electron injection into semiconducting nanoparticles which achieves charge separation

 23

across the solid/electrolyte interface is analogous to charge separation in the photosynthetic membrane.

Figure 4. Schematic representation of the principle of the nanocrystalline injection photovoltaic cell showing the electron energy level in the different phases. The cell voltage V obtained under illumination corresponds to the difference in the quasiFermi level of TiO2 under illumination and the electrochemical potential of the redox couple (M+/M) used to mediate charge transfer between the electrodes.

 24

4.2 Mesoscopic oxide semiconductor films

4.2.1 Light harvesting by monomolecular dye layers

Absorption of incident radiation by a molecular sensitizer adsorbed as a monolayer to the surface of a solid come up against the fundamental problem of limited light capture cross section of the dye molecules. The absorption cross section [cm2] is related to the decadic molar extinction coefficient [lmol1cm1] by the expression (20):

= 1000 ln(10) / NA

(20)

where NA is Avogadros number. Since characterizes molecules in solution which spatial orientation is random, favorable orientation of the chromophores upon adsorption on a surface can lead to an increase of the effective cross section by at most a factor of 2. Typical values for dyes lie between 104 and 2105 lmol1cm1 yielding for the light capture cross section values between 0.0038 and 0.15 nm2. The area the sensitizer molecules occupies on the surface of the supporting solid is much larger, e.g. about 12 nm2. Hence, at most a few percent of the incident light can be absorbed. Deposition of a multilayer of dye on the surface in order to increase its light absorption is generally a mistaken tactic, since energy transfer between sensitizer molecules rarely gives rise to efficient antenna effects and outer dye layers act only as a light filter, with no contribution to photocatalysis. A successful strategy to solve the problem of light absorption through such molecular layers is found in the application of high internal surface area films consisting of nanocrystalline oxide particles with a diameter of 1020 nm. The mesoporous morphology of the layer plays a crucial role in the harvesting of sunlight. Depending on

 25

film thickness, their real exposed surface area can easily be made 1000 times larger than the apparent geometric one. When light penetrates the dye-covered solid sponge, it travels through hundreds of adsorbed dye monolayers and is efficiently captured. Consider the case of a 3 m thick mesoporous film whose effective surface area is 300 times larger than that of a compact solid and that the film is covered by a monolayer of dye molecules each of which occupies an area of 1 nm. On the geometric projection of such a rough surface a dye coverage of = 31016 cm2 is reached. Its absorbance A [] is given by the equation:

A =

(21)

where is the chromophore surface concentration and its absorption cross section. Suppose that the dye molecule at the wavelength of its absorption maximum has a light capture cross section of 51017 cm2 ( = 1.3104 lmol1cm1). As a result the absorbance of the film would be A = 1.5. Neglecting light scattering by the film, its light harvesting efficiency (LHE), namely the absorptance, is given by Equation (22), implying that 97 % of the incident photons are absorbed.

LHE = 1 10A

(22)

4.2.2 Preparation and morphology of mesoscopic oxide semiconductor films

Over the recent years, nanocrystalline materials have attracted increasing attention from the scientific community because of their extraordinary physical and chemical properties. These result from the ultra-fine structure (i.e. grain size < 50 nm) of the materials. Nanocrystalline electronic junctions are constituted by a network of

 26

mesoscopic oxide or chalcogenide particles, such as TiO2, ZnO, Fe2O3, Nb2O5, WO3, Ta2O5 or CdS and CdSe, which are sintered together to constitute transparent mesoporous films, typically a few microns thick. As electrons can rapidly percolate between interconnected particles through the film, the entire surface-adsorbed molecular layer can be electronically addressed. Charge transfer events involving adsorbed molecule can thus be induced through the nanocrystalline support and recorded as electrical current. Optical monitoring is also facile as the signals arising from the grafted molecules are greatly enhanced due to the huge internal surface area of the junction. Since fifteen years titanium dioxide has become the semiconductor of choice. The material has many advantages for sensitized photo-electrochemistry: As most wide bandgap oxides, it is stable and does not tend to corrode in liquid electrolytes. The Lewis acidity of its surface affords a convenient handle for attachment of dye molecules by way of electron-rich anchoring groups. Moreover, TiO2 is a low cost, widely available, non-toxic, and even biocompatible, substance that is widely used in domestic applications. Mesoporous oxide films are commonly produced via a sol-gel type process involving a hydrothermal step. The procedure is illustrated for TiO2 in Figure 5. The initial precipitation of the oxide involves controlled hydrolysis of a Ti(IV) compound, usually an alkoxide such as titanium tetraisopropoxide or TiCl4, followed by peptization. Autoclaving of the obtained sols (heating at 200250 C for 12 h) allows for controlled growth of the primary particles and improves their crystallinity. During this hydrothermal growth, smaller particles dissolve and fuse to large particles by a process known as Ostwald ripening. After partial removal of solvent and addition of a binder, the sol is ready for deposition on the substrate. For the latter, a conducting glass (sheet resistance = 810 /square) is often used. The sol is deposited by doctor blading or screen printing and briefly fired in air. During the firing, the binder and possible organic

 27

contaminants are burned out, thus producing a clean, mostly dehydroxylated, oxide surface. The film thickness is typically 510 m and the film mass about 12 mgcm2.

Figure 5. Outline of the steps involved in the preparation of mesoporous TiO2 film electrodes.

 28

The electronic contact between particles is produced by sintering during the firing treatment at about 450 C. A mesoporous structure with a very high effective surface area is thereby formed. Analysis of the layers shows their porosity to be about 60 % and the average pore size 12 nm.

Figure 6. Scanning electron micrograph of a mesoporous TiO2 film supported on conducting glass. The predominant facets of the anatase crystals have the (101) orientation.

Figure 6 displays the morphology of such a nanocrystalline TiO2 (anatase) layer deposited on a transparent conducting oxide (TCO) glass. A large fraction of the particles has a bipyramidal shape, which is typical for anatase crystalline form. The exposed surface faces are mostly oriented in the (101) direction.[5] The mean particle

 29

diameter is 20 nm in this case. Their size and morphology can be adjusted by varying the conditions of the sol-gel process used for film preparation. Films of self-assembled rod-like particles have been obtained when the hydrothermal treatment of the TiO2 colloid is done in the presence of tetramethylammonium hydroxide at 190230 C. The rod-like particles were observed to have (100) faces terminated from the (001) side. The pores diameter of the film in this case is 4 nm with a very narrow size distribution.[6]

4.3 Photoinduced charge separation at the solid/electrolyte interface

The use of mesoporous oxide films as a substrate to anchor the dye molecules allow sunlight to be harvested over a broad spectral range in the visible region. Similarly to chlorophyll in the green leaf, the dye acts as an electron transfer sensitizer. Upon excitation by light, it injects an electron into the conduction band of the oxide, resulting in the separation of positive and negative charges. Charge transfer from photo-excited dyes into semiconductors was discovered more than a century ago in a famous experiment by J. Moser.[7] He observed that the photoelectric effect reported earlier by E. Becquerel on silver plates [8] was enhanced in the presence of erythrosine dye. The one-page publication describing his observations is shown in Figure 7. A few years before, H. Vogel in Berlin had associated dyes with the halide semiconductor grains to make them sensitive to visible light.[9] This led to the first panchromatic film, able to render the image of a scene realistically in black and white.[10] However, the clear recognition of the parallelism between the two procedures, a realization that the same dyes in principle can function in both systems [11] and a verification that their operating mechanism is by injection of electrons from photo-excited dye molecules into the conduction band of the n-type semiconductor substrates [12] date to the 1960s.

 30

Figure 7. A copy of the 1887 publication by J. Moser on the amplification of photoelectric currents by optical sensitization of silver halides by erythrosin.[7] The system described in this paper is indeed the first dye-sensitized photovoltaic solar cell.

In subsequent years the idea developed that the dye could function most efficiently if chemisorbed on the surface of the semiconductor.[13,14] The concept emerged to use dispersed particles to provide a sufficient interface,[15] then photo-electrodes were

 31

employed.[16,39] Finally, the use of nanocrystalline TiO2 films sensitized by a suitable molecular dye provided an important technological breakthrough.[17] These mesoporous membranes have allowed in effect for the first time the development of a regenerative photoelectrochemical cell based on a simple molecular light absorber, which attains a conversion efficiency commensurate with that of silicon based photovoltaic devices, but at a much lower cost.

4.3.1 Molecular engineering of dye sensitizers

Many studies based on the observed bulk photoelectrochemical effects and on direct probing of the processes occurring at the solid surface have provided firm evidences that the sensitizing mechanism involves as a primary step electron or hole injection by the electronically excited sensitizer molecule (S*) into the semiconductor (SC). S | SC + h S* | SC S+ | (e)cb SC + S | SC + h S* | SC S | (h )vb SC

(23)

(24)

Alternatively, charge injection into the semiconductor can involve the reductive or oxidative quenching of the dye excited state by a redox active species (a supersensitizer) followed by thermal interfacial electron transfer.[18]

S* | SC + D S | SC + D+ S | (e)cb SC + D+ S* | SC + A S+ | SC + A S | (h+)vb SC + A

(25)

(26)

 32

In the case of the injection of an electron from the excited state of a molecular sensitizer into the conduction band of a semiconductor [Equation (23)], the thermodynamics of the photoredox reaction requires the oxidation potential of the dye excited state (S+/S*) to be more negative than the conduction band flatband potential of the semiconductor, and thus :

(S+/S) < C + E0,0 / F

(27)

where (S+/S) is the oxidation standard potential of the dye, E0,0 its excitation energy, C (SC) the conduction band flatband potential, and F the Faraday constant. The redox potential for the dye can shift upon adsorption from solution due to Coulombic or stronger covalent interactions with the solid substrate. This potential change can amount to several hundreds of millivolts. While n-type semiconductors cannot be used generally to measure oxidation potentials of adsorbed dye sensitizers by conventional cyclic voltammetry, reduction potential (S/S) is often more accessible. Assuming oxidation and reduction potentials of the dye ground state on the surface are linked by a constant relation :

(S/S) = (S+/S) E0,0 / F + x,

(28)

the energetic threshold for charge injection from the dye excited state into the conduction band of the solid would require the reduction potential of the adsorbed dye to be (S/S) < CB + x, where the last term has been found for a large number of various organic sensitizer molecules to be x = 0.35 V.[19] The ideal sensitizer for a single junction photovoltaic cell should absorb all light below a threshold wavelength of at least 900 nm. In addition, it should be anchored to the semiconductor oxide surface and inject electrons to the conduction band with a quantum

 33

yield of unity. Its redox potential should also be sufficiently high that it can be regenerated rapidly via electron donation from an electrolyte or a hole conductor. Finally, it should be stable enough to sustain at least 108 redox turnovers under illumination, corresponding to approximately 20 years of functioning under natural light in day-night cycles. The best photovoltaic performance in terms of both conversion yield and long-term stability has so far been achieved with polypyridyl complexes of ruthenium and osmium.[2023] Sensitizers having the general structure ML2X2, where L stands for 2,2-bipyridyl-4,4-dicarboxylic acid (dcbpy), M for Ru(II) or Os(II), and X for halide, cyanide, thiocyanate, or water,[2022] are particularly promising. In recent years, the ruthenium complex dye cis-[RuII(dcbpy)2(NCS)2] has emerged as the model of a heterogeneous charge-transfer sensitizer for molecular photovoltaic cells. Reported for the first time in 1993,[20] its performances has been unmatched since then. Only recently, a credible challenger has been found with the black dye tri(thiocyanato)(2,2:6,2-terpyridyl-4,4,4-tricarboxylate)ruthenium(II) [ RuII(tctpy)(NCS)3] that exhibits better near-IR photo-response.[23]
COOH!

