Nanostructured Titania Dye Sensitised Solar Cells: Study of the effects of variations in the TiO2 Film Thickness and

Dyeing Times.

Course: Author: Supervisors: Date:

Chee4006, Individual Enquiry A Tate Brammer Professor Max Lu Indriana Kartini 17/05/04

Australia Research Council Centre for Functional Nanomaterials Division of Chemical Engineering School of Engineering The University of Queensland Brisbane QLD 4072 Australia

Acknowledgements:
There are several people I would like to acknowledge for their support and assistance in the completion of this individual enquiry. Firstly I would like to thank my supervisor Professor Max Lu for his guidance and support. His enthusiasm showed for the project has helped me to complete half of my thesis. Another person who has assisted me a great deal with the project is Indriana Kartini. Her technical assistance and support throughout the semester has been invaluable. I would also like to thank Paul Meredith who has given up his time when needed to provide technical assistance. Finally I would like to thank Luke Matthew and Chaoqing Lu who have assisted me with laboratory work throughout the semester.

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Abstract:
The following report is a preliminary study of the research and experimental procedures required to complete the thesis on, Nanostructured Titania Dye Sensitised Solar Cells: Study of the effects of variations in the TiO2 Film Thickness and Dyeing Times. The aim of this thesis is to study the mechanisms behind the operation of Titania solar cells. In particular the aims are as follows:

Research and obtain an understanding of Dye Sensitised Solar Cells Vary the thickness of the titanium dioxide semi-conductor films in these cells and analyse the effects. The effects of varying the dyeing time of the films will also be studied. Titania powder characterisation. experimentation, findings of this analysis report from are which conclusions the Titania and

The report is experiment based with the following methodology being used: research, The main recommendations will be formed. regarding powder characterisation. Properties of commercial grade Titania powder used in the production of semiconductor films were found to change after the powder has been calcined in furnace. Methods for the production of micron thick Titania films were also analysed. A repetitive dry coating technique was found to give a consistent film. The different methods used to produce the films will be further tested to find the light to electricity efficiency. From these results an optimum method and thickness will be found. This report is predominantly a review of the research which has been undertaken in this field. The procedures required to complete the experimentation and analysis of these solar cells are also detailed.

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Table of Contents
1 2 3 4 Introduction:..................................................................................................1 Problem Summary ........................................................................................3 Methodology: ................................................................................................4 Literature Review:.........................................................................................5 4.1 Photonic and optoelectronic devices:........................................................5 4.2 Dye Sensitised Solar Cells (DSSC): .........................................................6 4.2.1 Cell Structure: .....................................................................................6 4.2.2 Operating Principles (DSSC): .............................................................7 4.2.3 Nanocrystalline Titania Dioxide Films: ................................................9 4.2.4 Dye Uptake: ......................................................................................14 4.2.5 Quantitative measurements on cell Performance: ............................14 4.3 Summary:................................................................................................16 5 Experimental Procedure and Preparation.................................................16 5.1 Working Electrode Preparation ...............................................................17 5.1.1 Repetitive coating: ............................................................................18 5.2 Counter Electrode and electrolyte preparation:.......................................18 5.3 Cell Construction.....................................................................................19 5.4 Titania Dioxide characterisation ..............................................................20 5.5 Cell Testing Procedure ...........................................................................21 6 Results:........................................................................................................23 7 Discussion:..................................................................................................25 8 References: .................................................................................................27

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List of Figures
Figure 1: DSSC Structure .....................................................................................7 Figure 2: Principles of operation of DSSC ............................................................8 Figure 3: Light-to-electric energy conversion efficiency vs Number of layers .....12 Figure 4: I-V curves for (a) P25 single layer, multiple coats of Indrianas mesoporous Titania (b) 1 coat, (c) 2 coats, (d) 3 coats and (e) 4coats. ........12 Figure 5: Typical I-V curve ..................................................................................15 Figure 6: Constructed Titania Dye Sensitised Solar Cell ....................................19 Figure 7: Autosorb Equipment (N2 Adsorption/Desorption) on left and degassing machine on right ...........................................................................................20 Figure 8: Solar Cell testing equipment from UQ Physics Labs ...........................21 Figure 9: Solar Cell testing rig on right and computer set up for testing on left...22

List of Tables:
Table 1: Properties of TSS powders and P25 .....................................................14 Table 2: Structural Properties obtained for P25 commercial powder ..................23 Table 3: N2 Adsorption Isotherm for the commercial grade P25 powder before and after calcining.........................................................................................24

