Abstract

A unique nanostructured rod-like morphology of hematite has been investigated for direct splitting of water on the semiconductor/electrolyte interface. Photoelectrochemical properties of the naturally doped hematite has been studied by steady-state measurements on electrodes with controlled morphology and film thickness. The photocurrent response was in the A/cm2 scale but the incident photon-to-current conversion efficiency (IPCE) were significantly better than earlier reported. The highest photon-to-current conversion obtained was 7.5 % IPCE when illuminating through the substrate with a wavelength of 350 nm and water as a hole scavenger. From the spectroscopic and photon-to-current behaviour was the size of the bandgap estimated. The effect of film thickness and light intensity was also investigated as well as the effect of the cation mobility in the electrolyte. On the basis of present studies we concluded that charge carrier recombinations is a dominating problem even in the nanostructured rod-like hematite. However, the high IPCE values obtained indicates that purposed designed rod-like Fe2O3 is one way to strikingly lower the recombination rate.

Contents
Notation......................................................................................................................................... 4 1. Introduction.............................................................................................................................. 6 2. Theory Behind the Photoelectrochemical Cell...................................................................... 9 2.1. The Semiconductor................................................................................................. 9 2.1.1. The Bandgap................................................................................... 9 2.1.2. The Fermi Level............................................................................11 2.1.3. Doping...........................................................................................11 2.2. The Electrolyte......................................................................................................13 2.2.1. The Relation Between Energy and the Electrode Potential..........13 2.2.2. The Redox Potential......................................................................15 2.3. The Semiconductor in Contact With an Electrolyte..............................................17 2.3.1. Equilibrium....................................................................................17 2.3.2. The Flat Band Potential.................................................................18 2.3.3. Photoeffect.....................................................................................20 2.3.2.1. Ideal Single-Crystal.............................................20 2.3.2.2. Nanostructured Electrode....................................20 2.3.4. The Regenerative Cell...................................................................21 2.3.5. Charge Transfer Processes............................................................22 2.3.6. Water Splitting..............................................................................24

2.4.

Hematite, -Fe2O3................................................................................................27 The Nanostructured Semiconductor......................................................................28 2.5.1. The Nanosized Rod-like Hematite Structure.............................................29

2.5.

3. Experimental Section..............................................................................................................31 3.1. 3.2. 3.3. 3.4. Electrode Preparation............................................................................................31 Three electrode measurements..............................................................................31 Two electrode measurements................................................................................32 Characterisation.....................................................................................................33 3.4.1. Spectroscopic Measurements....................................................................33 3.4.2. Film Thickness Measurements..................................................................33 3.4.3. SEM Measurements..................................................................................33

4. Results and Discussion............................................................................................................34 4.1. 4.2. 4.3. 4.4. 4.5. 4.6. Three Electrode Measurements with 0.1 M NaOH as Electrolyte.......................34 Two Electrode Measurement with 10% TMA-OH...............................................35 Action Spectra and Calculation of the Bandgap...................................................36 The Influence of Film Thickness...........................................................................38 The Effect of Light Intensity.................................................................................40 The Effect of the Effective Radius of the Cation and Estimation of the Mobility of TMA+.................................................................................................41 4.7. Attempts with Catalysts for Oxygen Evolution....................................................44

5. Concluding Remarks and Future Outlooks..........................................................................45 Acknowledgements......................................................................................................................46 References....................................................................................................................................47

Notation
a C CB d eE Ec EF Eg Ev F ff h+ h activity capacitance Conduction Band thickness of the semiconductor electron energy energy of the conduction band edge Fermi energy band gap of the semiconductor energy of the valence band edge Faradays constant fillfactor Gibbs free energy hole Planck constant

IPCE I Lp k n NHE ND P PEC q r R SCE SE SEI SEM T u VB Vb Vfb v w y z

incident photon-to-current conversion efficiency current density diffusion length of the minority carrier Boltzmann constant moles the normal hydrogen electrode the dopant density population of orbitals photoelectrochemical elementar charge effective radius gas constant saturated calomel electrode substrate/electrode illumination semiconductor/electrolyte interface scanning electrode microscopy temperature the mobility standard reduction potential valence band band bending flatband potential the speed of the particle the width of the depletion layer the viscosity of the solution the number of electrons wavelength incident light intensity quantum efficiency monochromatic absorption coefficient electrostatic potential dielectric constant the permittivity of free space chemical potential for substance i electrochemical potential for substance i frequency of light

1. Introduction
As the non renewable energy resources are decreasing, the search for new renewable energy resources are increasing. One possible promising substitute is solar energy, and especially solar energy for splitting of water into hydrogen and oxygen. Hydrogen is rich in energy, easy to store, environmental friendly when produced from solar energy and new improvements in the fuel cell field have made hydrogen a very interesting and wanted commodity today. Hydrogen is also valuable as a chemical feedstock. The Ammonia synthesis and petroleum refining demands big quantities. Most hydrogen is nowadays produced by steam reforming of non renewable natural gas, another common process is by the high energy demanded electrolysis of water. Neither of these processes are optimal considering the energy and environmental costs and to meet tomorrows demand of priceworthy, environmental friendly and renewable hydrogen the industries must find

new ways of producing it. One solution, with a high potential, is extracting hydrogen from the direct splitting of water in a photoelectrochemical cell. Since the first report about direct splitting of water over a semiconductor-electrolyte interface1 several attempts have been made to improve the technique. The aim, direct splitting of water by photoelectrolysis, is not only of pure scientific interest, benefits like cost and energy savings over coupled photovoltaic-electrolysis system could also be achieved. However, the lack of a non corrosive, efficient light absorbing system in combination with suitable semiconductorredox energetics has kept photoelectrochemistry from reaching this goal. One obstacle to overcome is to find a direct water splitting semiconductor with a band gap optimised for the spectral distribution of the solar irradiation, i. e for reasonable efficiency the band gap should not be much bigger than 2.0 eV. However, semiconductors with band gaps in the proper range usually walk hand in hand with low resistivity against corrosion, like; silicon, gallium arsenid and sulfide based semiconductors etc. Another major road block in splitting water by photoelectrolysis is the energetics, since the band edge energies of the semiconductor must match the hydrogen and oxygen evolution reactions. These factors limit the choice of possible semiconductor candidates for water splitting. The most stable semiconductors are corrosion products like oxides which will not corrode further but their band gaps are either too large to efficiently convert solar energy or they have poor semiconductor behaviour. Grtzel and co-workers2 showed that dye-sensitization and nanosized surface morphologies are possible approaches to improve these limitations when they achieved a major break through for photoelectrochemical (PEC) solar cells with dye-sensitized, nanostructured TiO2 electrodes. The unique morphology of the nanostructured TiO2 film increased for a 10 m film the ration between illuminated area to inner surface area by a factor of 102 and proved also to be able to handle the photo induced charge separations. Other approaches recently reported is the photovoltaic tandem cell introduced by J. A. Turner and O. Khaselev.3 They achieved remarkable high efficiency for direct water splitting with a GaAs/InP based integrated monolithic photoelectrochemical-photovoltaic device. In this thesis we have studied the photoelectrochemical properties of a well known semiconductor of the traditional kind, however upgraded with a new purposed designed morphology; namely 2O3 with a nanosized rod-like structure. 2O3, also called Fe Fe hematite, was investigated intensely in the 70s but is nowadays often not even mentioned in many reviews about potential semiconductors for water splitting, see figure 1.

Figure 1.