COO-!

COOH! S! C! N! Ru! N! S! C! N! COOH! N! S! N! N!

S! C! N!

N!

Ru! C! N!

N! N!

COO-!

N!

C! S!

COO-! COOH!

cis-[RuII(dcbpy)2(NCS)2]!

RuII(tctpy)(NCS)3!

Scheme 2

 34 The efficiency of cis-[RuII(dcbpy)2(NCS)2] complex as a redox sensitizer of titanium dioxide is conferred by several important features of the molecule. Carboxylic groups carried by the ligands provide a good anchoring of the dye on the acidic surface of TiO2. Surface derivatization of the mesoporous oxide film is normally performed by dipping it into a solution of the dye in a 50:50 (v/v) solvent mixture of acetonitrile and tert-butanol. A monolayer of the sensitizer is formed spontaneously. The adsorption follows a Langmuir isotherm with a binding constant K = 5104 lmol1. The area occupied by one molecule at the anatase surface at full monolayer coverage is 1.65 nm2. The interaction between the carboxylic group and the oxide is of fundamental importance in determining the geometrical structure of the adsorbed dye state and influencing the electronic coupling with the Ti(3d) conduction band orbital manifold. The most likely configuration supported by IR analysis [24] involves the attachment of the dye via two of its four carboxylate groups. The carboxylate either bridges two adjacent rows of titanium ions through bidentate coordination or interacts with surface hydroxyl groups through hydrogen bonds. Of the two remaining carboxylate groups, one is ionized while the other remains in the protonated form. Model studies, using the dcbpy ligand adsorbed onto single-crystal TiO2 (110) rutile, investigated by means of X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and quantum chemical calculations,[25] are in favor of the bridging bidentate configuration illustrated by Figure 8. The ligand is oriented at an angle of about 40 degrees with respect to the (001) crystallographic direction. In addition to this linkage mode, calculations suggest the monodentate ester bond is also thermodynamically stable. The bidentate bonding, however, is stronger and thus would be the preferred anchoring configuration for the cis-[RuII(dcbpy)2(NCS)2] dye on titanium dioxide. The interfacial electron transfer events will be strongly affected by the electronic structure of the dye in the adsorbed state and the energy level matching between its excited state and the conduction band of the semiconductor. Generally, the optical

 35

transition of Ru complexes has metal-to-ligand charge-transfer (MLCT) character. Excitation of the dye involves transfer of an electron from a metal ion d-orbital to the * orbital of the ligand. cis-[RuII(dcbpy)2(NCS)2] exhibits two such transitions in the visible domain. The absorption maxima in ethanolic solution are located at 518 and 380 nm, the extinction coefficients being 1.33104 and 1.3104 mol1lcm1, respectively. The complex emits at 750 nm, the excited state lifetime being 60 ns.[20] Results from ab initio calculation [26] of a decarboxylated cis-[RuII(dcbpy)2(NCS)2] complex show that the highest occupied molecular orbital (HOMO) level is shared by both the Ru(II) metal ion and the N=C=S ligands. Application of photoelectron spectroscopy have confirmed that both Ru-4d and atomic orbitals centered on the NCS groups, in particular S-3p, contribute to the HOMO of the complex.[27] In a photovoltaic cell, the oxidized dye, after electron injection to the conduction band of the oxide, should quickly be reduced by a redox species in the surrounding electrolyte. The observation that the frontier molecular orbital contains a substantial amount of 3p character from the sulfur atom of the NCS ligand may play an important role in this process. The thiocyanate groups point in the direction of the electrolyte, which may facilitate reduction by mediators, making it particularly suitable for highly efficient solar cells. Ab initio calculations also show that the lowest unoccupied molecular orbital (LUMO) of the cis-[RuII(dcbpy)2(NCS)2] complex is concentrated on the * structure of the dcbpy ligands. Hence, absorption of visible light by the compound can be assigned to a RuNCS-bpy(*) charge transfer transition. Preliminary calculations also indicate that the dcbpy rings share their LUMO with the carboxylate groups, thus enhancing electronic coupling between the dye excited state and the acceptor levels manifold of the solid. The oxidation potential and excitation energy of the fully protonated form of the dye in solution being 0(S+/S) = +1.10 V/NHE and E = 1.65 eV, respectively, the
0,0

 36

oxidation potential of the MLCT excited state of the sensitizer establishes at

0(S+/S*) = 0.55 V/NHE.[20] The flatband potential of TiO2 in dry aprotic solvents
can be as negative as C = 1.25 V/NHE.[28,29] In such conditions, the conduction band of the solid would in principle be out of reach of the dye excited state and only deep localized sub-bandgap states could potentially act as acceptor levels in the injection process. Surface protonation via adsorption of the carboxylic groups results however in a positive shift of the flatband potential that can amount to several hundred millivolts. Moreover, complete deprotonation of the four carboxylic groups of cis-[RuII(dcbpy)2(NCS)2] was demonstrated recently to cause its oxidation potential to shift negatively by ca 300 mV.[30] Both effects combined together with the presence of traces of H2O render the interfacial electron transfer from the dye excited state to the conduction band of titanium dioxide thermodynamically favorable.

4.3.2 Dynamics of charge injection in wide-bandgap semiconductors

Photoinduced charge injection from an electronically excited molecular state into a wide continuum of acceptor levels, including the conduction band of a semiconductor, is one of the simplest photochemical surface reaction [Equation (23)]. This process is however rather special, in the sense that there are many channels available for the electron transfer. The reaction can choose its energetic path to yield an electron within the band of the solid that is characterized by a variable amount of kinetic energy. The energy excess should also be carried by the dye cation S+, produced concomitantly, in the form of vibrational excitation. As a consequence, provided the driving force is sufficiently large compared to the nuclear reorganization energy, the system can find an activationless path, optimizing in this way the electron transfer rate (Figure 9).

 37

Figure 9. Energetics and dynamics of electron injection from the electronic excited state S* of a dye to the conduction band of a semiconductor. Charge transfer from a specific vibronic state v of S* can lead to any vibrational state v of the product S+, provided there is a sufficient density of acceptor levels covering a wide enough energy range in the solid. Energy conservation requires that a lower lying electronic state in the conduction band (kinetic energy of the carrier in the conduction band Ek) corresponds to a higher vibrational state v of S+ (vibrational excitation energy Ev). This conditions implies that acceptor levels are quantified by the energy spacing h of the oxidized state oscillator. In terms of the Marcus model, the interfacial electron transfer process would be kinetically optimum when its free energy G is equal to the reorganization energy of the system. This ideal path is available as long as the excess energy Ex of the excited state of the dye to the lowest acceptor state in the semiconductor Ex is larger than .

 38

In terms of semiclassical electron transfer theory, the simplest kinetic model describing the charge injection as a non-adiabatic radiationless process is derived from Fermis Golden Rule. The rate constant for the reaction can be expressed as the product of a thermally averaged Franck-Condon factor FC, which depends on the driving force Go as well as the nuclear reorganization energy accompanying the electron transfer, and an electronic factor which is proportional to the square of the electronic coupling element |H| :

2 k et = 4! |H|2 FC h

(29)

For a large number of accessible acceptor levels, the summation over all the terms of the Franck-Condon factor reduces to the unweighted density of final states.[31,32]

2 k i = 4! |H|2 1 na h h"

(30)

In Equation (30), the actual density of final states is approximated by the reciprocal energy level spacing 1/h of the dye cation oscillator, multiplied by a factor 0 na 1 accounting for the density of empty electronic states available in the solid. Above the flatband energy level, the density of acceptor states in the conduction band of a semiconductor is usually very large and the density of final states solely determined by the density of energy levels of the dye cation (na 1). Below the band edge, empty trap states are present, whose density decreases gradually at lower energies (na 0). The density of accepting states NC(E) in the conduction band of a semiconductor is given by Equation (31) :[33]

NC (E) =

4!

* 3/2 2 mde h
2

E EC 1/2

(31)

 39

where EC is the energy of the conduction band edge, and m*de the density-of-state effective mass for electrons. The latter parameter depends strongly on the material. In TiO2, for instance, assuming m*de m*e 6 me, the calculated density of states would be at least two orders of magnitude larger than that in ZnO, for example, where m*de 0.24 me.[34,35] The density of states is also expected to be dependant upon the size of the semiconductor nanocrystallites. Strong quantum confinement indeed results in widely spaced electronic levels and therefore in a very low density of states. Although this size quantization effect would be negligible for TiO2 where the exciton binding energy is very small, it is expected, for example, to play a significant role for ZnO particles whose diameter is smaller than ~10 nm. Equation (30) can only be used when the electron transfer process takes place from a single prepared excited state of the sensitizer. In the general case, absorption of photons, whose energy h is larger than the electronic excitation energy E0,0 of the dye, leads to the population of higher vibronic levels of the molecule [Equation (32)]. Relaxation of these vibrationally excited intramolecular states (Equation (33)] and of the whole system along the classical reaction coordinate is expected to compete with the electron transfer process [Equation (34)].[36] In these conditions, the electronic coupling |H| between the donor and the acceptor states becomes a time- and excitation wavelengthdependent function and cannot be readily accessed anymore.[32]

S | SC + h (> E0,0) S* (v>0) | SC

(32)

S*( v>0) | SC S*( v=0) | SC +

kr

(33)

S*( v>0) | SC S+ | (e)SC +

ki

(34)

S*( v=0) | SC S+ | (e)SC +

ki

(35)

 40

S*( v=0) | SC S | SC + h +

kd

(36)

Two limiting cases could be considered that would, however, let us treat in a simple way the interfacial electron transfer process as involving a single prepared excited state of the sensitizer: (1) Charge injection is slow enough compared to the vibrational relaxation of the dye excited state ( ki << kr ). In this event, electron transfer would be able to take place only from the lowest excited state (v=0) [Equation (35)], and the injection quantum yield i would be simply controlled by the kinetic competition between the electron injection [Equation (35)] and the decay of the excited state [Equation (36)] :

i = ki / ( ki + kd ) = ki / ( ki + 1 / f )