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1 Introduction:
The aim of this thesis is to carry on the work started by Idriana Kartini in the Nanomac department at the University of Queensland (refer to Synthesis and Characterisation of Mesostructured Titania for Photoelectrochemical Solar Cells). The main goal is to produce a photoelectrochemical cell, of greater efficiency by varying certain properties of these cells. Due to the time constraints and the difficulty of the experimental procedure only a few of properties will be modified. The specific aims of this research are as follows: Develop an understanding of the principles behind the operation of photoelectrochemical solar cells. Acquire the ability to construct Titania Dye Sensitised Solar Cells Vary the thickness of the semi-conducting Titania film in the cells. Also vary the dyeing time of this semiconductor film. Characterise the Titanium Dioxide film powder Test and compare the variations in solar cells by measuring the photovoltaic performance. The following report gives an overview of Dye Sensitised Solar Cells (DSSC) and the research previously undertaken in this field. Titanium Dioxide Solar cells are of particular focus. The report also outlines the methodology behind the research being undertaken. The focus of the literature review in this report is photovoltaic devices, which convert sunlight to energy by imitating the process of photosynthesis. From this review an understanding of the operation principles and mechanisms behind DSSCs can be formed. A brief background on photovoltaic devices is provided and the characteristics of Titanium Dioxide as a wide band-gap semi-conductor are also discussed.

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The literature review contains the procedures used to characterise important properties of Titania i.e.: specific surface area, total pore volume and the pore size distribution. Another area looked at is the quantitative measures which are used to evaluate the solar cell performance with particular emphasis on measuring the overall white light to electricity efficiency and incident photon-to-current conversion efficiency (IPCE). These photovoltaic performance measures are obtained from the current-voltage curve, which can be drawn from data obtained in the test runs. The experimental procedures and preparation techniques used in the synthesis and evaluation of nanostructured Titania thin films as wide band-gap semiconductors are overviewed. The main areas are preparation of electrodes and electrolyte, construction of DSSC and the cells testing methods. The various equipment used in the testing and construction of the cells is also detailed. The information for this report was obtained from various websites, journals and books. So far a single set of data has been obtained for the characterisation of the Titania powder used in the films. This data was obtained using a nitrogen adsorption/desorption technique in the University of Queensland Nanomac laboratories. The cell testing procedures detailed in this report will be carried out in the later half of this year with the results, conclusions and recommendations being submitted at the conclusion of the experimentation.

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2 Problem Summary
Energy is what drives the earth in this day and age. There is currently a move away from the traditional non-renewable energy sources, toward sustainable sources of energy. One obvious source of energy is the sun and solar power. Current solar cells have a low efficiency of light conversion to energy. Photo electrochemical solar cells are at the cutting edge of green energy research. One particular type of these cells is the dye-sensitised solar cell (DSSC), which works on separated processes of light absorption and charge separation. The light absorption process is performed by the dye and a wide band-gap semiconductor completes the charge separation. These cells are of particular interest in the solar energy area due to their simple and inexpensive construction. One wide band-gap semiconductor, which is widely used in this process, is titanium dioxide (TiO2). Titanium dioxide is commonly used because it is an inert, non-toxic, readily available and cheap semiconductor. The effects of different synthesis conditions on the pore and surface structures of the TiO2 thin films will be investigated. The thickness of the TiO2 film will also be varied and the effect of this on the performance of the solar cell will be monitored. An optimal film thickness will be a focus of this project. Dyeing time will also be varied to investigate the effects on the overall light to electricity efficiency of the cell. During the investigation the TiO2 film will be prepared using a sol-gel technique.

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3 Methodology:
The following steps will be undertaken during this project: 1. Research of Current Technologies Current technologies and procedures for the preparation and testing of both the Titanium dioxide film and the Dye Sensitized Solar Cell will be researched to ensure an understanding of the mechanisms involved. 2. Preparation and Synthesis of the Titanium Dioxide films The titanium dioxide films will be produced using a sol gel technique. Different thickness of these films will be produced and systematically tested in the solar cells. The effect that different dyeing times have on the efficiency of the cell will also be investigated. 3. Preparation and testing of DSSC The solar cells will be prepared and tested with the variations on the semiconductor film thickness and the dyeing time. The powder, which the films are composed of, will also be characterised. 4. Analysis of Data The data obtained from the above experiments will then be analysed. The performance of the solar cells is given by two key parameters: the incident photon-to-current conversion efficiency (IPCE) and the overall white light-toelectrical conversion efficiency. 5. Conclusion and Discussion The results will then be discussed and a conclusion for the project will be determined.

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4 Literature Review:
The focus of this literature review is mesoporous Titanium Dioxide (TiO2) Solar Cells, which convert light to energy by imitating the process of photosynthesis. These cells were invented by Prof. Michael Gratzel and have been called the first real break through in solar technology since silicon cell work (Phani, Tulloch, Vittorio and Skrybin, 2001). These cells are photo electrochemical devices, which use the dye sensitisation of a thin nanocrystalline TiO2 film in contact with an aqueous electrolyte. In recent years many experimental studies have been carried out focusing on the fundamental aspects of the dye-sensitised solar cell (Zaban et al, 1997, Schwarsburg et al, 1999, Tennokone et al. 1999 and Nazeeruddin 1993). The following review will outline the research, which has been carried out in this field. An overview of the principles and history behind the photo electrochemical cells will also be provided. The formation and modification of the nano-structured Titania film will be reviewed. The effect of varying film thicknesses will be addressed with particular emphasis.