Position of energy bands at pH 1 of various semiconductor in the dark (d) and in light (l) with respect to the electrochemical scale. The position for hematite at pH 13 and pH 1 has by the author been added in the right hand part of the diagram.
4

The reason for this is because hematite has proven to suffer from bad semiconductor properties due to high recombination losses which made it not attractive for any practical use. 6, 7, 8 Studies have indicated though that a nanocrystalline morphology could be one way to increase the photon-to current yield by minimising the distance the minority carriers have to diffuse before reaching the interface. 5,7 With this in mind L.Vayssieres and co-workers at the University of Uppsala created a unique nanostructured fibre morpholgy for hematite, designed for a minimum loss by recombinations. The nanosized rod-like hematite proved to be able to generate high IPCE-efficiencies (7.5 % IPCE at a wavelength of 350 nm), well beyond the efficiencies earlier reported for single crystals and nanosized spherical particle systems of hematite. 7, 25, 26 Besides the wish for a not harmful, low priced and efficient semiconductor candidate for direct photoelectrochemical induced water splitting, this study of the hematite was also supposed to give a better understanding of the unique purpose-built rod-like nanostructured system.

2. Theory Behind the Photoelectrochemical Cell

2.1. The Semiconductor The heart of the photoelectrochemical cell is the photon-to-current transforming semiconductor. Most of the models describing the behaviour of semiconductors were derived by Grtner10 during the late 50s. Since then, the big market potential for semiconductors, has led to extensive

research to fully understand the behaviour of semiconductors and take advantage of their unique characteristics. 2.1.1. The Band Gap Solid materials can be divided into conductors, semiconductors and insulators according to the variation of their electrical conductivity with temperature, see figure 2. Metallic conductors conductivity decrease with temperature. The conductivity in semiconductors and insulators increases exponentially with temperature. The reason for the variation of electrical conductivity with temperature for different materials is found in the orbital theory. In a solid material the delocalization reaches a maximum with atom after atom laying in three-dimensional arrays taking part in bond spreading in the sample. Every atom contributes with their orbitals and when N different s orbitals are combined and overlapped N s-molecular orbitals are covering a band of finite width. If the atoms have p orbitals available, the same procedure leads to a p band. If the atomic p orbital lie higher in energy than the s orbital, then the p band naturally lies higher in energy than the s band. The void region which extends from the top of the filled valence band, Ev, to the bottom of the vacant conduction band, Ec, is called the band gap, Eg.
A W 6 c lesn ea nn o . er e r fr t v d r 0 l d a

v a a n s- id i Mi t h l . s co b

Figure 2.

Depending on the width of their band gap, Eg, solid materials can be divided into conductors (metals) and dielectric (insulators and semiconductors). Conductors have a continuum of electronic states, essentially a zero band gap, while insulators have a band gap of 4 eV or larger. Materials with band gaps in between are called semiconductors. At zero degrees Kelvin an ideal semiconductor has it valence band, VB, all occupied with electrons, while its conduction band, CB, is empty.

The transition of solar energy into electricity takes place when irradiation with higher or equal energy to the bandgap hits the semiconductor, i.e. when Eg hv as shown in figure 3, h is Plancks constant and is the frequency of the light. Light with less energy than the bandgap will not be absorbed at all and light with higher energy will excite electrons from the valence band, VB, to the conduction band, CB, where the electrons falls back to the lowest unoccupied energy state. The excess energy is transformed into heat.

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Energy [eV] Ec

Conduction band Band gap,Eg

The excess energy is transformed into heat when the electron falls back to the lowest level in the conduction band. Light, hv > Eg

Ev Valence band

Figure 3.
valence

When light with energy Eg h hits the semiconductor electrons might transfer from the band to the conduction band. Ec corresponds to the energy of the lowest unoccupied orbital in the conduction band and consequently Ev corresponds the energy of the highest occupied orbital in the valence band

An ideal semiconductor at zero degrees Kelvin has its valence band, VB, filled with electrons, while its conduction band, CB, is empty. At that temperature, the possibility of finding an electron in the valence band is therefore one, while the possibility of finding an electron in the conduction band is zero. As a zero energy reference point the vacuum level of the electron is used. When irradiated, electrons might move from the valence band to the conduction band and leave vacant electron orbitals. Those vacant orbitals are called holes, which can be seen as particles similar to the electrons, but positive charged, since they under the influence of electrical and magnetical fields behave like positive charged particles. The excited electrons in the upper band will be mobile and since the electrical conductivity depends on the number of electrons that are promoted across the gap the behaviour of semiconductors when heated is understandable. To get high efficiencies in a solar cell the band gap of the semiconductor must be suited to maximise the absorption of the energy distribution of the incoming solar irradiation. A small band gap will absorb most of the light spectrum and create a good photocurrent, however the photo voltage will be low. A broad band gap creates a bigger photovoltage but on the other hand only uses a small fraction of the sun spectrum which results in a low photocurrent. The optimum for efficient solar energy conversion is something in between. For direct splitting of water the bandgap should be around 2 eV which exclude many oxides which typically have bandgaps of 3.0-3.5eV. 2.1.2. The Fermi Level Similar to metals the free electrons and holes in the semiconductor are distributed after the Fermi-Dirac distribution which degenerates to the Boltzmann distribution when >>1

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(1) where is the population of the orbitals, the energy of the electrons, the Fermi level, and T have their usual meanings. The Fermi level indicates the chemical potential of the electrons in the semiconductor and is linked to an energy state which on the average is occupied by 0.5 electrons. In an insintric material in equilibrium the number of electrons in the conduction band are equal to the number of positive holes in the valence band, i.e. the Fermi level is situated half way between the valence- and the conducting band.
Energy

1 Population

Figure 4.

A typical Fermi-Dirac distribution. As the temperature is increased, the tail of the Fermi-Dirac distribution extends across the bandgap, and electrons populate the empty orbitals of the upper band.

2.1.3 Doping A way of changing the Fermi level and increasing the conductivity of a semiconductor is by implanted impurities and imperfections in the crystal which often give rise to new energy levels. The implants can be divided into two separated cases; acceptors and donors.

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Av n W d60 e r s n r f ra n d o . c lle e ae t r

v aMc t s - ild is a in hb . o

Figure 5.

Two dimensional representation of a silicon lattices. (a) n-doped semiconductor. (b) p-type semiconductor.

An arsenic atom with five valence electrons in an otherwise perfect four valence electrons silicon structure is an example of a donor as illustrated in figure 5a. The fifth electron will be very loosely bound to arsenic and might be considered as an electron donated to the conduction band. The electron is still, however, weakly bounded to the arsenic nucleus so it is not a completely free conduction band electron. Anyhow, the arsenic nucleus has a localised orbital in the bandgap, shown in figure 6 a, where the fifth electron can be accommodated. Electrons in the donor energy level should be close to the conduction band in energy so they can be easily thermally excited into the conduction band with a result of an increased conductivity. This kind of doping is called n-doping. Silicon might also be doped with trivalent atoms such as boron or aluminium as illustrated in figure 5b. Those kind of dopants introduce an energy level near the top of the valence band where electrons from the valence band can easily be excited that give rise to holes which will allow the remaining electrons to move and therefore increase the conductivity. This kind of doping is the opposite to n-doping and is called p-doping, see figure 6 b.

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A v n Wrd6 ce r s n ref a n d o .0 lle e a r t

v aM c t s -b . is a ino h ild

Figure 6.

(a) n-doped, a dopant with more electrons than its host forms a narrow band that supplies electrons to the conduction band which increases the conductivity of the material. (b) p-doped, a dopant with fewer electrons then its host can from a narrow band accept electrons from the valence band. The holes in the band are mobile and the conductivity naturally increases.