(37)

where f is the excited state lifetime of the sensitizer. (2) Charge injection is fast compared to nuclear relaxation of the excited state ( ki >> kr ). In this case, interfacial charge transfer would take place from the prepared hot vibronic level [Equation (34)] and the quantum yield for the primary injection process would be close to unity i 1. For both limiting cases, ki << kr and ki >> kr, relation (30) would be relevant, provided electron transfer is non-adiabatic. When the electronic coupling of the donor and acceptor becomes sufficiently large (typically |H| > 150 cm1 0.7 kT), the electron transfer will be increasingly adiabatic and, in the absence of solvent dynamics control, the rate constant will eventually be proportional to a nuclear vibration frequency factor n. In this case the electronic coupling element is not contained in the rate expression. For other cases, where |H| is small enough, the value of the coupling element is needed for a quantitative description of the electron transfer rate. There is obviously a considerable interest in the role of the

 41

electronic coupling factor, as the separation distance and anchoring geometry of the sensitizer on the surface will determine its magnitude. The Gamov expression (38) is frequently used to estimate the changes in |H| with separation distance in photoinduced electron transfer where the electron donor and acceptor are fixed relative to one another :

|H| = |H|0 exp [ ( r r0 ) ]

(38)

where the damping factor has values ranging from 0.85 to 2.5 1. Provided that other factors beside distance do not influence the electron transfer rate, Equation (39) can be used to estimate the rate at a known separation distance r :

ket = ket0 exp [ ( r r0 ) ]

(39)

where ket0 1013 s1. Other parameters, such as spin changes, symmetry factors, and the relative orientation of both reactant may influence the magnitude of the electronic coupling element.[37] In favorable thermodynamic conditions, where the lowest electronic excited state energy level of the sensitizer lies above the bottom edge of the conduction band, charge injection competes kinetically with the decay of the sensitizers excited state [Equation (36)]. Hence, for dyes that are characterized by emission lifetimes f of the order of one nanosecond, interfacial electron transfer rate constants of the order of ki = 1011 s1 suffice to ensure high injection quantum yields. Most of the previous knowledge on bulk semiconductor-electrolyte interfacial charge transfer is derived from steady-state photocurrent measurements achieved in photo-electrochemical cells. Obtaining electron transfer rate constants from such an indirect method, however, is difficult because photocurrent depends on many other interfacial and bulk processes.

 42

The rapid dynamics of electron injection can be investigated by application of transient laser spectroscopy to colloidal dispersions or nanocrystalline semiconductor films. Such materials are particularly amenable to time resolved optical studies, as they display a good transparency throughout all the visible and NIR spectral domains. Moreover, they are characterized by a high solid surface area exposed to the solution, yielding high sensitizer absorbance for only monolayer dye coverage. Most presently studied oxide semiconductor systems, namely TiO2, SnO2 and ZnO, are also of particular interest for the development of artificial photosynthetic and photovoltaic devices.[99] Earlier studies on dye sensitized TiO2 reported nanosecond time constants for the injection kinetics.[3841] These results were obtained indirectly from the measurement of the injection quantum yield and implicitly assumed that the interfacial electron transfer reaction was competing only with the decay of the dye excited state. Other works were based on the same assumption but used measurements of the dye fluorescence lifetime, which provided ps-fs time resolution.[4244] Direct time resolved observation of the build up of the optical absorption due to the oxidized dye species S+ has been employed in more recent studies.[4550] This appears as a more reliable way of monitoring the charge injection process as it does not require any initial assumption on the sensitizing mechanism. Figure 10a shows the transient difference spectra obtained upon nanosecond laser excitation of cis-[RuII(dcbpy)2(NCS)2] in ethanolic solution and of nanocrystalline titanium dioxide transparent films onto which the sensitizer was adsorbed. The dye is excited with 605 nm output of a laser system and the absorbance change observed immediately after the laser excitation is plotted as a function of the detection wavelength.[51] Luminescence quenching and photocurrent experiments have confirmed that 600 nm excitation of the sensitizer resulted in the formation of the charge separated state S+|(e)SC.

 43

Figure 10. (a) Transient absorption spectra obtained upon ns pulsed laser excitation of cis-[RuII(dcbpy)2(NCS)2] dye in ethanolic solution (1), and of a sensitized TiO2 transparent film (2). Spectra were recorded 50 ns (1a, 2a) and 0.5 s (1b, 2b) after the laser excitation pulse ( = 605 nm, 5 ns pulse duration). (b) Transient absorption spectra recorded 6 ps after ultrafast laser excitation ( = 605 nm, 150 fs pulse duration) of cis-[RuII(dcbpy)2(NCS)2] dye in ethanol (1), and of a fresh sensitized titanium dioxide film (2). Insert shows the temporal behavior of the absorbance of the latter system, measured at = 750 nm with sub-picosecond time-resolution.

 44

The spectrum obtained upon irradiation of dye sensitized TiO2 displays a broad absorption feature peaking around 800 nm which half lifetime exceeds 0.5 s. Such a lifetime is more than one order of magnitude longer than that of the isolated dye excited state in solution. The recorded spectrum is comparable to that of the one-electron oxidation product [RuIII(dcbpy)2(NCS)2]+ of the complex produced by oxidative quenching of the excited state in an alcoholic solution containing methylviologen as an acceptor,[46] or generated by pulse radiolysis.[52] It can be readily distinguished from the spectrum of the dye excited state obtained in solution, whose band maximum is located at 710 nm.[51] These observations demonstrate unambiguously that the transient spectral feature observed upon excitation of the sensitized semiconductor cannot be assigned to an excited state of the dye but must be attributed to the charge separated state S+|(e)cb resulting from interfacial charge injection, where both a LMCT transition of the NCS ligands to the Ru(III) metal ion center in S+ and absorption by conduction band and/or trapped electrons contribute to the spectrum. Further sub-picosecond data were collected.[46] Transient data measured for dyesensitized TiO2 films were compared with those obtained for control dye-coated ZrO2 films, as the high conduction band edge of the latter material should prevent electron injection. Figure 10b shows the absorption difference spectra obtained at a time delay of 5 ps after 605 nm pulsed laser excitation. The spectrum obtained for the dye-sensitized zirconia films exhibits a maximum at 710 nm as observed for cis-[RuII(dcbpy)2(NCS)2] dye in ethanolic solution and is therefore assigned to the dye MLCT excited state. On the other hand, the transient spectrum recorded for sensitized TiO2 displays a maximum at 800 nm that is characteristic of the dye cation S+. In contrast to the data obtained for dye-coated ZrO2 films, the difference spectra measured with sensitized TiO2 exhibited some temporal evolution for time delays less than 5 ps. Typical transient absorption data at a probe wavelength of 750 nm is shown in the insert of Figure 10b. The data show a fast ~100 fs instrument response limited signal growth followed by a slower

 45

kinetic phase extending on several picoseconds. A detailed multi-exponential analysis of the traces obtained revealed at least three kinetic components with lifetimes of <100 fs (35%), 1.3 ps (22%) and 13 ps (43%).[29,53] In a recent experiment,[35] mid-IR spectroscopy was used to probe directly the buildup of electron concentration inside the semiconductor. Careful examination at different wavelengths and time scales yielded a complex kinetics which could be described by two exponentials with rise times of 50 25 fs (> 84 %) and 1.7 0.5 ps (< 16 %), the slower component being very sensitive to the sample condition. The origin of such complex electron transfer kinetics is not clear yet. The participation of various electronic excited states of the Ru(II) dye sensitizer to the reaction was ruled out as one failed to observe any effect of the excitation wavelength. Nor was a significant difference observed in the results obtained for dyed TiO2 films exposed to air and in propylene carbonate, thus excluding possible effects due to the solvation dynamics.[53] Direct interfacial electron transfer to various localized defect states could be associated to different electronic coupling elements and could therefore result in a wide distribution of rate constants. The occupancy of these trap states can be modulated by sweeping the Fermi level below the flatband energy upon applying an external electrical bias. Modulation of the applied potential, does not appear, however, to result in any noticeable change in the injection yield and kinetics.[29] On the other hand, adsorption of potential determining cations, such as Li+, that causes the flatband potential of the semiconductor to shift positively, apparently also affects the electron injection rate.[54] An acceleration factor of 8 fold was observed in particular for cis-[RuII(dcbpy)2(NCS)2]-sensitized nanocrystalline titanium dioxide in pure propylene carbonate upon addition of 0.1 M Li+.[29] These observations suggest that the multiple time constants result from heterogeneities in the energetics of the nanocrystalline TiO2 films. In addition, adsorption of dye molecules on different surface sites and with various anchoring geometries could also cause an intricate kinetic outcome.[55]

 46

Figure 11. Energy scheme for cis-[RuII(dcbpy)2(NCS)2] dye sensitizer adsorbed on various oxide semiconductors. Molecular levels are based on the values of the oxidation potential of the complex: o(S+/S) = +0.86 V/SCE and excitation energy

E0,0 = 1.85 eV.[20] The flatband potentials fb(SC) of the different solid oxides were
estimated by monitoring the optical absorption at 750 nm of transparent nanocrystalline electrodes in propylene carbonate as a function of applied potential.[60]

The fastest kinetic phase of electron injection in cis-[RuII(dcbpy)2(NCS)2]-sensitized nanocrystalline titanium dioxide films apparently takes place in the femtosecond regime. Besides, the vibrational relaxation of the dye excited state is expected to occur typically within 0.41 ps (kr 1012 s1).[56,57] Observed injection rate constants of the order of 1013 s1 certainly preclude complete thermalization of the dye excited state S* to the v = 0 level prior to the reaction, and suggest that charge transfer can occur

 47

directly from hot (v > 0) excited sensitizer molecules. In systems where the v=0 energy level of the electronically excited state of the dye lies below the bottom of the conduction band of the semiconductor (na0), charge injection from vibrationally relaxed excited molecules of the sensitizer is either slow or unfeasible. However, if electron injection from a hot vibronic state of the dye is able to compete successfully with its nuclear relaxation (ki > kr), charge injection should become possible for higher excitation photon energy, and an excitation wavelength dependence of the quantum yield i = ki / ( ki + kr ) would be expected. Figure 11 schematizes the energetics of the cis-[RuII(dcbpy)2(NCS)2] dye sensitizer adsorbed on various oxide semiconductors. This dye was chosen because of its broad spectrum that should allow the excitation of hot vibronic states upon excitation by photons of energy h > E0,0. Picosecond resonance Raman studies have indicated that vibrational relaxation of Ru(bpy)32+ analogous complex dye is complete within ca 6 ps.[58,59] The presence of N=C=S ligands, that are characterized by a high frequency stretching mode ( 2139 cm1),[51] is expected, however, to reduce this relaxation time to 12 ps. In dry propylene carbonate, the flatband energy of amorphous (a-Nb2O5) and crystalline niobia (c-Nb2O5), tantalum pentoxide (Ta2O5) and zirconia (ZrO2) was found to be 0.2, 0.4, 0.7 and 1.1 eV respectively higher than that of TiO2.[60] As a consequence, the v=0 level of the MLCT excited state of the adsorbed dye lies below the bottom edge of the conduction band of these materials. Monitoring of the sensitizers ground state bleaching signal upon nanosecond laser flash photolysis of the Ru(II) complex clearly exhibited a biphasic kinetic behavior. Excited dye molecules that do not inject into the solid produce a recovery of the ground-state absorption within 15 ns. On the other hand, the dye cation S+, generated by the photoinduced electron transfer process, recaptures the injected electron much slower in the microsecond time domain.[51] Both kinetic steps, whose rate constants are two orders of magnitude apart

 48

from each other, can be easily separated. Quantitative evaluation of their respective amplitudes allows then the evaluation of the absolute injection quantum yield i at any excitation wavelength, independently of the absorption spectrum of the dye.[60] Results obtained for various RuII(dcbpy)2(NCS)2-sensitized semiconductors show a strong excitation energy dependence of i. For c-Nb2O5 a clear wavelength dependence of the injection efficiency is observed between = 650 nm, the onset of injection, and

= 500 nm, where the charge transfer quantum yield reaches a plateau value at ~0.75
(Figure 12).