4.1 Photonic and optoelectronic devices:

These systems involve the optical excitation of a device, leading to a useful purpose such as light-energy conversion to electricity, photochromic systems for digital display and optical sensors. In the design of these devices the molecules must be organised on a nanometric scale, controlling the arrangement, distribution, spectral and redox properties. A natural example of these devices is the process of plant photosynthesis where light is converted to energy for the plant to grow and live (Kalyanasundaram and Gratzel, 1998). There have been great efforts to understand the organization principles and the primary reactions of photosynthesis. Photovoltaic (PV) cells have been developed to mimic this

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process of photosynthesis. The process of converting light (or photons) to electricity (or voltage) is called the photovoltaic effect. Photonic and optoelectronic devices consist of three main components; the photosensitiser that absorbs light and electron donors and acceptors, which engage in electron transfer with the photosensitiser (Kalyanasundaram and Gratzel, 1998). Controlled spatial distribution and orientation of these components is achieved through the use of host supports or matrices. This control is necessary because otherwise the components would be randomly distributed throughout the system. The host support of interest in this study is Titanium Dioxide, which acts as a wide band-gap semiconductor in the dye sensitisation process.

4.2 Dye Sensitised Solar Cells (DSSC):

These cells were first developed by Gratzel et al. in 1991. They are closely related to fuel cells or batteries in that they are composed of two electrodes and an electrolyte. In batteries and fuel cells, however the energy is stored in the reactants and then released during the formation of chemical products (Kalyanasundaram and Gratzel, 1998). Photo electrochemical cells differ by using the incident light energy to drive electrochemical reactions. These cells have performance advantages over other solar cells. These advantages include the ability to perform well over a wide range of temperatures, and also to produce energy in low light and shade.

4.2.1 Cell Structure:

Dye Sensitised Solar Cells are made up of numerous layers; a collector electrode, a sensitising dye, an electrolyte solution and a catalyst coated counter electrode (see Figure 1). The collector electrode in the cell comprises of a nanocrystalline wide band-gap semiconductor film, eg TiO2, deposited on a sheet of transparent oxide conducting glass (Sommeling et al., 1998). A ruthenium complex-dye is
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chemically adsorbed onto the semiconductor film. The counter electrode is made up of a catalyst (usually platinum) attached to another piece of conducting glass. A redox pair consisting of Iodide (I-)/Triiodide (I3-) acts as an electrolyte in the cell. The light adsorbed by the dye or semiconductor produces a current through the cell, which then results in the production of electricity.

Glass
Working Electrode

SnO2 Conductor Nanocrystalline Titania Layer (TiO2)

Electrolyte
Counter Electrode

Adsorbed Complex Dye Platinum Layer

Glass

Figure 1: DSSC Structure (Phani, Tulloch, Vittorio and Skrybin, 2001)

4.2.2 Operating Principles (DSSC):

The principles of operation and key reactions involved in the operation of these cells are illustrated in Figure 2. The dye molecules are firstly photo-excited from their ground state (R) to an oxidised state (R*) by the visible light.
S + e S*

This leads to electrons being injected from the unstable dye molecule (R*) into the conduction band (CB) of semi-conductor layer, leaving an oxidised dye molecule (R+). The electron donor present in the electrolyte (I-) reduces the oxidised dye (R+) back to its ground state (R).

S+ + I - S + I

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While this is occurring the electrons, now in the conduction band collect at the back of the semi-conductor electrode (Zaban et al. 1997). They then pass through the external circuit to arrive at the conventional electrode where they effect the reverse redox reaction.

I + e- IThis process leads to the direct conversion of sunlight to electrical energy. Working Electrode TCO Photo Excited Dye ( R * / R +) eRedox Couple ( I ) eCounter Electrode

CB
Undesired Reaction Pathways

hv

( I- ) e-

e-

Semi conductor Layer

Ground ( R / R +) State Dye External Circuit e-

Error!

Figure 2: Principles of operation of DSSC (Kalyanasundaram and Gratzel, 1998) There are a number of undesired pathways in this process. The electrons in the conduction band can reduce the oxidised dye (R+) or can also regenerate the redox couple:

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S+ + e - S I + e- I

These undesired reactions compete with the forward reactions; therefore the performance of these cells depends on the kinetics of the electron transfer reactions (Kalyanasundaram and Gratzel 1998 & Kartini, 2004). One of the major limiting factors of these cells is the back electron transfer of these undesired reactions. The high back electron transfer is due to the fact the TiO2 lacks a depletion layer between the working electrode and electrolyte filling (Zaban et al. 1997).