Since the electron distribution changes with doping the position of the Fermi level changes as well. In a n-doped semiconductor the density of the electrons in the conduction band increases and the Fermi level is shifted upwards. The Fermi level moves in the other direction if the semiconductor is p-doped due to an increase of electrons in the valence band. When heavily doped the Fermi level of the semiconductor might end up somewhere in either band. The semiconductor is then called degenerated and behaves similar to a metal.

2.2. The Electrolyte 2.2.1. The Relation Between Energy and the Electrode Potential When a semiconductor is immersed into an electrolyte two branches of science are joint together as well, that is solid state physics and electrochemistry. The solid part, the semiconductors, were initially studied and developed by physicists which described the band theory with an energy scale based on an electron at vacuum level as the zero reference point. In the early days electrochemists were more interested in the redox reactions in the electrolyte, which had its theoretical base in thermodynamics. In contrary to the physicists they used the standard reduction potential scale to describe the redox systems. On this scale the Normal Hydrogen Electrode, NHE is by definition zero and the conditions for the half cell is described by Pt | H2 (1 atm), H+ (a=1) (2)

where all species are at standard state. Then the potentials of all redox species can be given numerical values with reference to this electrode. This is done by forming a cell consisting of the

14

redox couple whose potential is to be determined as one half cell and the standard hydrogen electrode as the other and measure the potential. The tabulated values for the redox species vs. NHE refer to the standard state since the half cell potentials are dependent on the concentrations. The standard reduction potential is a function of Gibbs free energy and the relation is described by (3) where z is the number of electrons, F Faradays constant, the standard reduction potential for the cell and Gibbs free energy. How Gibbs free energy changes with the composition of studied substance when the pressure, temperature and the amount of other substances being constant is called the chemical potential, (4) where the subscript n signifies that the amounts of all other components (those other than i) are constant. The chemical potential gives the energy level of electrons in the redox species. If an electrical field is involved electrical properties must also be taken into account which the electrochemical potential, , does (5) in which is the chemical potential of electrons in the redox couple, the elementar charge,F the Faraday constant and is the electrostatic potential Obviously, when studying the interface between the semiconductor and the electrolyte, there is a need to link the physicists and the chemists systems together. The systems have things in common. Firstly, the Fermi level in the semiconductor and the redox potential of the electrolyte are really the same thing, namely the electrochemical potential of the electron. Secondly, the standard redox potential quantities can be converted to energy units by multiplying with the elementary charge, q. However, there is also one big difference between the systems, namely the references. This have caused problems and various researchers have tried to describe the relationship between the NHE with the energy of an electron at vacuum level, but it has proven to be difficult without relaxing thermodynamic rigor.11 The energy of the reference electrode versus the vacuum level has been reported from -4.3 to -4.7 eV, and usually are the latter used which leads to the relation:

15

16

E
17

(6) between the two different scales where is the elementar charge and is the redox potential vs. NHE. The energy scale and the potential scale are opposite directed, when the potential increases the energy of the electrons decreases as illustrated in figure 7.

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Figure 7.

The opposite directed energy and potential scales.

2.2.2. The Redox Potential The redox potential describes how easy a substance accepts or donates electrons and is energetically situated where the activity of the reduced form equals the activity of the oxidised form. The higher redox potential, i.e. the lower Fermi energy, the easier a substrate accepts electrons. Accordingly, substances with low redox potential, i.e. high Fermi energy, have less ability to accept electrons and are usually classified as electron donors. The redox potential is of importance in chemistry since it is the electrochemical conception which equals the Fermi level. Saying that a redox couple have a single, joint redox potential is a simplification though, since the effects of eventually supporting electrolytes are not taken into account. A more complete description is obtained by taking the dissolved redox couple and their polarisation of the nearby solvent molecules and ions in the solution into consideration. Since the energy states of the ions is determined by the polarisation of the solvent, the standard electrode potential of a redox couple is solvent dependent. Consider the reaction O + ne ---> R. During the reaction the suburbing dipoles will rotate and change positions. This give the reduced form a lower energy level. Since the molecules of the solvent is in constant movements it is commonly assumed that the distribution function for the density of states of the redox couple is Gaussian as described in figure 8.

18

A n v n d W o r d 6 . 0 c e l le r s e n a r e f r a t

v is a M a c in to s h - b il d .

Figure 8.

The Gaussian behaviour of the distribution function for the redox couple. The redox potential is located between the potentials of the reduced and oxidised form.

The redox potential, is defined as: (7) Which also corresponds to a state which on the average is occupied by 0.5 electrons. The redox potential is therefor equal to the electrochemical potential (or Fermi level) of the electron in the solution.

2.3. The Semiconductor In Contact with an Electrolyte 2.3.1. Equilibrium

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Figure 9.

The semiconductor in contact with an electrolyte

When a solid e.q. single crystal semiconductor is immersed into an electrolyte with a redox potential Vredox, an equilibrium will be established so that the electrochemical potentials and the Fermi levels of the two phases become the same. For a n-doped semiconductor the equilibrium is created by electrons leaving the semiconductor (the transfer process take place like a reduction reaction) until the electrochemical potential of the electron is adjusted to the redox potential in the solution. Compare (a) and (c) in figure 9. This process gives a deficiency of electrons in the surface region of the semiconductor. This region is called the depletion layer or the space charge layer due to the lower electron concentration compared with the bulk of the semiconductor. A negative counter charge region is correspondingly developed in the electrolyte, which is called the Helmholtz layer. Compare (b) and (d) in figure 9. The layers have different thicknesses since the charge carrier concentration in the semiconductor is much lower compared to the ionic concentration in the solution which gives the depletion layer a thickness several orders of magnitude larger than the negatively charged Helmholtz layer.

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If the solution has a low ion strength the potential in the Gouy layer extending further into the electrolyte solution must be taken into account. The counter charges in the semiconductor give a strong electric field which bends the valence and conduction bands as illustrated in figure 9c and the semiconductor achieves the important ability to separate electrons and holes produced by excitation of electrons in the semiconductor. The photo generated holes migrate to the surface and the electrons move simultaneously towards the back of the electrode. For the case of p-doped semiconductors the equilibrium will result in a accumulation of electrons in the semiconductor and the band-bending will consequently be in the opposite direction.

2.3.2. The Flat Band Potential The Fermi energy of the semiconductor can be changed in relation to the reference level by an externally applied voltage, the reason for this is found in the definition of capacitances. The counter charges which arise when the semiconductor is in equilibrium with the electrolyte can be associated with capacitances since charged particles are stored in the layers. The capactitance of the depletion layer, , is in series with the capacitance of the Helmoltz layer, , and the total capacitance can be described as: (8) where usually which give: (9) Since , a change of the potential over the interface mainly affects the capacitance of the depletion layer which leads to a change of the Fermi level in the semiconductor and consequently to a change of the band bending, Vb. The definition of the band bending, Vb, is the difference between the potential at the surface relative to some reference level and the potential in the bulk relative the same reference level. The potential where the band bending becomes zero, i.e. no depletion layer, is called the flat band potential, , and is measured with respect to a reference electrode. This means that the band bending at equilibrium is also defined as the difference between the redox potential and the flatband potential. See figure 10.

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Figure 10.

The n-type semiconductor/electrolyte interface, SEI, in equilibrium.