Figure 12. Dependence upon excitation photon energy h of electron injection quantum yield i obtained for various oxide semiconductors sensitized by cis-[RuII(dcbpy)2(NCS)2].

 49

Measurements carried out in identical conditions with dye-sensitized TiO2 gave an injection quantum yield close to unity that was independent of the excitation wavelength. On amorphous niobia, whose flatband potential is intermediate between those of TiO2 and c-Nb2O5, the injection onset is shifted to the red by approximately 0.2 eV compared to the crystalline material. On tantalum pentoxide, the injection onset is found in the blue at = 480 nm. The shift of the electron injection threshold by +0.6 eV for Ta2O5 compared to c-Nb2O5 is larger than the energy difference measured between the positions of the respective conduction band edges of both materials (0.3 eV) and should probably be related to a lower density of trap states in tantalum oxide. Finally, in accordance to the energy scheme, no charge injection was observed for cis-[RuII(dcbpy)2(NCS)2] adsorbed on ZrO2 up to an excitation energy of 2.7 eV. The dependence of the photosensitization efficiency upon the excitation wavelength has also been observed in a photo-electrochemical cell based on TiO2 sensitized by FeII(dcbpy)2(CN)2 complex.[61] The absorption band selective photon-to-current conversion efficiency measured in this case suggested that charge injection into the semiconductor is occurring via an ultra-short-lived, upper excited state of the dye. These observations of an excitation wavelength dependence of the charge injection process show that photoinduced interfacial electron transfer from a molecular excited state to a continuum of acceptor levels can take place in competition with the relaxation from upper excited levels. The rather slow growth of the injection quantum yield above the energy onset suggests it actually reflects the density of acceptor states in the solid that are present below the conduction band edge. In conditions where the injection quantum yield is unity (ki >> kr) and electron transfer takes place to the conduction band of the semiconductor (na 1), the occurrence of the electron transfer process from a single prepared state S*(v > 0) validates the simple model of Equation (30) and allows to estimate the electronic coupling matrix element |H|. Assuming a frequency of the dye cation oscillator 1500 cm1, a value of |H| 113 cm1 ( 1/2 kT) would be

 50 ki = 1013 s1

calculated

from

the

rate

constant

measured

typically

for

[RuII(dcbpy)2(NCS)2]-sensitized nanocrystalline TiO2. Although the value used for the cation vibration wavenumber , and therefore that determined for |H|, are here probably over-estimated, this figure corresponds to a rather strong electronic coupling and suggests the electron injection rate could have reached the adiabatic limit. Modulation of the injection efficiency between excited Ru(II) complexes and nanocrystalline TiO2 and SnO2 transparent films was observed upon biasing the Fermi level of the oxide electrodes.[62,63] Applying a negative bias voltage to the film impaired the photosensitized charge injection, turning on the photoluminescence of the adsorbed dye. Basing on this results it has been suggested the rate of heterogeneous electron transfer depends directly upon the driving force of the reaction,[63] and follows a normal Marcus-type of behavior. Alternatively, such an effect could also be rationalized by the reduction of the density of acceptor states, which are gradually populated upon raising the Fermi level of the solid. The Franck-Condon factor, that comprises parameters such as the reaction free energy G0, the nuclear reorganization energy and the temperature T, is expected to play only a negligible role in systems that are kinetically near optimum in terms of the Marcus theory and that are characterized by a large number of acceptor states. According to Equation (30), the rate of interfacial electron transfer for a given sensitizer is controlled only by the electronic coupling matrix element |H| and the acceptor states density. The activationless nature of the charge transfer process has been experimentally confirmed by the observation of temperature independent injection kinetics.[47] Other reported data show that, in energetically favorable conditions, the rate of electron injection is not controlled by the energetics of the sensitizers excited state, nor by the medium reorganization, but rather by the density and occupancy of electronic states in the solid.[29]

 51

Table 1. Electron injection rate constants ki, reported for various dye sensitizers adsorbed on nanocrystalline TiO2.

Dye-sensitizers RuII(bpy)3 [b] RuII(dcbpy)3 RuII(bpy)2(dcbpy) Eosin-Y [RuII(dcbpy)2(CN)2]3 Fluorescein 27 RuII(dcbpy)3 Coumarin-343 Perylene RuII(dcbpy)2(NCS)2 H2TCPP ZnTCPP FeII(CN)64 [c] Alizarin [c]

Medium H2O, pH10 H2O, pH3 air H2O, pH3 EtOH H2O, pH3 EtOH CH3OH vacuum EtOH PC PC D2O, pH2 EtOH

ki [s1] [a] 2105 3107 2108 9108 6109 31012 [a] 41012 51012 [a] 51012 1013 [a] 1013[a] 1013 [a] >21013 >21013

|H| [cm1] [d] 2102 2101 4101 1 3 6101 7101 8101 8101 102 102 102 >1.6102 >1.6102

References [16] [16] [41] [38,45] [64] [49] [42] [43,50,65] [47] [46] [29] [29] [66] [67]

[a] Only the fastest kinetic component is taken into account when multiexponential kinetics were reported. [b] Linkage of most of the dye molecules onto the surface is ensured by a carboxylic or phosphonic anchoring group. In case such a group is lacking, adsorption occurs through purely electrostatic interactions. [c] Fe(CN)64 and alizarin form charge transfer (CT) surface complexes on TiO2 that are the relevant chromophores in the photosensitization process. [d] Electronic matrix elements |H| coupling dye excited states with the acceptor states of the semiconductor were calculated with Equation (30), assuming for all systems na = 1 and = 1500 cm1.

 52

On titanium dioxide, the photoinduced charge injection process were reported to take place on time scales ranging from less than 100 fs to several microseconds, depending on the sensitizer used (Table 1). Such a variation of eight orders of magnitude can be accounted for only by very different values of the electronic coupling between the dye excited state and the acceptor orbitals at the surface of the semiconductor. Using Equation (30), and assuming for all systems na = 1 and a collective vibrational mode frequency of the dye oxidized state = 1500 cm1, the electronic coupling matrix element can be calculated for each sensitizer. Obtained values of |H| vary from 0.02 cm1 to > 160 cm1. Considering relation (38), and assuming a damping factor

= 1.2 1, this range of figures implies a difference in the electron transfer reaction
distance of the order of 8 between the slowest and the fastest system. Various types of association of the sensitizer with the oxide surface could explain such a difference. Adsorption through electrostatic interaction is clearly insufficient. In aqueous medium, adsorbed water molecules on TiO2 can act as spacers and force the dye sensitizer to stay several angstroms apart from the solid. Moreover, in the case of the symmetric Ru(bpy)32+ complex, the LUMO of the dye is delocalized over all three ligands, thus considerably increasing the average separation distance for interfacial electron transfer. Strong electronic coupling between the * molecular orbital of the dye excited state and the empty TiIV3d orbital manifold of the semiconductor is achieved by directly linking the sensitizers moiety that carries the lowest energy * orbital to the surface. Carboxylic and phosphonic anchoring groups are quite good in coupling dye sensitizers onto the surface of TiO2. Charge injection rate constants obtained with such systems appear to be hardly dependent on the type of chromophore used, as they all establish at ca ki = 1013 s1, which value is probably close to the adiabatic limit.

 53

4.3.3 Recapture of the injected electron

Figure 13 schematizes the energetics and dynamics of processes that take place after charge injection from a molecular excited state to the acceptor levels of a semiconductor. Thermalization and trapping of hot injected carriers is known to occur typically with a rate constant kth 1013 s1.[6870] Reverse transfer of a hot electron (ki) is therefore generally prevented. The kinetics of back-electron transfer from the conduction band to the oxidized dye follow a multiexponential time law, occurring on a microsecond to millisecond time scale. Two reasons are suggested for the relatively slow rate of the recapture of the injected electron : (1) While electron injection is kinetically near optimum, the high exoergicity of the back electron transfer can make the system lie deep in the inverted Marcus region, where the rate of the charge transfer process is expected to decease with increasing driving force. (2) Alternatively, the dynamics of trapping and detrapping of electrons localized in intraband-gap states can control the overall reaction kinetics that would not depend upon the sole interfacial electron transfer rate. Efficient dye sensitizers of oxide semiconductors are generally characterized by an oxidation potential of their excited state o(S+/S*) that is close to the conduction band flatband potential fb of the solid. As a consequence, the free energy Gbo of the back electron transfer can be as negative as 1 to 2 eV, depending on the potential assumed for free and/or trapped electrons involved in the reaction. The total reorganization energy associated with the heterogeneous charge transfer process is typically of the order of 0.5 eV, and is therefore smaller than the reaction driving force < Gbo. In terms of current electron transfer theory, this situation, depicted by Figure 13, corresponds to an inverted kinetic region.

 54

Figure 13. Energetics of the charge recombination following electron injection (ki) from a dye excited state S* into the conduction band of a semiconductor. Thermalization and/or trapping of injected electrons (kth) takes place prior to the interfacial electron back transfer to the dye oxidized state S+. The reaction free energy associated to the latter process depends upon the population of the electronic states in the solid and can be distributed over a broad range of values. Numerical potential data shown in the Figure are those of the cis-[RuII(dcbpy)2(NCS)2] | TiO2 system.