4.2.3 Nanocrystalline Titania Dioxide Films:

Titanium dioxide is the most commonly used wide band-gap semi-conductor in the DSSC process. The nanoporous TiO2 layer has a high specific surface area; this increases the contact of the dye with light and therefore amplifies the light harvesting efficiency of the cell. The band gap of the TiO2 is approximately 3.2 eV (Skryabin, Phani and Tulloch, 1997). As a non-toxic, inert and relatively inexpensive compound titanium dioxide serves as an attractive candidate for this process. Titania is already used in a number of products including: cosmetics, paints, plastics and paper. There are three main crystalline phases of TiO2: anatase, rutile and brookite. Rutile is the easiest to produce because it is thermodynamically most stable. Rutile is used extensively in the paint industry due to its chemical stability and light scattering properties. Anatase is harder to produce but is much more photoactive and therefore is the desired DSSC phase (Park, Lagemaat and Frank, 2000). Brookite, finally is the least studied phase, however it is known to transform into rutile at fairly low temperatures (Diebold, 2002). The performance of DSSC is directly linked to the characteristics of the semiconductor layer. Important properties such as the pore size distribution, porosity and pore structure can be controlled due to recent advances in colloid chemistry.

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Advances in precursor chemistry, hydrothermal growth temperatures, binder addition and sintering conditions have also contributed to the optimisation of certain properties of the films. The transparent nature of Titania films helps with maximum sun light adsorption. Film thickness is an important factor, which has not been thoroughly studied. Thickness affects the performance of the cells because the injected electrons have to be transported across a large number of colloidal particles and grain boundaries. As the thickness increases the chance of recombination should increase. Therefore there exists an optimum film thickness to obtain a maximum photo-voltage and fill factor (Kalyanasundaram and Gratzel, 1998). One study by S.Ito et. al. has shown that the efficiency of the cells increase with the thickness of the TiO2 layer until an optimum thickness is obtained (Ito, Kitamura, Wada and Yanagida, 2003).

4.2.3.1 Preparation:
The preparation of the semiconductor film consists of two steps: the preparation of TiO2 solution and the application of this solution onto the electrode. Generally Titania is prepared using sol-gel or colloidal chemistry and precipitation. These techniques can be modified through thermal or solvo- and hydrothermal treatments (Kartini, 2004). There are two main dispersion methods commonly used to prepare the coating paste to create high efficiency DSSCs. The first (method A), involves preparing the TiO2 by precipitation in conjunction with a hydrothermal treatment and the second (method B) which is easier, uses a mortar and pestle to mix the solution (Ito, Kitamura, Wada and Yanagida, 2003). There are a number of methods which can be used to apply the TiO2, including: doctor blade, spray coating, spin coating, vapour deposition, screen-printing and reactive spluttering.

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The doctor blade technique is the most widely used in experimental procedures due to its simplicity. Two pieces of tape can be attached to the edges of the conducting glass so as a constant thickness can be obtained. After application the films are dried and calcined at approximately 450C for about 30mins (Kartini, 2004), different calcining times may produce different optical properties. Once the films have been dried and calcined their thickness is approximately 5-10m (Xagas, Androulaki, Hiska and Falaras, 1999). Studies have shown that a deposition of a second oxide layer such as TiCl4 on the nanostructured film improves the cell performance. This secondary layer may increase electron perculation through the film. Different thicknesses of the film can be obtained by either using repetitive coating or by varying the thickness of scotch tape used in the doctor blade method.

4.2.3.1.1

Repetitive Coating:

As discussed earlier the thickness of the TiO2 film has an effect on the overall efficiency of the cell. There are two repetitive coating techniques which can be used: repetitive dry (RD) coating or repetitive combusted (RC) coating. In the repetitive dry method the film is dried after each coat is deposited (Ito, Kitamura, Wada and Yanagida, 2003). When using the RC method after each coat the film is combusted at 500C for a short time. Experiments have shown that the efficiency of the cell is improved as the thickness increases see figure 3. However a peak is reached at some thickness when the structure of the film deteriorates. The RD coating technique has been the most successful one. Cavities have formed in the RD technique and it is not known whether they may be the cause of the increasing efficiency (Ito, Kitamura, Wada and Yanagida, 2003). Cavities are not formed in the RC coating technique and experimental results show that the efficiency falls at a thinner film than in RC.

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Light to electricity conversion efficiency %

Number of Layers / Times

Figure 3: Light-to-electric energy conversion efficiency vs Number of layers (repetitive combustion , repetitive dry ) (Ito, Kitamura, Wada and Yanagida, 2003) Limited studies, varying the thickness of the TiO2 film, have also been conducted by I. Kartini at the University of Queensland. An example of the current voltage curve obtained by Kartini is shown below (Figure 4).

Figure 4: I-V curves for (a) P25 single layer, multiple coats of Kartini's mesoporous Titania (b) 1 coat, (c) 2 coats, (d) 3 coats and (e) 4coats. (Kartini, 2004)
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These results show that the amount of energy produced by the cell increases with thickness until a limit is reached between 4 and 5 times coating. At 5 times coating the energy conversion drops rapidly. This rapid drop is most likely due to compression of the film.