The flatband potential, , is important as it approximately gives the position of the conduction band of a n-type semiconductor and the valence band of a p-doped. A way of determine the flat band potential is by solving the Poisson equation, for doped semiconductors. This leads to the so-called Mott-Schottky equation: (10) where is the depletion layer capacity, , the dielectric constant of the semiconductor, the permittivity of free space, the dopant density, and the band bending. By plotting the inverted square rot of the capacitance over the space charge layer vs the potential of the semiconductor a straight line is obtained. Extrapolating the Mott-Schottky plot to 1/ = 0 gives the electrode potential when the potential over the space charge layer is close to zero. Accordingly we have: at 1/ = 0, =0 and (11)

The flat-band potential, and consequently the positions of the energy bands have been found to vary with the pH of the electrolyte for some semiconductors, especially oxides. The reason for this is mainly due to the surface acting as an acid-base couple, having the possibility to accept or donate protons according to (12) Then it can be shown that the potential difference between the surface of the semiconductor and the bulk of the electrolyte, i.e. approximately the potential drop over the Helmholtz' layer, can be described by. 22

(13) Note to temperature dependence. At 25C, when RT/F = 25.69 mV and equation 13. becomes (14) Hence, each unit decrease in pH increases the electrode potential by 59 mV, which is called the Nernstian shift.

2.3.3. Photoeffect 2.3.2.1 Ideal Single-Crystal If a semiconductor in contact with an electrolyte is illuminated with light of energy equal or greater to the band gap the systems departs from equilibrium. In the n-doped case the electron concentration in the valence band decreases and electron concentration in the conduction band increases (the opposite occurs in a p-doped semiconductor as earlier discussed), changing the Fermi level upwards and decreasing the band bending. In these processes the strong electrical field over the depletion layer play an important part since it separats the electrons and the holes. The redox potential of the electrolyte remains however the same under the irradiation which leads to a potential difference and a photovoltage. The photovoltage can be written as: (15) Where is the difference of Fermi levels in the semiconductor under illumination, and equilibrium, , as illustrated in figure 11 (page 18). By increasing the light intensity you eventually reach the flatband situation. The highest possible photovoltage is therefore equal to the bandbending, .

2.3.2.2. Nanostructured electrode Contrary to the single crystal electrodes nanostructured films is less influenced by a built-in electric field, the important separation process of the electrons and the holes is rather dependent on the diffusion of the charge carriers. In a three dimensional nanostructured electrode the electrolyte is able to penetrate the film all the way to the back contact and every particle is in contact with the electrolyte. Since the particles are usually too small to store an electric field the photoinduced current is instead dependent on the electron transport to the back-contact which is commonly assumed to be a diffusion process. 12

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2.3.4. The Regenerative Cell A regenerative cell can be designed by connecting a counter electrode to the irradiated semiconductor. Under illumination with light of the right energy, Eg h, electrons in an ndoped semiconductor will excite into the conduction band, CB, and be promptly extracted from the back contact of the working electrode and transferred via an outer circuit to the counter electrode; an useful electrical work can be gained. At the counter electrode-electrolyte interface the electrons will reduce A2+ to A+ and the photocreated positive holes at the semiconductorelectrolyte interface will simultaneously oxidise A+ to A2+ which keeps the net concentration of the couple in the electrolyte constant However, a concentration gradient is created in which the components of the redoxcouple will diffuse.
Av n W d60 e rs n r f ra n d o . c lle e ae t r

v aMc t s - ild is a in hb . o

Figure 11.

When the regenerated cell is illuminated the system departs from equilibrium and a useful photo voltage can be gained. The size of the photo voltage is direct proportional to the size of Ef.

By altering the resistance, R , between the two electrodes it is possible to control the behaviour of the power output from the system. When electrons in the valence band of the semiconductor are excited into the conduction band the Fermi level of the semiconductor rises, and depending on the value of R , the Fermi level of the counter electrode will also rise. The two extreme cases, R =0 and R =, are interesting since they give important information characteristics about the cell. R =0 corresponds to a short circuit of the electrodes and consequently the two electrodes will have the same Fermi level. This maximise the photocurrent, denoted by Isc. However, since no photovoltage is obtained no power can be drawn from the device.

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The other extreme, R =, corresponds to a maximised photvoltage, denoted by Voc. Since no electrons flow in the outer circuit there is no power developed in the external resistance in this case either. The remaining case is the situation where R has some intermediate value between R =0 and R =. The change in the Fermi level of the semiconductor is then equal to the sum of the potential drop over the resistance and the developed over potential at the counter electrode. The latter is dependent on the rate at which the charge transfer reaction at the counter electrode can occur. The current generated in the outer circuit then equal to I=V/R and the power developed in the resistance is P=V*I. By varying R it is possible to obtain a set of corresponding photocurrents and photovoltages which can be plotted in a diagram as I vs V. The effect of the cell can then be visualised and the maximum power can easily be obtained as the set of I and V, matching the rectangle with maximum area in the graph.

2.3.5. Charge Transfer Processes

A W 6 c le sn ea n n o . e r e r fr t vd r 0 l d a

v a ai t s b . i M n h id s c o- l

Figure 12.
backside (electrolyte/

A semiconductor film on a transparent conducting glass can be irradiated either from the denoted SE (substrate/electrode) illumination or direct from the frontside, called EE electrode) illumination.

In an optimal minority carrier transfer process between the interface of a semiconductor/metal junction Grtner10 proposed a model which describes the photocurrent response for a frontside illumination, EE, as defined in figure 12. The current density, , was calculated as the sum of the flows from the depletion layer , , plus the flow from the diffusion region, , and he assumed the photocurrent was directly proportional to the incident light intensity. By adopting this model Butler13 expressed the photocurrent density over the liquid junction interface for EE illumination by (16) where indicates the wavelength of the monochromatic light, is the incident light intensity, is the monochromatic absorption coefficient, the width of the depletion layer and is the diffusion length of the minority carrier. The width of the depletion layer was derived by Grtner

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to be (17) where q is the charge of an electron, is the relative dielectric constant, the permittivity of free space, the dopant density, and the electrostatic potentials of the semiconductor bulk and the surface, respectively. Thus the difference between those electrostatic potentials equal to the band bending. Butler also showed that near the bandgap region one can determine the nature of electron/hole production in the illuminated semiconductors by studying the photocurrent vs. the wavelength. The expression was (18) where is a constant dependent upon the applied potential, =1/2 for direct gap semiconductors and 2 for indirect gap semiconductors. By plotting the vs. it is possible to determine the size of the indirect bandgap of the material studied. Since the formula is based on Grtner's theory (photocurrent and the absorption spectrum are proportional) equation 18. can easily be adapted for an absorption spectra. Lindquist et al.14 took the theory further and derived a Grtner-Butler expression for SE illumination (19) where d is the thickness of the semiconductor. By differentiating equation 19. and combining the obtained maxima for with the equation for EE illumination, equation 16. (assuming <<1)they derived an expression of the quantum efficiency for EE illumination, , as a function of the depletion layer, , and the film thickness, . The equation could be written (20) using the value of the quantum efficiency for EE illumination when has a maximum in its action spectra. Practically the experimental photocurrent density observed is smaller than predicted by the Grtner-Butler model. This is due to recombinations of charge carriers and other factors which

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effect the efficiency of the photocurrent, see figure 13. To avoid recombinations the material dependent life time of the electrons and the holes created have to be long enough.

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Figure 13.
the

1) 2)

Direct recombination of excited electrons and holes. Recombination via local energy levels due to deficiencies in the bulk or the surface of semiconductor.

3)

The hole oxidise the surface of the semiconductor. This leads to a degradation of the semiconductor which is a major stability problem in some PEC systems.