For a non-adiabatic process the ET rate constant is generally expressed by Equation (29). Within the classical limit where the energy of the vibrational modes associated with the activated complex formation is small (h << kT):

FC =

2! " kT exp ( #G / kT )

(40)

 55 and G = (Go + )2 / 4,

(41)

where G is the reaction activation energy. However, this classical expression is not generally adequate to describe the kinetics of electron transfer within the inverted region. Introducing a quantum modification of the Franck-Condon factor by assuming a single collective high frequency vibrational mode (h > kT) yields :
" ($G o + w h# + "o) 2 "i " w 2! "o kT exp ! w1! h#i exp h# w=0 4 "o kT

FC =

(42)

where i and o are the high frequency mode (inner sphere) and low frequency modes (inner- and outer-sphere) terms of the reorganization energy, respectively. The quantum treatment of high frequency vibrational modes has a marked effect in the inverted Marcus region. The large Franck-Condon coupling that characterizes generally the inverted region renders nuclear tunneling a dominant process. The first consequence of this effect is a drastic decrease of the dependence of the electron transfer rate upon its energetics. Nuclear tunneling underneath the nuclear reorganization barrier also means the electron transfer process in these conditions becomes activationless. As a second consequence, it is therefore expected that the temperature dependence of the electron transfer kinetics vanishes. In accord with the experimental findings that the charge recombination process exhibits inverted region kinetic behavior [7173] and the predictions of the semiclassical model above, pseudo-activationless kinetics were indeed observed. The dynamics of the electron back transfer from the conduction band of TiO2 nanoparticles to the cations of various organic sensitizers was shown to be essentially insensitive to temperature.[74] The temperature and medium dependence of the kinetics of the back electron transfer

 56

process taking place from the conduction band of mesoporous TiO2 to the oxidized form of the adsorbed cis-[RuII(dcbpy)2(NCS)2 ] dye sensitizer was also

investigated.[75,76] As expected from the thermodynamics of the process (Go 1.75 eV in ethanol), that should make the reaction lie deep in the inverted region, the effect of the temperature on the reaction rate was very weak. A decrease of the rate constant by less than a factor of 2 was observed when the temperature was varied from 300 K down to 100 K. This and the fact that hardly any medium dependence of the electron transfer rate could be observed suggested that the Franck-Condon barrier to electron transfer is dominated by high frequency modes which make its rate of crossing mainly controlled by nuclear tunneling. The insignificant role played by the Franck-Condon factor implies the electronic coupling dictates to a large extent the kinetics of the charge transfer process. Fitting of experimental temperature dependence data by Equations (29) and (42) yielded values of the electronic coupling matrix element |H| of the order of only a few cm1.[74] This electronic coupling is fairly weak compared to that of the charge injection, where |H| was found for the same sensitizer to be one or two orders of magnitude larger. This difference could be explained by the configuration of the sensitizer molecules in the adsorbed state. In efficient systems, forward electron transfer is favored by directly anchoring the sensitizers moiety that carries the LUMO of the dye to the surface. In molecules that possess a large transient dipole moment, charge recombination requires the electron must be transferred from the semiconductor to the oxidized center over a longer distance. This effect is particularly evident for Ru(II) complexes such as cis-[RuII(dcbpy)2(NCS)2]. Electron injection into TiO2 takes place from the carboxylated bipyridyl ligands that are linked to the oxide surface and carries the lowest * orbital. The distance separating the center of the * system in the sensitizers excited state and the first layer of Ti(IV) ions in the solid is approximately 5.5 . The reverse reaction, however, involves an electron transfer from the semiconductor to the Ru(III)

 57

center of the oxidized state, about 8 apart. According to the Gamov expression [Equation (38)], and assuming = 1.2 1, a difference of 2.5 in the ET distance would imply a variation of the value of the electronic coupling by a factor of 20, in good agreement with experimental data. For systems that do not apparently benefit from this favorable effect, charge recombination was reported to occur in the subnanosecond time scale.[48,49,77] Logically, the value of the electronic coupling in these cases was estimated to be of the same order of magnitude (|H| 50100 cm1) than that of the electron injection process.[49,78] Whether charge transfer occurring through the solid/liquid interface proceeds directly from free electrons in the conduction band or is mediated by surface states is an important clue in the understanding of the mechanism and kinetics of the back electron transfer reaction. In principle, a distribution of energetically different traps for electrons could be responsible for a non-single-exponential recombination rate. Multiexponential kinetics of back electron transfer processes were indeed reported in several recent publications. Durrant and co-workers have presented some new data on this issue, showing the reaction to be strongly dependent on applied potential and electrolyte composition.[79] In agreement with the conclusions reached by Lian and coworkers,[65,80] these observations show that kinetics of charge recombination between electrons injected into nanocrystalline TiO2 films and adsorbed dye cations are strongly dependent upon occupancy and energetics of the electronic states in the solid. They also suggest the back-electron transfer dynamics is controlled by electron transport between energetically distributed trap sites within the oxide nanoparticles.[81] This may be of relevance for the performance of the cell and should be considered in the modeling of the electrical performance together with the reaction between the electrolyte mediator and conduction band electrons.[82]

 58

4.4 Charge separation in molecular photovoltaic devices

Upon irradiation, redox dye photosensitizers adsorbed on the surface of wide bandgap metal oxide semiconductors readily inject an electron in the conduction band of the solid. While charge injection has been found for numerous efficient systems to occur in the femtosecond time frame, the electron back transfer takes place much more slowly, typically in the microsecond-millisecond domain. This charge recombination process can be intercepted by reaction of a reducing mediator M with the oxidized dye [Equation (43)]. The overall efficiency of the light-induced charge separation then depends upon the kinetic competition between back electron transfer and dye regeneration processes.

S+ | e (SC) + M

e (SC) + S | SC + M+

(43)

Photovoltaic cells based on the sensitization of mesoporous titanium dioxide by Ru(II) complex dyes in conjunction with the I3/ I redox couple as a mediator have proved very efficient at exploiting this principle. In such systems, the ionic mediator travels back and forth by diffusion from the working- to the counter-electrode to shuttle to the sensitizer the electrons that have gone through the electrical circuit.[17,20,83] Recently, solid-state devices have been described where the liquid electrolyte present in the pores of the nanocrystalline oxide film is replaced by a large bandgap p-type semiconductor acting as a hole-transport medium.[8487]

 59

4.4.1 Interception of dye cations by a redox mediator

The interception of the oxidized dye by the electron donor in the electrolyte, i.e., iodide, is crucial for obtaining good conversion yields and high cycle lifetime of the sensitizer. For cis-[RuII(dcbpy)2(NCS)2] dye, time-resolved laser experiments have shown the interception to take place within about 10 ns under the conditions applied in the solar cell. The S+/S couple shows reversible behavior in different organic solvents, the standard redox potential in acetonitrile being o = 0.83 V/SCE. The lower limit of 1 s can be derived for the lifetime of the oxidized dye from cyclic voltammetry. This means that interception is 108 times faster than intrinsic degradation of the oxidized sensitizer, explaining the fact that cis-[RuII(dcbpy)2(NCS)2] can sustain 100 million turnovers in continuous solar cell operation without loss of performance. Lack of adequate conditions for rapid regeneration of the dye leads to dye degradation. The I3/I redox couple has been found to be particularly suited fore dye-sensitized photo-electrochemical solar cells based on nanocrystalline TiO2, as it rapidly regenerates the sensitizer [Equation (44)] and ferries charges between the two electrodes. In these devices no other known redox couple works nearly as well. Although in solution I is capable of quenching reductively the excited state of many dyes [Equation (25)], on a semiconductor surface such as SnO2 and TiO2, the iodide quenching is not able to compete kinetically with the ultrafast charge injection.[88]

S+ | TiO2 + 3/2 I

S | TiO2 + 1/2 I3

(44)

The detailed mechanism of the two-electron transfer dye regeneration reaction [Equation (44)] has not been fully elucidated and many factors appear to influence its rate.[22,83] The following one-electron transfer reactions can in principle take place on

 60

the surface of the oxide and account globally for the oxidation of iodide to triiodide :[22,89]

S+ | TiO2 + I S | TiO2 + I I + I I2 S+ | TiO2 + 2 I S | TiO2 + I2 2 I2 I + I3

(45)

(46)

(47)

(48)

Oxidation of iodide to I2 radical is thermodynamically more favorable than the reaction leading to the iodine atom.[90] Thus, reaction (47) is favored over reaction (45), provided that (I, I) or (S+, I) ion pairs are present in significant amount.[22,89] The kinetics of the oxidation of iodide by the oxidized state of

cis-[RuII(dcbpy)2(NCS)2] sensitizer adsorbed on nanocrystalline TiO2 films was measured by transient laser spectroscopy.[91] Figure 14 shows the transient absorption kinetics recorded in propylene carbonate with various electrolytes added. In all cases, the recovery of the ground-state absorption of the dye, after the fast electron injection into the solid, does not follow a simple kinetic law. In the absence of any electrolyte (trace a), the time needed to reach half of the initial absorbance (t1/2) through back electron transfer is 2 s. Total recovery of the initial absorption, however, requires several hundreds of microseconds to milliseconds. Traces b, c, and d were recorded after addition of a common concentration of 0.1 M of iodide in the form of tetrabutylammonium (TBA+), Li+, and Mg2+ salts, respectively. Addition of the

 61

electrolyte in all three cases lead to a considerable acceleration of the dye regeneration with t1/2 < 200 ns and complete suppression of the slow kinetic tail.

Figure 14. Time course of the transient absorbance changes measured upon laser excitation of cis-[RuII(dcbpy)2(NCS)2] dye adsorbed on nanocrystalline TiO2 films. Bleaching signals were measured at = 520 nm in anhydrous propylene carbonate, without electrolyte (a), and in the presence of TBAI 0.1 M (b), LiI 0.1 M (c), and MgI2 0.05 M (d). The insert displays the dependence of the half lifetime t1/2 of the dye ground-state absorbance recovery upon the concentration of Li+ cations. Concentration of iodide [I] = 0.1 M was kept constant while pLi+ log[Li+] was varied.

The rate of the reaction leading to the regeneration of the dye ground-state was found to depend strongly on the nature and concentration of cations present in the solution. Small

 62 cations able to specifically adsorb onto the oxide surface, such as Li+ and Mg2+, were found to favor the fast oxidation of iodide by the sensitizers oxidized state. A sudden acceleration of the electron transfer process was observed at a critical cation concentration (see insert of Figure F4.4/1). Electrophoretic measurements showed that this concentration corresponds to the reversal of the titanium dioxide particle surface charge from negative to positive upon adsorption of -potential-determining species. This observation was interpreted in terms of a change in the reaction mechanism characterized by different rate constants. The slower reaction path, that does not require the iodide anions to be adsorbed onto the surface, was attributed to the thermodynamically unfavorable oxidation of I to iodine atom [Equation (45)]. Alternatively, the encounter of a (S+, I) complex with a second iodide anion could yield I2 radicals directly as a product of the electron transfer process [Equation (49)]. (S+, I) + I S + I2

(49)

These reactions should be prevalent as long as the solid surface is negatively charged. When the surface charge is reversed to positive upon adsorption of the cations, a faster mechanism becomes predominant. Because it requires high local concentration of I on the surface of TiO2, the latter was suggested to be due to the thermodynamically more favorable oxidation of I to I2, that involves prior formation of (I, I) ions pairs on the surface [Equation (50)].