4.2.3.1.2

Surface Modification

Much of the early research into the development of higher efficiency DSSC has centred on the complex sensitising dyes used in the process. Surface modification is also a very important factor. As mentioned earlier in section 4.2.2 one of the major limiting factors of these cells are the undesired back electron reactions. Kamat et al. found that back electron transfer could be mostly suppressed if a coupled semiconductor system was used (Kamat et al. 1998). The study by Kamat et al. shows that surface modification is an important improvement.

4.2.3.2 Characterisation of Titanium Dioxide Powders

There are a number of ways to characterise the various properties of the Titanium dioxide powders. Most of the characterisation of these powders has been undertaken in various studies. Kartinis work included characterising the powders specific surface area, total pore volume and average pore diameter. The effect of the calcining process on these particle properties was investigated, see Table 1. As can be seen the calcining process has a positive affect on the TS1 powder by increasing all of the properties investigated.

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Table 1: Properties of TSS powders and P25 (Indriana, 2004) Specific Surface Total Pore Volume Sample TS1 TS2 P25 2.70 506.90 55.74 Area (m /g) Before Calcined 50.80 73.80 N/A 0.02 0.29 0.10
2

Average Pore diameter (nm) Before 3.00 1.50 60 Calcined 3.80 6.10 N/A

(cm /g) Before Calcined 0.09 0.17 N/A

The opposite effect can be seen on the TS2 powder except the average pore diameter, which increases after calcining. The effect of the calcining process on the P25 powder has not yet been studied.

4.2.4 Dye Uptake:

The morphology of the semiconductor layer affects the dye uptake (Kalyanasundaram and Gratzel, 1998). The time at which the TiO2 film is immersed in the dye will thus effect the dye uptake and an optimum time for a certain dye should be obtained for efficient conversion of light to energy.

4.2.5 Quantitative measurements on cell Performance:

There are two key parameters used to assess the performance of solar cells, the incident photon-to-current conversion efficiency (IPCE) for monochromatic radiation and the overall white light-to-electrical conversion efficiency () (Kartini, 2004). The IPCE, which can be considered as the effective quantum yield of the device, is the ratio of the number of electrons flowing through the circuit to the number actually incident on the cell. The IPCE value is the product of three factors (Kalyanasundaram and Gratzel, 1998): the light harvesting efficiency LHE, the charge collection efficiency el and the charge injection yield inj: IPCE= (LHE)(inj)(el) (1)

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Experimentally the overall efficiency can be found using the current-voltage (I-V) curve (Figure 5). The maximum power output of the cell is obtained at the short circuit current. At this point the voltage is zero because the cell is short-circuited. The open circuit voltage point is the opposite, therefore the maximum voltage occurs but there is no current. Power production can only take place in between the open circuit voltage point and the short-circuit current point. Maximum power is produced when the product of the voltage and current is equal.

Figure 5: Typical I-V curve (PVCHAP, 1998) The short-circuit current Isc and open- circuit voltage, Voc, can be obtained from the I-V curve and then a fill factor can be calculated using the following equation (2). FF=(ImpVmp)/(IscVoc) (2) This factor is a quantitative measure of the quality of the module. The energy conversion efficiency, can now be calculated using equation (3). below. Where the Pmax is the maximum power output and Pinput is the radiation power incident on the cell. = Pmax/Pinput = (IscVocFF)/Pinput (3)

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Generally, the efficiency of current commercially produced solar cells is between 12% and 15% (Kartini, 2004). As mentioned earlier the highest experimental efficiency for DSSC using TiO2 as the semi-conductor is about 10.4%, obtained by Gratzel et al (Kalyanasundaram and Gratzel 1998 & Nazeeruddin et al, 2001). The ruthenium complex-dye was the major variable in these experiments.

4.3 Summary:
Dye sensitised solar cells are currently at the forefront of photovoltaic and solar cell research. These cells could be a valid source of green energy for the future due to their ability to directly convert sunlight to electricity and low manufacturing costs. These cells consist of a counter electrode made up of a nanocrystalline Titania Dioxide layer sensitised with a complex dye, a platinum doped working electrode with an aqueous electrolyte solution filling in between. Due to the high specific surface area of the Titania, the light harvesting ability of the counter electrode is very high. If these cells are to be a valid energy source the overall efficiency must be improved. There are many aspects of these cells, which can to be optimised to increase the energy output. The majority of research to date has focused on the ruthenium dye complex, cell make up and preparation of the Titanium solution. Surface thickness is also an important property and must be studied, so as to construct an optimal DSSC. Dyeing times of the TiO2 layer should also be modified discover its effect on the global efficiency of the cell.