4) *)

The photogenerated electron react with the electrolyte. The desired process for photocurrent generation

2.3.6. Water Splitting Storage of energy in the form of electricity has proven to be a problem, batteries are heavy and inconvenient and there are high energy losses when transporting electricity to and from the batteries. Another, more attractive, way to store solar energy is by producing hydrogen and oxygen by a direct splitting of water in a photelectrolysis cell. Hydrogen can be stored more easily than electricity and heat. Hydrogen is also an attractive substitute to fossil fuels, it is renewable, nonpolluting and easy to convert to different forms of energy e.g. heat via combustion, work via combustion engines and electricity via fuel cells. Hydrogen is also valuable as a chemical feedstock, the ammonia synthesis and petroleum refining demands big quantities. Since the current supply of hydrogen is mainly from steam

27

reforming of natural gas, a method based on solar energy and water would be a major improvement. Since the first report by Fujishima and Honda1 of direct photodissociation of water over TiO2 electrodes several approaches have been tried to improve the performance of the technique. The most common approach nowadays is still to use a semiconductor-liquid junction to produce the electric field needed to separate the electron-hole pairs created by the absorption of light in the semiconductor. The separated electrons will reduce water or hydrogen ions at a cathode region and simultaneously the holes will oxidise water into oxygen at an anode region. A second possible approach based on semiconductor-liquid junctions is to absorb dye molecules on the semiconductor surface which upon light absorption will inject electrons (into n-type semiconductors) or holes (into p-type semiconductors). Recently did J.A. Turner and O. Khaselev3 report about direct water splitting with remarkable high efficiency for a tandem cell of GaAs/InP. The reported efficiency of 12.4 percent (based on the short-circuit current and the lower heating value of hydrogen) for the integrated monolithic photoelectrochemicalphotovoltaic device is to be considered as the world record for PEC solar cells for direct splitting of water at present. Apart from a net chemical change in the electrolyte the biggest difference from the traditional regenerative cell, previously described, is that different redox reactions proceed at the two electrodes in the photoelectrolysis cell. For splitting water the reactions are: cathode: anode: total: (21b) ---------------------------------------(22) (21a)

which shows one of the obstacles with direct water splitting of water; we need four electrons to yield one O2 molecule. Figure 10 shows the principles of a photoelectrolysis cell for splitting water. Since there is no resistance in the circuit the Fermi level of the counter electrode will follow the semiconductor's. In order to split water it is necessary that the flat band potential of the semiconductor is at a lower potential (higher energy) than the redox potential for H2/H+. At the same time the band gap of the semiconductor must at least be equal to 1.23eV, which is the position of Eo(H2O/O2) in reference to the Eo(H2/H+). The electrode potential of the latter is by definition zero. To the

28

difference of 1.23eV the necessary overvoltage should be added which gives an optimum bandgap for water splitting by Gerischer estimated to 2.2eV15 If the upper part of the band gap (the lower edge of the conduction band) is not situated at an energy level high enough for reducing hydrogen an extra bias can be applied to help the system go round. However, an applied bias should be avoided for economical reasons.
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Figure 14.

For a direct photoelectrolys of water on a semiconductor interface the flatband potential, U fb, has to be at an higher energy level than the redoxpotential for the H 2/H+ couple and the valence band has to lie lower in energy than the redox potential for H20/O2. When irradiated with light of energy bigger than the bandgap the Fermi level will raise and reach over the redox level for H2/H+. Water will then split into to hydrogen and oxygen.

2.4. Hematite, -Fe2O3

29

The problem with the cell created by Fujishima and Honda1 was low efficiency in sunlight irradiation since TiO2 is a wide band gap semiconductor which only absorbs in the UV-region (referens). The following years extensive research were put into polycrystalline thin film semiconductor electrodes with appropriate bandgaps. Although the efficiency of these cell were acceptable, degradation of the film due to photocorrosion remained an unsolved problem. Several attempts with the more stabile oxides were also made, one of the more studied was hematite. 5-8, 18, 20-26 With a band gap around 2 eV and with a good stability hematite is an attractive semiconductor material to consider for photoelectrochemical purposes. Hematite is also an inexpensive material and not too harmful to handle or produce which also contributes to the interest. With a valence band edge at +1.6V/SCE at pH14 it also makes it suitable for photoinduced oxygen evolution from water splitting. The deep red 2O3 is also a good Fe absorber of light, it absorbs in the UV-region as well in the visible region and it permits the use of about 40% of the solar photon flux incident on the earth's surface. Due to these characteristics several researchers have tried to use hematite for conversion of solar energy, by splitting of water, into hydrogen and oxygen. However, single crystal and polycrystalline hematite has showed low efficiencies as photo anodes for the oxidation of water and other substrates. Some of the reasons for this are low mobility of the charge carriers, a short diffusion length (20-40)16 and fast surface recombination. For these reasons the interest for hematite declined during the late 80's. However, studies have recently indicated that nanocrystallised hematite could be one way to increase the efficiency by minimising the distance the minority carriers have to diffuse before reaching the interface.

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Figure 15.

The crystal structure of 2O3 Fe

17

consists of close packed layers of oxygen ions and two of the

18

three available octahedral interstices are occupied by Fe3+.

30

2.5. The Nanostructured Semiconductor The increasing knowledge of morphology, particle size and orientation and how they effect the performance of semiconductor films have brought new opportunities and new challenges to the solar cell field. Especially the thin nanostructured systems have been of interest since a nano structured material offers good porosity and a big surface to volume ratio which have proven to increase the performance of the photoelectrochemical (PEC) cell.2 The unique morphology of the nanostructured thin film electrodes make them behave differently from single-crystal or polycristalline electrodes. In some aspects the nanostructured material is actually more similar to a colloid solution than to a bulk material with respect to its behaviour under illumination. The band bending is small, due to the nanosized particles, and it can be assumed that there is no electrical field over the nanostructured film due to screening by the electrolyte.12
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Figure 16.

The nanostructured electrode with SE and EE illumination shown. The electrode consists of a glass disc (1), a conducting layer (2) and the interconnected nanosized colloidal particles.

When illuminated, light absorption in any individual nanoparticle will generate an electron-hole pair and charge separation will occur if it is kinetically favoured. If the holes created have a high oxidation potential, which is the case for several semiconductors with wide band gap, the holes usually react with the species in the electrolyte at high rate constants. However, for a successful charge separation the rate for the hole at the surface must exceed the rate for recombination. This leads to a charge separation determined rather by kinetic differences between electron and hole transfer into the electrolyte at the interface instead via a space charge layer which is the case for single-crystal or polycristalline electrodes. If the colloidal particles are in electric contact then electrons can travel, if not lost to the electrolyte, via the network of particles to the back contact. It is clear that there will be an increased probability of recombination with increasing film thickness, as the electron has, on the average has to travel a longer distance. Hagfeldt et al.19 reported that the action spectra for SE and EE illumination on nanostructured TiO2 were just the opposite of the spectra for thin solid polycrystalline films of same semiconductor. In the nanosized structure the best result was obtained when illuminated from the back (SE) which is just the opposite compared to the polycrystalline structure. The most efficient charge separation seems therefore to take place close to the back contact in nanostructured material i.e. the electron that has the shortest way to travel will have the highest probability to reach the back contact.

31

This indicates that a thin nanostructured films would be the optimum. On the other hand the absorption of the incoming light increases with thickness so there seems like there would be a trade off between recombination and absorption to obtain a maximum photocurrent.

2.5.1. The Nanosized Rod-like Hematite Structure J. Moser and M. Grtzel5 reported a high quantum yield in photoinduced oxidation of iodide as hole exceptor in a suspension of 120-nm-sized iron oxide colloids in acidic environment. The promising result encouraged U. Bjrksten et al.7 to go on and prepare Fe2O3 film with a nanocrystalline morphology of a similar kind already established for TiO2. The resultant was disappointing and showed that bulk and/or grain boundary recombinations remains high even for particles in the 25-75-nm size range. The higher quantum yields obtained on colloids in suspension pointed at grain boundary recombination in the electrodes. With this in mind L. Vayssieres and co-workers9 at the institute of physical chemistry at the University of Uppsala designed a nanosized fibre structured Fe2O3 film.
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Figure 17.