S+ + (I, I) | TiO2

S + I2

(50)

Apart from recapture of the injected electrons by the oxidized dye, there is an additional loss channel in the nanocrystalline dye-sensitized cell which involves reduction of triiodide ions in the electrolyte present within the mesoporous network :

 63

I3 + 2 ecb(TiO2) 3 I

(51)

The back electron transfer reaction between conduction band electrons and I3 [Equation (51)] is the ultimate fate of photoinjected carriers. This reaction can be directly followed by measuring the dark current of the photovoltaic cell. The latter should be kept at a minimal level as it determines the photovoltage and, hence, the overall conversion efficiency of the device.[9294] On mesoporous TiO2 electrodes sensitized by cis-RuII(dcbpy)2(NCS)2, the rate of the back reaction of injected electrons with I3 was measured from intensity modulated experiments and was observed to be second order in the electron density, with k = 8.4103 M1 s1.[94] As for the direct recombination processes discussed above that also imply the reaction of conduction band and trapped electrons with acceptor molecules at the surface, the rate of charge transfer is expected to depend strongly on the distribution and occupancy of intrabandgap states in the semiconductor, and therefore upon the light intensity, the applied potential bias, and the nature and concentration of adsorbates.

4.4.2 Charge carrier percolation through mesoporous solid films

The migration of electrons within the TiO2 conduction band to the current collector involves charge carrier percolation over the mesoscopic particle network. This important process which leads to nearly quantitative collection of injected electrons is presently attracting a great deal of attention.[81,9598] The mesoporous electrode is very different compared to a compact semiconducting layer because (1) the nanocrystalline film possess only a very low inherent conductivity, (2) a space charge layer is unable to establish within minute-size individual particles that are smaller than

 64

the Debyes length, and (3) the oxide particles and the pores filled by the electrolyte form interpenetrating networks whose phase boundaries produce a junction of huge contact area. In an approach to rationalizing the transport phenomena, mesoporous films may be viewed as an ensemble of individual nanoparticles through which electrons can percolate by hopping from one crystallite to the next, rather than regarding them as perforated compact electrodes.[99] A first attempt to model carrier transport in nanocrystalline TiO2 films suggested diffusion to be the operative mechanism.[95] It turned out, however, to be erroneous to describe the electron motion by a single value of the diffusion coefficient. The transport phenomenon is complex as it involves trapping and detrapping of charges. The traps have various depths, leading to a distribution of trapping and detrapping times. Which type of trap the electron experiences during its random walk through the oxide film depends on its quasi-Fermi level under illumination, i.e., on the light intensity.[96] At low light levels, deep traps participate in the electron motion with a correspondingly low diffusion coefficient De and slow motion is expected. Increasing light intensity ends up in the filling of deeper trap states under steady-state conditions. The transport in this case is faster since it involves only shallow traps, resulting in a higher value for De . The central importance of trap states in these systems has recently been discussed by Nelson,[81] who applied a dispersive transport model based on the continuous-time random-walk theory of Scher and Montroll.[100] Another currently debated issue concerns space charge control of the photocurrent. It is generally assumed that the negative charge of the moving electron is efficiently screened by cations in the electrical double layer surrounding the semiconductor nanoparticles, making it move with its image charge as an essentially neutral species. There is evidence, however, that the charge compensation on the electrolyte side of the junction can lag behind the electron movement in the solid network. This effect is particularly important in ion-paired organic electrolytes when high photocurrents are

 65

drawn. Therefore, it was observed in photocurrent transient measurements that the photocurrent response times became longer with decreasing electrolyte

concentration.[101] As well, the calculated value of the effective diffusion coefficient of carriers in the oxide semiconductor De = 1.5105 cm2 s1 is several orders of magnitude smaller than that in the bulk crystalline material and strikingly similar to the diffusion coefficient of ions in the solution. A description of the coupled electron-ion motion [82] and a quantitative model of the mass transport by the electrolyte in mesoporous systems [102] have been proposed, albeit employing a constant value for the electron diffusion coefficient. Simple calculation shows that the steady-state carrier concentration in full sunlight corresponds to approximately one electron per TiO2 particle.[103] However, using this value together with De = 1.5105 cm2 s1 ends up in a resistance for the illuminated nanocrystalline film which is at least a thousand times higher than the experimentally measured value. This discrepancy may be explained by a Mott transition occurring during the photodoping of the anatase particles that results in a large increase of their conductivity.[104] Clearly, a central question remains, which is how, in the dyesensitized liquid-junction solar cell, an initially very poorly conducting network of TiO2 nanoparticles can attain the excellent photocurrent-voltage characteristics presented below in section 4.6.

4.4.3 Charge separation across a solid-state heterojunction

In dye-sensitized photovoltaic cells, practical advantages may be gained by the replacement of the liquid electrolyte with a solid charge-transport medium. Inorganic p-type semiconductors such as CuI [85] and CuSCN,[87] and organic hole conductors [84,105,106] have been proposed in this regard. Recently, the use of

 66

2,2,7,7-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9-spirobifluorene

(spiro-

MeOTAD) to constitute an amorphous hole transmitting material, in conjunction with a mesoporous TiO2 film sensitized by cis-[RuII(dcbpy)2(NCS)2], allowed to build a solid-state dye-sensitized solar cell with high photon-to-electron conversion efficiencies.[84]

Figure 15. Energetic scheme of electron transfer processes taking place in a dye-sensitized heterojunction photovoltaic cell. Also shown is the structure of the spiroMeOTAD molecule that constitutes an efficient organic hole transport material (HTM).

 67

Figure 15 shows an energetic scheme for the electron transfer processes taking place at the dye-sensitized heterojunction of such a device. Electron injection from the sensitizers excited state into the conduction band of TiO2 is followed by regeneration of the dye by hole injection into the hole transport material (HTM). Conduction band electrons in the metal oxide, as well as holes in the organic medium are then transported by electronic conduction to the anode and the cathode, respectively. Pulsed picosecond laser photolysis has shown that the hole injection from the oxidized dye-sensitizer [RuIII(dcbpy)2(NCS)2]+ into the spiro-MeOTAD hole conductor proceeds over a broad time ranging from < 3 ps to > 1 ns.[107] This wide time-scale was attributed to a statistical distribution of the dye-hole conductor distances, and suggested that the dye was not perfectly and uniformly contacted by spiro-MeOTAD molecules.

4.5 Charge separation in nanocrystalline heterotriads

Charge separation resulting from light absorption by molecular chromophores has been extensively studied along two parallel routes: On the one hand, numerous molecular assemblies of donors (D), chromophores (S) and acceptors (A) in many variations have been synthesized, forming dyads, triads, tetrads or even pentads, to achieve charge separation in solution or in monolayers. On the other hand, charge separation at chromophore-semiconductor interfaces (heterodyad SA) exploited on films of nanocrystalline metal oxides has allowed the development of dye-sensitized nanocrystalline solar cells. Combining the intramolecular with the interfacial lightinduced charge separation strategies is expected to increase the light-to-electricity conversion yield of the photovoltaic systems. The maximum voltage delivered by the dye-sensitized solar cell corresponds to the difference between the potential corresponding to the quasi Fermi energy level of the

 68

electrons in the semiconductor F = E*F,n / F and the redox potential (M+/M) of the mediator in solution. A higher cell voltage can hence be obtained by lowering the quasi Fermi potential which depends on the electron concentration in the conduction band of the illuminated sensitized semiconductor. This concentration relaxes to a steady state where the electron injection Iinj flux equals the electron escape flux (Figure 16). The escape flux is composed of two contributions: the electron-sensitizer recombination flux Ib [Equation (52)] and the electron leak to the mediator in the contacting electrolyte IM [Equation (53)].

S+ | (ecb)TiO2 S | TiO2

(52)

M+ + ecb M

(53)

DS* | TiO2 DS+|(ecb)TiO2 D+S|(ecb)TiO2

(54)

D+S|(ecb)TiO2 DS|TiO2

(55)

Lowering the quasi Fermi potential by reducing the former flux requires a lengthening of the lifetime of the charge-separated state S+ | (ecb)TiO2, a goal which can be reached by removing the hole on S+ away from the semiconductor surface. This was achieved by replacing the simple chromophoric sensitizer S by a dyad sensitizer SD in which D is an electron donor possessing a redox potential lower than that of the sensitizer but higher than that of the redox mediator. Consequently, after electron injection, the hole will be transferred from S+ to D [reaction (54)]. The recombination after Equation (55) is expected to be slower than the direct recombination [Equation (52)], because of the exponential decay of the electron transfer rate ket(r) with the distance r, according to

 69

Gamovs expression (39) The whole system DS|TiO2 constituted by the dyad adsorbed on the semiconductor, considered as an acceptor, will be referred to as heterotriad. The quantitative influence the different rates of electron transfers on the photopotential

F of the illuminated electrode was established according to the following model. In a

heterodyad S|TiO2 in open circuit (Figure 16, top), the electrons injected into the TiO2 conduction band at the flux Iinj can either recombine with the oxidized sensitizer with the pseudo first-order rate constant kb or reduce the oxidized redox mediator M+ in solution with the second-order rate constant kM. The steady-state electron density n in the semiconductor is thus given by Equation (56). The quasi Fermi level E*F,n of the semiconductor is varying with the electron density according to Equation (57), where EC is the conduction band level and Nc is the effective density of states in the conduction band, a constant value for a given material at a given temperature.[108] The corresponding photopotential F of the electrode is obtained by division by the Faraday constant F [Equation (58)]. Combining Equations (57) and (58) affords the photopotential as a function of the kinetic parameters [Equation (59)]. In a heterotriad DS|TiO2 (Figure 16, bottom), the quenching of the oxidized dye by the linked donor is by far the fastest process (kq >> k'b see examples below). Ib is therefore negligible and the relevant fluxes for the determination of 'F are IM which is independent of the sensitizer, I'inj and the recombination flux I'b with the oxidized donor. The open-circuit photopotential difference F between the two systems is then expressed by Equation (60), that can be further simplified if I'inj = Iinj, which can be considered true if the chromophore is the same in the heterodyad and in the heterotriad.

n = Iinj / (kb + kM [M+])

(56)

E*F,n = Ec kT ln (Nc /n)

(57)

 70

F = c (kT/F ) ln (Nc /n) F = c (kT/F ) ln (Nc (kb + kM [M+]) /Iinj )

(58)

(59)

F = (kT/F ) ln (kb I'inj / k'b Iinj)

(60)

Figure 16. Electron fluxes for charge separation and recombination processes in a heterodyad (top) and heterotriad (bottom), in the presence of a redox mediator in solution, under open-circuit conditions. In the heterodyad, the injected electrons can either recombine with the oxidized sensitizer S+ (Ib) or reduce the oxidized mediator M+ (I ). S+ is reduced either by the conduction band electrons or by the redox
M

mediator M (Ii). In the heterotriad, the electron transfer from the linked donor D to S+ is much faster than the recombination. The new recombination process occurs at k'b < kb due to the larger distance.