5 Experimental Procedure and Preparation

The following section outlines the preparation involved in setting up the experiment and also the procedures, which are going to be used when experimentation takes place. Extensive research and practical work was

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required so as to gain an understanding of the solar cell preparation and testing procedures.

5.1 Working Electrode Preparation

Film preparation involves the production of a titanium dioxide solution and then the application of this solution onto conducting glass. The following procedure, based on the research work by Indriana Kartini at the University of Queensland, has been used to obtain a film of titanium dioxide with a few micron thickness for use in the DSSC. The Titania slurry was made of a mixture of: 1 g TiO2 powder, 4ml of distilled water, 5 drops of Triton X-100 (Sigma-Aldrich) and 2 drops of acetylacetone (Sigma-Aldrich). By adjusting the quantity of Triton X-100 and water the desired viscosity was obtained. This slurry was mixed using a mortar and pestle until uniform. The solution was then applied to a piece of F:SnO2 conducting glass (8/cm2 TCO, TEC8) and a semi-conductor film was produced. The application technique used was the doctor blade method. Before the application, the conducting glass was thoroughly cleaned using isopropanol, distilled water, acetone and a sonication process. Throughout the preparation of these electrodes the TCO glass should not be touched with bare fingers. Once the glass has been cleaned it is taped to the laboratory bench and a slip coat of the solution was applied using a glass rod. The film is then dried at room temperature for 45mins and cut with a scalpel into a 0.5*0.5cm square. The working electrode is then calcined at 450C for 30-mins. Once the calcining process is complete the film turns to a yellow colour; which is due to the temperature dependent band-gap narrowing in the titanium oxide. (Meyer, A. and Meyer,T, 1998)

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Nitrogen is used to cool the film to approximately 80C. The electrode is then immersed in a ruthenium dye solution (0.3mM N3, a Ru-red-dye, in 1:1 acetonitrile:1-butanol) for about 18 hrs (Kartini, 2004). The dye is fully adsorbed on the film when there are no white areas visible. For different thicknesses of the film the dyeing time will vary. It is very important that no water enters the dye solution. Small amounts from humidity in the air are acceptable. If any other water comes into contact with the constructed dye sensitised electrode it becomes useless. (Meyer, A. and Meyer,T, 1998) Once the dyeing is finished the electrodes are cleaned with acetonitrile to remove excess dye (Kartini, 2004).

5.1.1 Repetitive coating:

Greater thickness of the TiO2 film is produced by repeating the doctor blade method with drying at 50 C in between coats. The surface is either cooled to room temperature or kept at 50C for the next coat, this technique is referred to as repetitive dry coating. Repeating the doctor blade method with calcining inbetween each coat can also produce multiple coats. This is called repetitive combustion coating. Another method of obtaining thicker films is by using thicker layers of tape for the slip coating procedure (current tape in use is 3M Scotch Tape). Various limitations of these procedures are discussed later.

5.2 Counter Electrode and electrolyte preparation:

The counter electrode is prepared by platinising the TCO glass (Papageorgiou et al. 1997). A 5mM hexachloroplantic acid in an anhydrous isopropanol solution is slip coated over the cleaned glass and then dried in air for about 15 minutes (Nazeeruddin, 2001). The counter electrode is heated at 2C/min to 385C and left at that temperature for 15 minutes (Kartini, 2004). After this occurs the counter electrode is transferred to a closed glass vessel and cooled to room

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temperature. A hole is now drilled into the electrode, so the electrolyte solution can be injected into the cell. The electrolyte solution comprises of 0.04M I2, 0.5M LiI and 0.05M of 4-tertbutylpyridine in acetonitrile. This electrolyte solution should preferably be made in a nitrogen environment. One option for producing this electrolyte is to flush a beaker with nitrogen while mixing the solution.

5.3 Cell Construction

The cell must be constructed as soon as the electrodes have been completed as leaving the electrodes will be detrimental to the performance. Firstly the counter electrode is attached to the working electrode using a piece of 200 micron Dupont SurlynTM cut into a window to fit around the semi-conductor (Kartini, 2004). To seal these electrodes together the working electrode is heated to 80 100C and then adhered to the counter electrode using the SurlynTM. The electrolyte solution is then injected into the hole in the counter electrode and the cell is sealed using a piece of microscope slide and a square of SurlynTM. See figure 6 for a photo of the completed cell.
Electrolyte Space

Dye Sensitised Titania Film

Electrical Contact

Figure 6: Constructed Titania Dye Sensitised Solar Cell While this construction is taking place the cell must be kept out of sunlight so as not to oxidise the dye. The working electrode can only be heated for a short time to prevent oxidisation.

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To complete the cell, copper electrical contacts (0.2 mm wire) are attached using a conductive silver pen. A mixture of indium rod and silver powder is used as a solder paste. Once the electrical contacts are attached they must be cured for about 3hrs at 60-70C (Meyer, A. and Meyer,T, 1998).