(a) traditional nanocrystalline morphology; electrons diffuse via a random walk over grain boundaries between particles to the back contact. (b) designed nanosized rod-like hematite; e lectrons can easily diffuse direct to the back contact of the electrode.

The unique structure of the hematite film, see figure 18, was designed to give a high photocurrent yield by making it easy for the holes and the electrons to separate and to minimise recombinations. The diameter of the rod-like hematite matches physically the minority carrier diffusion lengths allows for fast hole release from the valence band and fast capture at the semiconductor/electrolyte interface by a redox couple. The latter is achieved since the electrolyte penetrates the system all the way to the back contact so the holes are always close to the semiconductor-electrolyte interface. Simultaneously, the photo induced electrons can easily penetrate the fibres to the back contact without passing through grain boundaries as illustrated in figure 17. The purposed designed film with its unique morphology in which orientation of the particles and particle size are optimised would hopefully significantly lower the hematite bulk recombination losses.

32

Figure 18.

SEM picture. Topview of the anosized rod-like hematite film.

33

3. Experimental section
3.1. Electrode preparation. The nanosized fibres structure was created on top of a fluorine doped and highly transparent SnO2 conduction glass (Libbey Owens Ford, 8/square). The film thickness used for the most characterisations of hematite was 700 nm (that is the thickness of the film if not anything else mentioned). However, films with other thicknesses were also prepared. 3.2. Three electrode measurements When making photoelectrochemical measurements it is important to fix the measured values of the light induced reactions to a certain energy scale relative to some reference. One practical way of doing this is by using three electrode measurements where a potentiostat keeps an applied potential constant between a reference electrode (of known potential) and a working electrode. The photogenerated electrons are promptly extracted from the back contact of the working electrode and transferred via an outer circuit to the counter electrode where the electron at the electrode-electrolyte interface undergo a chemical reaction. Between the working electrode and the reference electrode the current is negligible and by installing the reference electrode close to the working electrode the effect from inner resistance in the electrolyte is minimised. By altering the applied potential and/or the energy of the light, the characteristics of the semiconducting film and the photoinduced currents can be studied in a convenient way. The working electrode was installed in an ordinary three electrode set-up in a Teflon vessel with quartz glass for the incoming light. An Ag/AgCl electrode in KCl sat. (211.5mV vs NHE at 20oC) was used as a reference electrode. To avoid reflections of the incoming light the inner surface of the vessel was covered with black Teflon. For the measurements with monochromatic light a 450W Xenon lamp with an accompanying monochromator (Schoeffel 252) was used. For simulated solar radiation a Light Drive 1000, type 1400-E211 was used. All chemicals used, were of reagent grade; the water used was Milli-Q (Millipore Corporation). and the electrolyte was mechanically stirred and degassed by bubbling through nitrogen (Nitrogen Plus, AGA, 99.99% N2) before and during each experiment. The photocurrent as a function of the applied voltage (IV-curve) was measured at a wavelength of 470 nm hitting from the back contact side, SE illumination, of the sample. Also simulated

34

solar radiation, was used to study the photocurrent response as a function of the applied potential. lllumination of the hematite film was also carried out in a wavelength interval of 300-700nm. Front-side illumination, light incident on the electrode electrolyte interface known as EE illumination, as well as back-side illumination were performed. The photoresponse and the light intensity were measured and the IPCE was calculated according to: (23) where is the photocurrent in Amperes, is the light power intensity in Watts and is the wavelength in nm. Since the transmission through the glass is less than 50 % below 350 nm and the photocurrents are low, this part of the corrected SE action spectra contained relatively large errors in the calculated IPCE and was therefore excluded.

3.3. Two electrode measurements The power a solar cell produce is the product of its operating current and voltage. The I-V characteristics are therefore often used to characterise the cells. Under open circuit conditions the voltage is maximised (Voc) but no current flows; no power is provided to the circuit. At the other extreme, under short circuit conditions, the current is maximised (Isc) but voltage is zero; power is again zero. Somewhere in between these two extremes are the condition for maximum power located, i.e. Im.Vm=Pmax. The closer the product of Voc and Isc is the optimum Pmax the better. The closeness with which maximum power approaches the product of Voc and Isc is by definition, called the fillfactor, ff (24) The two electrode measurements were carried out by putting the hematite electrode (working electrode) on top at a platinum foil (counter electrode) with electrolyte in between and illuminate with simulated solar radiation of 0.1 Sun. The open circuit voltage and the short circuit current was then obtained by altering the resistance over the cell. 10% TMA-OH (Tetra Methyl Ammonium Hydroxide) was used as electrolyte. No bias was applied.

35

3.4. Characterisation 3.4.1 Spectroscopic Measurements Spectroscopic measurement was carried out to get an idea in what wave length interval the hematite absorbed light. The spectrophotometer used was an Hewlett Packard, HP8453, where SnO2-covered glass was used as a reference. No correction was made for losses due to reflections and scattered light which means that the registered absorbance of light might be slightly high. 3.4.2. Film thickness measurements The thickness of the hematite films was measured by profilometry (Tencor Alpha Step). This method is based on the movements of a mechanical stylus following the topography of a filmsubstrate step. The accuracy of the method is by some extent limited by the roughness of the substrate, vibration of the equipment and by stylus penetration of soft films. 3.4.3. SEM Measurements The structure of the film has earlier been determined by Scanning Electron Microscopy, SEM9 which clearly showed highly nanosized rod-like structure. It would have been good to have carried out SEM studies even on these batches of the hematite studied here, but the shortage of time and lack of instruments made it not possible.

36

4. Results and discussion

4.1. Three Electrode Measurements with 0.1 M NaOH as Electrolyte
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(a) Figure 19
700 nm.

(b)

3-electrode measurements with Ag/AgCl as reference electrode, hematite filmthickness of

(a) O.1 M NaOH (pH 13) used as electrolyte, 1.0 Sun irradiation, (b) 0.1 M KI buffered at pH 7, irradiated with monochromatic light at a wavelength of 470 nm from a 450 W Xenon lamp.

The result indicate that hematite has a strong n-doped behaviour which is confirmed by other studies of hematite.6-8,
21-26

The reason for this is probably due to an oxygen vacancy

concentration, especially observed at higher temperatures.20, 21 According to other studies of water splitting with hematite the process is enhanced by increased pH.7, 22 The hematite surface probably acts as an acid-base couple changing the flat-band potential and consequently the position of the energy bands. The curves for 0.1 M NaOH (pH 13) electrolyte and 0.1 M KI (pH 7) electrolyte are very similar in shape suggesting that the ratelimiting-step is more or less the same in both solutions. The photocurrent as well as the dark current in 0.1M KI are shifted around 400 mV in the anodic direction compared to 0.1 M NaOH. This represents a shift of ~67 mV/pH which is slightly higher than the theoretical value of 59 mV/pH. J. H. Kennedy and M. Anderman22 reported a shift of ~70mV/pH for polycristalline 2O3 which is also somewhat larger then the expected shift of the flatband potential. The Fe

37

measurements also proved that 0.1 M NaOH as electrolyte could handle +400 mV of applied voltage without yielding a dark current high enough to mention. The onset potential for the photocurrent in 0.1M NaOH is around -500 mV vs the Ag/AgCl indicating that the flatbandpotential, Vfb, should be somewhere in the same region. This may not be explained by classical semiconductor theory. As we will see from the action spectra further on, page 36, the present hematite films behave like a porous nanostructured film where charge transport depend on diffusion and no depletion layer is formed. Never the less the position of the Fermi level increase on increasing illumination and will at high intensities reach a value corresponding to Vfb in a none-porous film. A flatbandpotential around -500mV in pH 13 is in good agreement with the literature23, 24, 26 (referenser), however for a more precise determination of the flatband position a Mott-Schottky study should be carried out. Scanning the electrode potential further down in the cathodic region, way past the onset potential, the electrode stopped behaving reversible indicating a more severe damage. This is probably due to some kind of reduction of the photoanode itself where Fe3+ + e- ---> Fe2+. Figure 19 also shows that oxygen and hydrogen can be produced with just a small over potential. Theoretically an energy of 1.23 eV is needed for splitting water and according to the diagram hydrogen seems to start evolving at an applied voltage around -600 mV and oxygen at an applied voltage near +600 vs Ag/AgCl. No detection equipment for hydrogen and oxygen evolution were used, but sodiumhydroxide in water as electrolyte should not yield anything else than oxygen and hydrogen.