 71

An improved solar cell voltage can also be achieved by raising the redox potential of the mediator. The substitution of the heterotriad to the heterodyad is for that case an advantage too. In fact, the higher redox potential of the (M+/M) couple results in a reduced driving force for the regeneration of the dye (S+ + M S + M+) which will be accompanied, in the normal Marcus region, by a reduced rate. If this rate decreases, the competitive recombination flux increases, unless, again, the lifetime of the chargeseparated state is prolonged by fast transfer of the hole to a linked donor. Argazzi et al. followed that strategy to elaborate a nanocrystalline solar cell which incorporates a molecular dyad based on ruthenium bipyridine as a sensitizer and phenothiazine as a donor (Scheme 3).[109]

Scheme 3

In compound H0, the respective redox potentials of the S (RuIII/II) and D (PTZ+/0) moieties are 1.33 and 0.97 V/NHE, giving a 0.36 V driving force for the charge transfer. In the model compound where the donor is absent, charge recombination was determined by transient laser spectroscopy to follow a biexponential process, with the kinetic components kb1 = 8.5106 s1 (77%) and kb2 = 5.1105 s1 (23%).

 72

H2|TiO2
TiO2
O O P O N N N Ru N N N

18.1 10.1
N

OCH3

OCH3

E / VNHE -0.6 0.0 TiO2

fast

S*/S+ -0.55 V

30 s

(3 s )

h! S/S+ 1.5 V
ns <5

1.0

D / D+ 0.95 V

H3|TiO2
TiO2
O O P O N N N Ru N N N

24.4 16.4
O N

OCH3

OCH3

-0.6 0.0 TiO2

fast

S*/S+ -0.55 V

300 s

h!
+

1.0 S/S 1.5 V

ns 10

D / D+ 0.85 V

H5+A1|TiO2
O

12.2
O P O O O P O O N N N Ru N N N N

OCH3

TiO2

A1
OCH3

H5

-0.6 0.0 TiO2

fast

S*/S+ -0.55 V

h!

3 s

1.0

S/S+ 1.36 V

ns <5

D / D+ 0.80 V

N N N Ru N N N C S

PO3

H4

 73

Figure 17. Distances, energy levels and electron transfer half-lives in the heterotriads H2|TiO2, H3|TiO2 and H5+A1|TiO2. The distances were calculated by molecular mechanics using CAChe software, assuming a perpendicular arrangement of the molecules on the surface. The energy levels are those obtained and calculated by electrochemistry as well as absorption and emission spectroscopy. The half-lifetime reported for the electron transfer processes were obtained by laser flash photolysis. The value of 3 s for the S+ | (ecb)TiO2 S|TiO2 recombination was obtained with the heterodyad H5|TiO2.

In heterotriad H0|TiO2, electron transfer from the phenotiazine moiety to the oxidized sensitizer took place within the laser pulse (< 30 ns) while the charge recombination occurred at the rate k'b = 3.6103 s1, which means a decrease by a factor of 2000 compared to the heterodyad, and a half-lifetime of the charge-separated state of 300 s. According to Equation (60), the photopotential of the heterotriad should be 200 mV higher than for the heterodyad. A difference of 175 mV was measured in the absence of redox mediator. The former system still afforded a 100 mV higher open-circuit voltage than the latter in a cell where the I3/I couple was present. Bonhte et al. investigated three systems based on ruthenium-terpyridine-phosphonate as sensitizer and triarylamines as donors.[110] The excited form of the considered sensitizer was reported to efficiently inject electrons into TiO2 [111,112] while triarylamines are known to form very stable cation radicals.[113] In the two heterotriads H1|TiO2 and H2|TiO2 (Figure 17), the donor and the sensitizer are covalently linked at different distances while the co-adsorbed phosphonated triarylamine A1 and rutheniumterpyridine sensitizer H3, or H4 constitute bimolecular heterotriads. The redox potentials of the different constituents of the heterotriads are given in Figure 17. The

 74 driving forces for the D S+ charge transfer were 0.55 V for H1, 0.65 V for H2, and 0.56 V for A1 + H4. Resonance Raman spectroscopy indicated that in the excited assemblies H2* | TiO2 and (A1 + S*) | TiO2, one electron is promoted from the metal center to the terpyridine ligand linked to the semiconductor, whereas in the system H1* | TiO2 the excited electron is located on the ligand linked to the donor. The quantum yield of the charge separation reaction (54) was found to be close to unity for the two former assemblies, but only 60 % for the latter one. In all three cases, the electron injection was very fast (< 1ns) and the hole transfer to the donor was fast (1020 ns). The half-lifetime of the charge separated state was 3 s for (A1+ + H4) | (ecb)TiO2, as in the model system H4+ | (ecb)TiO2; it was 30 s in H1+ | (ecb)TiO2 and 300 s in H2+ | (ecb)TiO2, as with H0+ |(ecb)TiO2. The differences in the recombination rates of the different heterotriads can be correlated with the mean distance separating the amine from the surface of the oxide. Perpendicular attachment of the molecules on the surface would imply D TiO2 distances of 12, 18 and 24 for the heterotriads (A1+ + H4) | TiO2, H1 | TiO2, and H2 | TiO2, respectively (Figure 17). Assuming a typical damping factor = 1.2 1 for through-space electronic coupling between conduction band electrons and D+, a decrease of the recombination rate by one order of magnitude is expected to correspond to an increase of the mean electron transfer distance by 1.9 . The discrepancy between that value and the 6 distance difference expected from perpendicular anchoring can be explained by the fact that, very likely, a large portion of adsorbed molecules adopt a tilted conformation on the surface, leading to a broad distribution of distances for the charge recombination, and hence to a complex kinetic behavior. In fact, attempts to fit the observed temporal curves demonstrated that they are multiphasic, certainly because the adsorption geometry of the molecules is not fixed. This geometry is likely to be dependent on the surface coverage. In a compact monolayer, perpendicular anchoring

 75

should be favored, whereas molecules widely dispersed on the surface should be freer to lean over. It was indeed observed for all three heterotriads that the rate of the recombination depends drastically on the surface concentration. At 50 % surface coverage, upon irradiation by a laser pulse of fixed energy, a 50 % reduction of the number of charge separated pairs is expected. Considering a second-order kinetic law, the rate of recombination is expected to decrease accordingly. It was observed on the contrary that the slowest kinetic components measured for H2 | TiO2 at surface saturation disappeared under partial coverage conditions, while the half-lifetime of the charge separated state 1/2 was reduced by more than one order of magnitude. An effect of the same amplitude was observed with heterotriads H1 | TiO2 and (A1 + H4) | TiO2. Heterotriad H2 | TiO2 represents obviously the most promising system of the series for long-lived charge separation. In an attempt to further increase the lifetime of H2+ | (e
cb)TiO2

state, the photodynamics was studied in the ambient temperature liquid salt 1-

ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide [114] which was shown to behave at the molecular scale like a solvent of low dielectric constant ( 10), where the medium reorganization energy should be minimized. The charge recombination was indeed slowed down significantly, with a twice as long 1/2 as in propylene carbonate. A very long tail in the kinetic curve, accounting for a few percents of the initial absorbance, was even found to extend up to several hundreds of milliseconds (1/4 = 5 ms, 1/8 = 120 ms). Careful degassing the molten salt did not affect this long time kinetic phase, indicating that removal of the conduction band electrons by molecular oxygen was not competing with the charge recombination. Under full sun illumination (AM1.5) in propylene carbonate, heterotriad H1 | TiO2 gave a 82 mV higher photopotential than H4 | TiO2 of which only 58 mV can be accounted for by the 10 fold reduced recombination rate. Another contribution of 10 mV is expected from the 50 % higher injection flux Iinj of the former system, due to the wider absorption spectrum. In spite of a 100 fold lower recombination rate

 76

compared with H4 | TiO2, expected to yield a 116 mV gain, the heterotriad H2 | TiO2 gave the lowest photopotential of the series. This observation must be related to a supplementary contribution to Ib represented by the short-circuiting pathway constituted by the lateral charge percolation from triarylamine to triarylamine and finally to the SnO2, as shown by the electrochromism of H2 | TiO2. This was confirmed by the observation that the quantum yield of the whole charge separation process increased when H2 was diluted on the surface by non-electroactive molecules. In a regenerative solar cell, with the I3/I redox couple, the open circuit photovoltage of H1 | TiO2 was now 139 mV higher than that of H4 | TiO2. This increased difference can be attributed to a reduced electron-triiodide reaction rate (kM), shown by the measurement of IM in the dark, under 550 mV reverse bias, probably as a result of a restricted access of the triiodide ions to the semiconductor caused by the presence of the bulky triarylamine groups. Heterotriad H2 | TiO2, which photopotential was 31 mV lower than H4 | TiO2 affords in the regenerative cell a 59 mV higher photovoltage, very likely because, in addition to a lower IM , the reduction of H2+ | TiO2 by iodide competes with the lateral electron transfer. Despite of the limitations caused by lateral charge percolation, the development of heterotriads as efficient charge-separation systems appears promising.

4.6 Photovoltaic performances of dye-sensitized nanocrystalline solar cells

A scheme of the photovoltaic device used in the generation of electric power from light is shown in Figure 4. The mesoporous semiconductor oxide film is sandwiched between two conducting glass plates, its pore space being filled with a redox electrolyte or a hole conductor. We have shown above how the molecular properties of the sensitizer are chemically engineered to ascertain efficient electron injection from the dye excited state

 77

(S*) into the conduction band of titanium dioxide. We also discussed how the recapture of the electrons by the oxidized dye (S+) is intercepted by transferring the positive charge to a redox mediator M+/M, i.e. the triiodide/iodide couple, present in the electrolyte and hence to the counter-electrode. Via this last charge transfer, in which the mediator is returned to its reduced state, the circuit is closed. The system converts light into electricity in a catalytic fashion, i.e. without permanent chemical transformation.

Figure 18. Typical spectral response curve of the incident photon-to-current conversion efficiency (IPCE) for a mesoporous TiO2 electrode sensitized by N3 and the black dye. A normalized solar irradiance spectrum under AM1.5 conditions is superimposed for direct comparison.