5.4 Titania Dioxide characterisation

There are many properties of the Titania Dioxide which are important if an efficient cell is to be produced. Three of these properties include specific surface area, total pore volume and average pore diameter.

Figure 7: Autosorb Equipment (N2 Adsorption/Desorption) on left and degassing machine on right The nitrogen adsorption/desorption device, pictured below was used to find the values for the above characteristics. To obtain accurate results for these

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properties the sample was degassed to clean the pores in the powder before N2 adsorption/desorption.

5.5 Cell Testing Procedure

The DSSCs must first be white-light tested so as to determine the light to electricity efficiency. A Thermo Oriel Xenon lamp fitted with AM1.5D filters is used to obtain the current to voltage curves (I-V) for the cells. This lamp pictured below in the white-light testing rig (figure 8) is situated in the UQ Physics labs.

Thermo Oriel Xenon lamp

Photodiode

Monochromator

Spectra Physics 407A meter

Figure 8: Solar Cell testing equipment from UQ Physics Labs By using a Spectra Physics 407A power meter as a reference an incident power density of 100mW/cm2 can be obtained. A Keithley 2400 source meter will be used in conjunction with Labview software to record the current across a linear voltage sweep (-0.5 to 0.8V) over the Titania film in the cell (active area of

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0.25cm2). The efficiency () of the cells can now be calculated using equation (3) in section 4.2.5 of this report. (Kartini, 2004)

Figure 9: Solar Cell testing rig on right and computer set up for testing on left. The incident photon-to-current conversion efficiency (IPCE) must also be found experimentally. The photocurrent action spectra can be found by directing the output of the Thermo Oriel lamp into a monochromator (Yvon Jobin HRS2). The monochromator must be calibrated against the NIST standard for Xe. Turning the source lamp on for an hour before testing is started can ensure thermal stability. (Kartini, 2004) The quantum efficiency can be obtained as a function of wavelength if the monochromator is coupled onto the test rig. Before this is undertaken the light source is calibrated using a silicon photodiode (Newport 818-UV) to find the amount of photons incident on the cell. The testing rig pictured in figure 9 was made in the University of Queenslands Physics department and is used for all of the solar cell testing.

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6 Results:
After experimenting with different repetitive coating techniques the most effective way of obtaining a smooth TiO2 layer is by using a repetitive drying or combustion coating method. Testing must be undertaken on these different films to find an optimum technique for maximum efficiency. Changes in the tape thickness have also been used to obtain a thicker coat. At certain thicknesses the surface of the films has cracked. Different dilutions of the TiO2 slurry have been used attempting to reduce the degree of cracking. With dilute solutions the thickness can be varied by smaller increments. The only results, which have been obtained so far for the project, are for the characterisation of the commercial grade P25 Titania powder before and after calcining. As explained above a N2 adsorption/desorption technique was used to characterise certain properties of the powder. Table 2: Structural Properties obtained for P25 commercial powder (obtained from Autosorb) Specific Total Pore Average pore Surface Area Sample Volume (cm3/g) Diameter (nm) (m2/g) P25 before 53.79 0.128 9.559E+01 calcining P25 after calcining 53.88 0.313 2.327E+02

The curve below is a type II Isotherm obtained from the Autosorb equipment in the Nanomac laboratories at the University of Queensland.

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450

400

350

Partial Pressure (P/Po)

300

250

200

150

100

50

0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Volume (cm3/g STP) adsorption P25 adsorption calcined P25

Table 3: N2 Adsorption Isotherm for the commercial grade P25 powder before and after calcining.

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7 Discussion:
Currently, the most promising area of solar cell research is Dye Sensitised Solar Cells (DSSC). Titania Dioxide is the most widely researched semi-conductor layer in these cells. Two areas that need to be addressed in the production of Titania DSSC are the film thickness and dyeing times. The above report is a preliminary study of these cells. The following goals have been achieved:

A high understanding of the mechanisms behind the operation of the Titania DSSC has been formed. An overview of the research, which has been undertaken in this field. The procedures required in preparation of the nanocrystalline TiO2 layer have been detailed. The step by step methods used to construct a DSSC test cell have also been outlined Test equipment and techniques have been researched and a comprehensive testing process has been formulated based on former work by Kartini, 2004.

Analysis methods comparing different variations in the cell preparation have been varied and analysed. The thickness of TiO2 semiconductor film have been varied and analysed. Results for the characterisation of the P25 before and after the calcining process have been obtained using N2 adsorption/desorption.