4.2. Two Electrode Measurements with 10% TMA-OH By altering the resistance over a two electrode set-up with 10% TMA-OH, pH 14 as electrolyte and 0.1 Sun irradiation the short circuit current as well as the open circuit voltage was determined.
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38

Figure 20.

Two electrode measurements

Open Circuit Voltage, Voc: Short Circuit Current, Isc: Fillfactor, ff:

0.2295V -5.683A 0.1645

At the first look the results might not seem too impressive, however the measurements were done without any applied bias. This is interesting and promising since there is nothing in the literature indicating that this has been done before. The straight line between Isc:and Voc:is an indication of a high serie resistance in the cell circuit

4.3. Action Spectra and Calculation of the Bandgap

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Figure 21.

The action spectra for hematite was carried out with a three electrode set up and an applied voltage of 300 mV vs Ag/AgCl where high photoconversion efficiencies were obtained. The measurements were corrected for dark currents. The electrode was of the thickness 700nm. 1% TMA-OH was used as electrolyte and the irradiation source was a 450W Xenon lamp.

The efficiency for back-side illumination (SE) and front side illumination (EE) is quite higher than earlier reported results for hematite.7, 25, 26 The action spectra also shows how the SE illumination is more efficient than the EE illumination which is typical for a nanostructured system19 where the charge carrier produced in the vicinity of the back contact usually are collected more efficiently. The photocurrent action spectra obtained with the rod-like hematite

39

mimics the absorption spectrum well in the visible region indicating that the material is able to handle the charge carrier generation quantum yield similarly over that range. For the UV region the matching is not as good, the absorption is more or less constant in the range 350-450 nm while IPCE is increasing.

An action spectra for a rod-like hematite structure with a film thickness of 200 nm was also carried out, see figure 22. The action spectrum confirms the diffusion problem of the electrons in Fe2O3 showing a huge increase of the IPCE for EE illumination compared to the film with a thickness of 700 nm. The lower IPCE for SE illumination of the thinner film is more difficult to understand. The drastic drop can not be theoretically explained and until further studies have been carried out no explainations to the behaviour can be found.
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Figure 22.

Same condition as in figure 21. apart from the electrode having a thickness of 200 nm.

The difference in the IPCE values under EE and SE illumination, especially distinct in the thicker film, indicates that the collection of the photogenerated electrons across the hematite film is somewhat poor. However the difference here is significantly smaller than those reported by Bjrksten et al.7 for a nanosized hematite particle systemwhere the particles were of the size 2575 nm. Compared to the well studied TiO2, the photocurrent yield for hematite19 is lower which is probably due a combination of the short hole diffusion length for hematite and the crystallite size which is slightly larger in the Fe2O3 than in the TiO2 films. This means that the minority carriers have to diffuse over a larger distance in the hematite film before reaching the surface

40

and the scavenger. Taking the small hole diffusion length of 20-40 in hematite into account it is natural that charge carrier recombinations is a dominating problem. However, the high hematite efficiencies obtained with the action spectra in this study indicates that purposed designed rod-like Fe2O3 is a way to lower the charge carrier recombinations which is particularly encouraging.

From the near bandgap region of the action plots, one can determine the nature of electron/hole production in semiconductors materials. 13 The relation ship is given by equation 18. (18) with n=2 (indirect bandgap) or n=1/2 (direct bandgap). Log-log experimental plots of Ihv versus hv-Eg indicate that the lowest transition in hematite is best described by n=2 and thus is indirect. Following these arguments, the data of figure 22 were replotted in figure 23 as vs. , also a bandgap approximation was made by using the absorption spectra plotting vs , where is the optical absorption coefficient.

41

42

43

44

(a) Figure 23.

2.05 eV.

(b)

(a) The photocurrent response of hematite anode. The data indicate an indirect optical gap of

(b) The absorption response of hematite anode. The data indicate an indirect optical gap of 2.15 eV

According to the literature24-26 hematite is supposed to have a indirect bandgap just above 2 eV. The result from the replot of the action spectra and the absorption spectra indicates that the bandgap should be situated around that position. The reason the absorption plot gives slightly higher values is probably due to difficulties with obtaining an absolute correct absorption spectrum when measuring through the conduction glass. 4.4. The Influence of Film Thickness By altering the length of the fibres it is possible to find an optimum in the trade off between porosity and absorption. In terms of production it might even be better to go for a thinner film than the optimum suggests. A thin film has advantages in forms of preparation time, costs and less problem with cracking during preparation. To compensate for the lower absorption of the incoming light one option is to place several electrodes after each other in a row. Since every electrode has its own back contact the problems with recombinations, electron losses and bad porosity will not occur at the same scale. This is confirmed practically, Bockris et al reports about a current three times higher for a stack of ten 60-nm-thick hematite photoelectrodes that obtained for a single electrode of thickness 600 nm. 6 Two different film thicknesses, d, were produced by altering the preparation time; one with the thickness of 700 nm and one with the thickness of 200 nm. The thinner one was noticeably less coloured which was confirmed by spectroscopic measurements. Wavelength [nm 350 400 500 600 Table 1. IPCE-SE/d [100*m-1] 10.89 6.55 1.80 0.19
700 nm

SE/d [m-1] 0.109 0.0655 0.0183 0.00287

IPCE-EE/d [100*m-1] 1.85 1.36 0.70 0.14

EE/d [m-1] 0.019 0.013 0.007 0.002

Transmittance [%] 0.028 0.029 1.70 33.88

Transmittance and IPCE/d values for SE and EE illumination for a hematite film of thickness

45

Wavelength [nm] 350 400 500 600 Table 2.

IPCE-SE/d [100*m-1] 14.65 6.53 1.42 0.102

200 nm

SE/d [m-1] 0.15 0.066 0.016 0.00142

IPCE-EE/d [100*m-1] 9.108 4.85 1.12 0.12

EE/d [m-1] 0.092 0.049 0.013 0.00167

Transmittance [%] 0.76 0.97 11.54 71.78

Transmittance and IPCE/d values for SE and EE illumination for a hematite film of thickness

Comparing table 1. and 2. it is observable how the ratio between the IPCE and the thickness, IPCE/d, has increased in the UV-region by making the film thinner. The difference is especially pronounced when the illumination is from the EE side. Since the chances of recombinations increase with the diffusion length, and the electrons have a shorter distance to travel to the back contact in a thin film compared to a thicker film when irradiated from the EE side, this indicates once again the problem with bulk recombinations in hematite. However, the significant higher IPCE value for EE illumination of thinner film is interesting for practical applications outside the laboratory and the study indicates as well that an ensemble of electrodes might be one way to increase the efficiency of the conversion of light to hydrogen. Apart from thin film electrodes also thicker and more light absorbing electrodes were prepared. One way of doing that is by putting two or three layers of fibres hematite on top of each other on a single back contact. The result by putting two layers on each other was an increase of the absorption by a factor of three (at 550nm), still though, the film yielded a lower photocurrent than the case for a single layer of hematite which is probably due to bad porosity of the film and/or high electron losses in the boundaries between the different layers. This only confirms what Bjrkstens et al7 reported; the importance of a highly porous nanostructured film. A second way to produce a more light absorbing film is by making the hematite fibres longer. However, a longer preparation time seemed to mainly make the fibers grow in the side direction (making the film more compact and less porous), since the film thickness came to a maximum of around 700 nm after some time and did not increase with did not become bigger with extra preparation time but the absorbance of light in the film increased. The photocurrent response for those electrodes were, as expected, low

4.5. The Effect of Light Intensity

46

Hematite has over the years proven to have problems with recombinations. 6,7,23 A short study was done to verify how the recombinations vary with the incident light intensity and the applied potential, see fig 24.
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(a) Figure 24.