 78

The maximum voltage V that such a device could deliver corresponds to the difference between the Fermi potentials in both conducting electrodes, and thus to the difference between the redox potential of the M+/M mediator couple and the conduction band edge potential of the semiconductor. Figure 18 compares the spectral dependence of the conversion efficiency of incident monochromatic light in electric current (IPCE) for cis-[RuII(dcbpy)2(NCS)2] ( N3) and RuII(tctpy)(NCS)3 ( black dye) sensitizers. Very high efficiencies of current generation approaching 0.8 were obtained. When corrected for the inevitable reflection and absorption losses in the conducting glass serving to support the nanocrystalline film the yields are practically quantitative in the plateau region of the curves. However, the response of the black dye extends 100 nm further into the infrared than that of N3. The photocurrent onset is close to 920 nm, i.e., near the optimal threshold for single junction converters. The overall conversion efficiency of the photovoltaic cell can easily be calculated from the integral photocurrent density measured at short-circuit isc, the open-circuit photovoltage Voc, the fill-factor of the cell f, and the intensity of the incident light IR :

= isc Voc f / IR

(61)

Figure 19 gives an example for the current-voltage characteristics of a nanocrystalline injection solar cell based on the cis-[RuII(dcbpy)2(NCS)2] dye. The overall solar to electric conversion efficiency under standard AM1.5 sunlight conditions, i.e. 1000 W m2 incident intensity, is = 0.10, which is commensurate with the performance of silicon-based conventional photovoltaic devices. Nanocrystalline injection solar cells based on the RuII(tctpy)(NCS)3 sensitizer displayed similar results with confirmed overall energy conversion efficiency as high as 10.4 %. Comparison of the latter value with the maximum thermodynamic conversion efficiency o = 0.27, earlier discussed in section 2, shows that theoretically avoidable losses amount to ca

 79

63 % of the available free energy. As inferred from the very high current yields obtained in such molecular photovoltaic devices, losses are essentially due to the waste of potential in electron transfer processes and to the dark current of the cell. The driving force of the charge injection process is minimal in the case of N3-sensitized TiO2 in dry nitrile solvents. While partial degradation of the injected electron energy through trapping in the solid network cannot be neglected, it is apparent that the potential mismatch between the redox couples of the sensitizer S+/S and the complex mediator I3/I is responsible for a major part of losses.

Figure

19.

Photocurrent-voltage

characteristic

of

nanocrystalline

photoelectrochemical cell sensitized with cis-[RuII(dcbpy)2(NCS)2]. i(sc) is the maximum (short circuit) current density, and V(oc) the maximum (open circuit) voltage delivered by the cell. The conversion efficiency is calculated by use of Equation (61).

 80

5. Water Cleavage by Visible Light

As pointed out by Allen Bard and Marye Anne Fox in a recent review,[115] the photo driven conversion of liquid water to gaseous hydrogen and oxygen:

H2O H2 + 1/2 O2

Go = 237.7 kJ/mole

(62)

is the Holy Grail of all photo-catalytic reactions. Is has been a long standing challenge of practical artificial photosynthetic systems. The hydrogen produced from sunlight and water can be subsequently employed in the catalytic reduction of carbon dioxide to produce fuels such as methane or methanol. The latter could also be used as feed stock for the production of organic chemicals. Alternatively, hydrogen could serve directly as a fuel for transportation purposes or for the production of electricity in fuel cells, without producing pollutants and green house gases upon combustion. For a practical system, a conversion efficiency of at least 10 % is required, implying that the hydrogen and oxygen produced have a fuel value of at least 10 % of the solar energy incident on the system. As the peak solar power incident on earth is about 1 kW m2 a panel of one square meter collector surface should produce hydrogen at a rate of about 36 liter (at standard temperature and pressure) per hour when exposed to direct sunlight. As water is transparent to sunlight, a sensitizer or semiconductor is required in order to absorb the solar photons and transform their radiant energy to generate the chemical potential required to split the H2O molecules. The optimal absorption threshold for a single photoconverter has been calculated to be at an energy of 1.6 eV,[116] implying that all solar photons below 770 nm should be absorbed. Such a system could split water with an efficiency of up to 30 %. Higher efficiencies of up to 42 % can be obtained by using a tandem device where two photosystems operate in series.

 81

The brute force approach to achieve this goal is to employ a solid state photovoltaic cell to generate electricity that is subsequently passed into a commercial-type water electrolyzer. Although efficiencies obtained are relatively high, i.e. close to 8 %, these devices are very expensive. Hence the price of hydrogen produced this way can not compete with conventional sources. The long-term outlook is better for systems that borrow their principles from natural photosynthesis (see section 4.1 above).

5.1 Analogues of photosystem II of green plants

Researchers have long attempted to prepare catalysts capable of oxidizing water to oxygen [Equation (17)], as the reaction constitutes the most difficult part in a complete water cleavage system. However, despite considerable efforts there are few man-made catalysts of any kind available and none have made an impact on industrial chemistry.[117,118] The difficulty of promoting this seemingly simple reaction has both thermodynamic and mechanistic origins. The catalyst must break the strong OH bonds on two water molecules (enthalpy 500 kJoules mole1) in a concerted fashion. This has to be coupled to the removal of 4 protons and 4 electrons. The chemical intermediates formed during the process are so reactive that self-destruction of the catalyst often occurs. Nature solved this problem through evolution of a unique metalloenzyme required for oxygenic photosynthesis in all plants and cyanobacteria. This enzyme is called the Photosystem II water oxidizing complex, or WOC. Its active site is comprised of an oxo-bridged tetra-manganese cluster one Ca2+ ion and one or more Cl ion. In association with tyrosyl this core catalyzes reaction (4.4.2) using a chlorophyll cation radical as terminal electron acceptor. The most intensively studied molecular systems mimicking the action of the WOC are based on the -oxo bridged ruthenium dimer [cis-(bpy)2Ru(OH2)]2O4+ where each

 82

ruthenium is associated with two bipyridyl ligands and one water molecule. The catalytic water oxidation cycle involves abstraction of 2 electrons from each of the Ru(II) centers forming two dioxo-ruthenium(IV) moieties which convert back to the starting state under oxygen release and subsequent re-aquation of the ruthenium metal centers.[119]

5.2 Colloidal semiconductor systems

Photocatalytic water cleavage systems based on aqueous dispersions of semiconductor particles has been extensively studied in the eighties and this work has been reviewed.[120] They have the advantage of being cheap but their efficiency is generally below 1 %. The additional drawback is that hydrogen and oxygen are generated simultaneously. Apart from the problem of gas separation, this produces a slow down of the photoreaction as the two gases accumulate and back react with each other. A way to avoid the latter problem is to seperate the hydrogen and oxygen generating half reactions as reported recently by Arakawa and co-workers.[121] However the efficiency of the process remains low.

5.3 Tandem systems for water cleavage by visible light

The most promising approach to reach the goal of water cleavage by visible light is by way of a tandem system. The main reason for this is that the constraints imposed by thermodynamics are relaxed when 8 photons of light are used instead of four to accomplish the production of two molecules of hydrogen and one molecule of oxygen from water. A tandem system is particularly favorable when complementary parts of the

 83

solar spectrum are exploited by the two photosystems that operate in series. The maximum thermodynamic efficiency of such device is 42 %. Khaselev and Turner [122] reported on a direct water electrolysis system based on a novel, integrated, monolithic photoelectrochemical cell. This was patterned after the GaInP2 / GaAs p/n, p/n tandem cell device grown at the National Renewable Energy Laboratory in Golden Colorado. The solid-state tandem cell consists of a GaAs bottom cell connected to a GaInP2 top cell through a tunnel diode interconnect. The top p/n GaInP2 junction, with a band gap of 1.83 eV, is designed to absorb the visible portion of the solar spectrum; and the bottom p/n GaAs junction, with a band gap of 1.42 eV, absorbs the near-infrared portion of the spectrum transmitted through the top junction. The conversion efficiency achieved was 12 %. A tandem device that achieves the direct cleavage of water into hydrogen and oxygen by visible light was developed in collaboration with two partner groups from the Universities of Geneva and Bern.[123] This is based on the in-series connection of two photosystems. A thin transparent film of nanocrystalline tungsten trioxide or ferric oxide absorbs the blue part of the solar spectrum.

WO3 + h WO3 (e, h+)

(63)

The valence band holes (h+) created by band gap excitation of the WO3 or Fe2O3 serve to oxidize water to oxygen:

4 h+ + H2O O2 + 4 H+ ,

(64)

while the conduction band electrons are fed into the second photosystem. The latter consists of the dye sensitized nanocrystalline TiO2 film. It is placed directly behind the WO3 film capturing the green and red part of the solar spectrum that is transmitted

 84

through the top electrode. The photovoltage generated by the second photosystem enables the generation of hydrogen by the conduction band electrons.

4 H+ + 4 e 2 H2

(65)

The overall reaction corresponds to the splitting of water by visible light.

Figure 20. The Z-scheme of biphotonic water photolysis.

There is close analogy to the Z-scheme operative in the light reaction of photosynthesis in green plants (Figure 2). This is illustrated by the electron flow diagram shown in Figure 20. In green plants, there are also two photosystems connected in series, one affording water oxidation to oxygen and the other generating the NADPH used in carbon dioxide fixation. As discussed above, the advantage of the tandem approach is

 85

that higher efficiencies than with single junction cells can be reached if the two photosystems absorb complimentary parts of the solar spectrum. At present, the overall AM1.5 solar light to chemical conversion efficiency achieved with this device stands at 4.5 %. Figure 21 shows a photograph of a such a cell producing hydrogen and oxygen bubbles vigorously under visible light illumination. Present endeavors aim at further improving the efficiency of the device.

Figure 21. Photograph showing the decomposition of water by visible light in a tandem cell consisting of a mesoporous WO3 film and a mesoporous dye sensitzed TiO2 which are superimposed.

 86

6. Future Outlook and Concluding Remarks

Intensive research is presently carried out around the world focusing on the following issues: i) the molecular design and synthesis of new sensitizers having enhanced near- infrared light response, examples being phthalocyanines or the black dye discussed above. ii) a better understanding of the interface, including experimental and theoretical work on dye adsorption processes. iii) the analysis of the dynamics of interfacial electron transfer processes down to the femtosecond time domain. iv) the unraveling of the factors that control electron transport in nanocrystalline oxide semiconductor films. v) the replacement of the liquid electrolyte by solid materials that serve as a hole conductor. A great advantage of dye sensitized cells is that they can be used to produce directly high-energy chemicals from sunlight. Such photosynthetic devices solve the principle problem of conventional photovoltaic cells that is the lack of capacity for energy storage. The Holy Grail of all photoconversion processes is the splitting of water into hydrogen and oxygen by sunlight and the improvement of the tandem devices described above will be one of the primary targets of future research. Rapid progress is expected in these areas as an impressive number of competent teams around the world are actively pursuing this research. These systems will undoubtedly promote the acceptance of renewable energy technologies, not least by setting new standards of convenience and economy.

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Acknowledgements
Recognition is due to the members of the electrochemical photovoltaics development team of the Swiss Federal Institute of Technology (EPFL), some of whose work is referenced below; to those industrial organizations whose interest in the molecular photovoltaic system has induced them to license the concept and thereby support our research; to EPFL; and to OFEN (Swiss Federal Office of Energy) for past encouragement and support. Thanks are also due to Dr Pierre Bonhte for valuable help in the writing of section 4.5.

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