A number of problems were encountered in the experimental lead up work. Difficulties in the production of uniform semi-conductor films were one problem. When producing the films using repetitive coating techniques the surface of the TiO2 forms cracks and fissures. The effect of these fissures on the efficiency of the cell is not yet known but they may be beneficial in helping the dye adsorption

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into the films. Different dilutions of the TiO2 slurry used to create the films have been experimented with so as to minimise the cracking in the films and to provide a smaller variation in the thickness. Problems in the production of smooth dilute solutions were also encountered. Longer or better mixing techniques will overcome this inconvenience. There have been difficulties in the construction of the cells. When joining the electrodes together the SurlynTM did not adhere well to the glass. One way to overcome this problem was to use an adhesive glue. Other adhesives, which could be used are Amosil 4, SX 1170-25 (25 micron thickness) or SX 1170-60 (60 micron thickness). (Meyer, A. and Meyer,T, 1998) Troubles were also encountered injecting the electrolyte into the single hole. These are due to a pressure build up in the space between the electrodes. One way of avoiding this problem would be to drill two holes so as to release the pressure while the electrolyte is injected. As can be seen from the results in section 6 of this report the particle characteristics of the commercial grade P25 powder do not change a great deal after the calcining process. The major change is the increase in the average pore diameter of the powder. The following work is yet to be completed for this project:

Further cell construction including testing different methods for the production of thicker films. Cell testing with the variations in film thickness and dyeing time. Analysis of the results. Recommendations for further research. Some surface modifications will also be undertaken, time-permitting.

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8 References:
Deb, S.K., Ferrere, S., Frank, A.J., Gregg, B.A., Huang, S.Y., Nozik, A.J., Schlichthorl, G. and Zaban, A (1997). Photochemical Solar Cells Based on Dye-Sensitization of Nanocrystalline TiO2. National Renewable Energy Laboratory (NREL), Golden, Colorado. Diebold, U. (2002) .Structure and properties of TiO2 surfaces: a brief review. Appl. Phys. A. 76, 17. Ito, Seigo., Kitamura, T., Wada, Y. and Yanagida, S. (2003). Facile fabrication of mesoporous TiO2 electrodes for dye solar cells: chemical modification and repetitive coating. Elsevier. Solar Energy Materials & Solar Cells. 76, 3-13. Kalyanasundaram, K. and Gratzel, M. (1998). Applications of functionalised transition metal complexes in photonic and optoelectronic devices. Elsevier Science. Kartini, I. (2004). Synthesis and Characterisation of Mesostructured Titania for Photoelectrochemical Solar Cells. Nanomac University of Queensland. Meyer, A. and Meyer,T. (1998). Dye Solar Cell Assembly. [Online] Available at http://www.solaronix.ch/products/DSC/Instructions.html Nasr, C. Kamat, P.V. and Hotchandani, S. (2002). J. Phys. Chem. B 102, 10047. Nazeeruddin, M.K., Kay, A. Rodicio, I. Humphry-Baker, R. Muller, E. Liska, P. Vlachopoulos, N. and Gratzel, M. (1993). J. Am. Chem. Soc. 115, 63826390. Nazeeruddin, M.K., Pechy, P., Renouard, T., Zakeeruddin, S.M., HumphryBaker, R., Comte, P., Liska, P., Cevey, L., Costa, E., Shklover, V., Spiccia, V., Deacon, G.B., Bignozzi, C.A. and Gratzel, M.(2001). Engineering of efficient panchromatic sensitisers for nanocrystalline TiO2based solar cells. J.Am.Chem.Soc. 123, 1613-1624.

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Papageorgiou, N., Maier, W.F., and Gratzel, M. (2001). An Iodine/ Triiodide Reduction Electrocatalyst for Aqueous and Organic Media. J. Electrochem. Soc., 144(3), 876. Park, N.G., J. van de Lagemaat, and A.J. Frank. (2000). Comparison of DyeSensitized Rutile- and Anatase-Base TiO2 Solar Cells. J.Phys. Chem., 104, 8989-8994. Phani, G., Tulloch, G., Vittorio, D. and Skryabin, I.(2001)., Titania solar cells: new photovoltaic technology. Renewable Energy. Pergamon. PVCHAP. www.cs.jmu.edu/common/projects/UNPEPP/PVCHAP.html 1998, JMU, Virginia. Schwarsburg, K., Willig, F.(1999). J. Phys. Chem. B, 103. 5743. Skryabin, I.,Phani, G. and Tulloch, G.(1997). STA Titania Nanocrystalline Solar Cell Project. Sustainable Technologies Australia. Sommeling,P.M., Spth, M., J.A.M. van Roosmalen., Meyer,T.B., Meyer, A.F., and O. Kohle.(1998). Dye-Sensitised Nanocrystalline TiO2 Solar Cells on Flexible Substrates. ECN Solar and Wind Energy. Tennokone, K. Kumara, G.R.R.A., Kottegoda, I.R.M., Perera, V.(1999). Chemistry. Commun, 15. Xagas, A.P., Androulaki, E., Hiskia, A. and Falaras, P.(1999). Preparation, fractal surface morphology and photocatalytic properties of TiO2 films Thin Solid Films. 357, 173. Zaban, A., Ferrrere, S., Sprague, J. and Gregg, B.A.(1997). J. Phys. Chem. B. 101,55.

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