(b)
The photocurrent density as a function of the incident light intensity. The values are corrected for darkcurrents and the measurements were performed in a three electrode setup with 1% TMA-OH as electrolyte.

The result showed that the nanosized hematite electrodes gave a lower photon-to-current conversion efficiency, (IPCE), for light of higher intensities. According to the classical semiconductor theory developed for thin films by Grtner 10, equation. 16. and equation 17. the IPCE should increase steeply as soon the applied potential of the semiconductor electrode departs from the flatband potential and a depletion layer is formed. That would explain, if there is band bending at all in the nanosized film, why there is an increased efficiency with an increased applied potential. In the present nanostructured hematite film the charge transport depend likely on diffusion and no depletion layer is probably formed. Never the less the position of the Fermi level increase on increasing illumination and will at high intensities reach a value corresponding to Vfb in a none-porous film. The decrease in efficiency per unit Watt with intensity, clearly shown in figure 24b, is probably due to a high rate of recombinations of electrons and holes at higher intensities. This can be explained either by the reactions for recombinations being of the 2nd order, i.e the rate of recombinations increases with the concentration of both the photoinduced electrons and the photogenerated holes. It might also be explained by slow kinetic for the hole accepting reaction. Anyway, no matter what the reactions are behind this phenomena the result clearly confirms the high rate of losses of electrons from the conduction band in hematite which will be one obstacle to overcome before making hematite semiconductor films with really good efficiencies.

47

4.6. The Effect of the Effective Radius of the Cation and Estimation of the Mobility of TMA+ A study of the effect of the cation in alkaline solutions was done. Electrolytes with different effective cation sizes were studied and the photocurrent was measured versus the applied potential in a three electrode set-up. The study was supposed to quickly give a hint whether the effective size of the cation had an effect on the photo induced reactions or not. The idea was that screening of the anode (the semiconductor, hematite) might be one road block to overcome for efficiently splitting water. Following these arguments a cation with low mobility would interfere less in the semiconductor-electrolyte interface and make it easier for the photogenerated holes to oxidise water. The resultant indicated, as illustrated in figure 25 and table 3 that this might be the case since the cation with the lowest mobility TMA+ (Tetra Methyl Ammonium ion) gave the highest photo current. The other cations placed each other in order with the cation of the best mobility as the one generating the lowest photocurrent.
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Figure 25.

I-V diagram based on a three electrode set-up on four different electrolytes with four different sized cations. Corrected for dark currents, about 1 Suns irradiation, N2 bubbling through.

Cation TMA+ Li+ Na+ K+

Ionic mobilities in water at 25C, u/cm2s-1V-1 (3.23 10-4 )* 4.01.10-4 5.19.10-4 7.62.10-4

48

Table 3.

Ionic mobilities of cations in water at 25C.

27

* The mobility of TMA is estimated by using electrochemical methods, see below.

From the result above we were able to estimate the mobility of the TMA+ ion. Waldens rule says that the product of the viscosity and the conductivity is approximately constant for the same ions in different solutions. The rule is a consequence of Stokes law of the frictional force for a spherical particle in a solution (25) where F is the force on a particle with the effective radius r, y the viscosity of the solution and v the speed of the particle. This force is balanced in an electrical field by the electrical force on the particle, which gives (26) Where E is the electric field, z the number of charge carriers and q the elementary charge. The speed of the particle, v, can be expressed as a function of the mobility of the particle and the electric field (27) where u is the mobility of the particle. If equation 27. is inserted into equation 26. a relation between the effective radius and the mobility is obtained (28) The effective radius were calculated for the cations of known mobility. The reason for the effective radius increasing from Li+ to Cs+ even though the ionic radii increase is due to small ions giving rise to stronger electric fields than large ones. Small ions are therefore more extensively solvated than big ions and may have larger effective radius since they drag many solvent molecules through the solution as it migrates. By plotting the photocurrent versus the effective ionic radius of the cations a straight line was obtained where the effective radius of TMA+ and consequently the mobility of TMA+ could be estimated.

49

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Figure 26.

The effective radii for the alkali metal ions versus the current density. The effective radius and consequently the mobility in water for TMA+, could easily be estimated.

From figure 26. the effective radius of the TMA+ was estimated to 2.95 10-10 m which gave a mobility of 3.23 10-4 cm2s-1V by using equation 28. with the viscosity of water at 25C equal to 8.91 10-4 kgm-1s-1. 27 Apart from a relation between the effective radius of the cation and the photocurrent response it was also noticed that TMA-OH yielded the best photon-to-current yield of those four candidates. TMA-OH was therefore used in other measurement as a good and effective electrolyte.

4.7. Attempts with Catalysts for Oxygen Evolution To split water by electrolysis or directly on a semiconductor surface under irradiation the difficult part to overcome is the oxygen evolution. One of the reasons for this is the fact that four electrons are needed to create one molecule of oxygen and for this reason can be expected to be complex. To increase the oxygen evolution rate a catalyst is usually needed. Extensive research have been put into finding a sufficiently good catalyst for oxygen evolution where a good one would save enormous costs for the electrolysis industries. However, since the reactions involved for oxygen evolution is not fully understood it is hard to design a suitable catalyst. For splitting water on a semiconductor surface where usually alkaline environment are used another problem arises as well; the catalyst has to be stabile in that pH range. Apart from the catalyst itself another obstacle to overcome is the attachment of the catalyst on the top of the nanosized hematite which is not easily done. The catalyst must be evenly attached over the whole surface 50

without decreasing the porosity of the nanosized system and there may also be difficulties with getting the catalyst to stick permanently to the surface of the hematite. Two different metal oxide catalysts were used separately in an attempt to improve the oxygen evolution on the hematite electrode. According to the literature28 are RuO2 and NiO two good candidates which have proven to decrease the overpotential for oxygen evolution. Unfortunately, the result of attaching the catalysts were disappointing since none of the treated electrodes has shown any improvement of oxygen evolution. The only thing noticed was a slight increase of the dark current which can not be classified as an improvement. If the lack of improvement was due to a fail of attaching the catalyst properly or due to a disturbance of the highly porous nanosized system is hard to say. Further investigations has to be done in this field since a well working catalyst would probably increase the performance of the system significantly.

5. Concluding Remarks and Future Outlooks.

At this stage of studies it can be concluded that the morphology of the nanosized hematite electrodes plays an important role for the photoelectrochemical characteristics of these films. The nanosized rod-like hematite has proven to be able to generate high IPCE-efficiencies well beyond the efficiencies earlier reported for single crystals and nanosized spherical particle systems of hematite. The rate of losses of electrons from the conduction band remains however a problem to solve in combinations with ensemble optimisations and the search for a sufficiently good catalyst before hematite practically can be used as a good and efficient photoconverter for water splitting.

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Acknowledgements

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