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Recent studies suggest that the performance of dye-sensitised solar cells (DSC) has appeared to have reached a limit, therefore solar cells based on semiconductor materials, such as extremely thin absorber (ETA) solar cells and tandem solar cells are currently the subject of intense research in the framework of low-cost photovoltaic devices as sources of harvesting sunlight to generate electricity. Generally, semiconductor solar cells have been divided into two different types, namely anodic and cathodic type solar cells. Extensive research and development work has been focused on anodic semiconductor sensitised solar cells to date. In contrast, the cathodic semiconductor sensitised solar cells have received no attention which is very surprising. Developing the cathodic semiconductor sensitised solar cell concept is very important in the development of tandem solar cells as well as other new solar cell configurations. The main reason for the lack of research in this area was due to the rarity of p-type semiconductor materials, which made it difficult to find suitable materials to match the energy band edges for cathodic semiconductor sensitised solar cells (CSSC) as well as solid-state cathodic semiconductor solar cells (SS-CSSC). The primary aim of this thesis was to construct cathodic semiconductor sensitised solar cells as well as their solid-state analogues (SS-CSSC). The work conducted within this doctoral study presents state-of-art materials and thin film processing/preparation methods, their characterisation and developing CSSCs and SS-CSSCs employing such films in cascade configurations. No reports have been published in the literature on SS-CSSC to date. The first stage of this thesis is focused on optimising the morphology and the texture (porosity) of the CuI and NiO semiconductor photocathode, by the introduction of new deposition methods namely, pulsed-electrodeposition (PED) and Aerosol-Assisted Deposition (AAD) and Aerosol-Assisted Chemical Vapour Deposition (AACVD). The electrodes prepared by employing the methods mentioned above and controlling the deposition parameters systematically, we have achieved significant improvement in the film morphology and the texture of the deposited films. The resulting electrodes showed excellent improvement in the photoelectrochemical performance which made it suitable for application in construction of both CSSC and SS-CSSC. The photoelectrochemical performance of the electrodes can be seen clearly through the photocurrent density data. For the case of bare CuI, the PEC performance of electrode prepared by the AAD and PED compared against that of continuous-electrodeposition (ED) electrodes. The photocurrent density achieved for the electrodes prepared by AAD and PED was reported around 175 and 75 µAcm-2 respectively which are way higher than the ED case. At the second stage of this study, the work focused on fabrication and characterisation of the CSSCs. Cathodic sensitised PEC solar cells (CuI/Cu2S/(Eu2+/Eu3+) and NiO/Cu2S/(I3-/I-)) were fabricated by deposition of p-Cu2S on the texture controlled CuI and NiO photocathodes. The morphological properties of the photocathode, in particular layer thickness, particle size and film porosity, play an important role in the PEC performance of CSSCs. Optimisation of these parameters led to increased adsorption of the Cu2S light harvester on the photocathode s surface. As a result, the charge injection from Cu2S to the wide band gap photocathode material (CuI and NiO) was significantly improved. Due to this, the CSSC performance showed significant improvement as semiconductor sensitised cathodic solar cells (CSSC). The IPCE and photocurrent density of the CSSC achieved in this study was around (19 and 7 %) and (1 and 0.5 mAcm-2) for the CuI/Cu2S and NiO/Cu2S electrodes respectively. Finally, the SS-CSSC has been fabricated by employing n-Fe2O3 electron transport layer. The construction of SS-CSSC for the first time using the n-Fe2O3 electron transport layer (CuI/Cu2S/Fe2O3 and NiO/Cu2S/Fe2O3) allowed us to study the materials, optical and photoelectrochemical properties of this device. Under AM 1.5 illumination, the SS-CSSC shows a photocurrent density of 6 and 9 µAcm-2 for CuI/Cu2S/Fe2O3 and NiO/Cu2S/Fe2O3 solar cells, respectively. The results of this work indicated low performance for both SS-CSSC compared to CSSC results, due to the lack of adsorption between the absorber and Fe2O3 electrode. However, this study proved the concept of SS-CSSC based on semiconductor material, which is valuable for the future work of cathodic semiconductor sensitised solar cells as well as solid-state tandem solar cells.

<p>Dye-sensitised solar cells (DSC) have attracted much attention during the last few years due to their high efficiencies and their potentially low production costs. The technology is based on a thin layer of nano sized, high band gap (3.2 eV) TiO2 film. A Ru containing dye (from hereon called the Ru dye) is chemisorbed onto the TiO2 film. This combination acts as the working electrode. The counter electrode consists of a platinum layer which is the catalyst for the regeneration of the Iodine/Iodide electrolyte. The work that is presented here is focused on the results that were obtained during studies of the performance of the DSC under certain reverse bias conditions. When one cell in the series connection in a module is shaded, the current will pass this cell in reverse bias. In such a case the shaded cell will be subjected to a voltage in the reverse direction coming from the other lit cells in the module. This reverse voltage could permanently modify or damage the cell if it is not properly protected. Although the work is focussed on the chemical stability of the dye, various techniques were employed to determine the physical changes in the cell. It was found that a cell that was subjected to a reverse bias of 2 V for 500 min showed a 58% recovery and a cell that was subjected to 4.5 V reverse bias was irreversibly damaged. The UV-vis spectra showed a blue shift (higher energy), the Raman showed no peak at 1713 cm-1 (which indicates the absence of free carboxylate groups) and the FT-IR showed the disappearance of the NC-S absorption band at 2100 cm-1. The combined conclusion is that the &ndash / NCS ligand has been depleted and replaced with I3- ions. When measuring the impedance, the Nyquist plots showed an increase in the charge transfer resistance at the counter electrode when subjected to a reverse bias potential of 2 V. This is confirmed by the Bode plots. This indicates a partial oxidation of the Pt catalyst on the counter electrode. It can therefore be stated with confidence that the changes in the cell after being subjected to a reverse bias potential of 2 V for 500 min are changes on the -NCS bonds on the Ru dye as well as the Pt in the counter electrode.</p>

<p>Dye-sensitised solar cells (DSC) have attracted much attention during the last few years due to their high efficiencies and their potentially low production costs. The technology is based on a thin layer of nano sized, high band gap (3.2 eV) TiO2 film. A Ru containing dye (from hereon called the Ru dye) is chemisorbed onto the TiO2 film. This combination acts as the working electrode. The counter electrode consists of a platinum layer which is the catalyst for the regeneration of the Iodine/Iodide electrolyte. The work that is presented here is focused on the results that were obtained during studies of the performance of the DSC under certain reverse bias conditions. When one cell in the series connection in a module is shaded, the current will pass this cell in reverse bias. In such a case the shaded cell will be subjected to a voltage in the reverse direction coming from the other lit cells in the module. This reverse voltage could permanently modify or damage the cell if it is not properly protected. Although the work is focussed on the chemical stability of the dye, various techniques were employed to determine the physical changes in the cell. It was found that a cell that was subjected to a reverse bias of 2 V for 500 min showed a 58% recovery and a cell that was subjected to 4.5 V reverse bias was irreversibly damaged. The UV-vis spectra showed a blue shift (higher energy), the Raman showed no peak at 1713 cm-1 (which indicates the absence of free carboxylate groups) and the FT-IR showed the disappearance of the NC-S absorption band at 2100 cm-1. The combined conclusion is that the &ndash / NCS ligand has been depleted and replaced with I3- ions. When measuring the impedance, the Nyquist plots showed an increase in the charge transfer resistance at the counter electrode when subjected to a reverse bias potential of 2 V. This is confirmed by the Bode plots. This indicates a partial oxidation of the Pt catalyst on the counter electrode. It can therefore be stated with confidence that the changes in the cell after being subjected to a reverse bias potential of 2 V for 500 min are changes on the -NCS bonds on the Ru dye as well as the Pt in the counter electrode.</p>

Organic solar cells are cheaper and much easier to fabricate than the conventional inorganic solar cells, but they suffer from low efficiencies due to low carrier mobilities in organic films. In this study Copper Phthalocyanine (CuPc) and Buckminster Fullerene (C60) based Schottky diodes were fabricated on ITO coated glass substrates to study their performance and a study of the effect of thickness on the cell parameters of CuPc Schottky diodes was made. Also, TiO2 based devices were studied to see the effect of TiO2 layer on the cell parameters. The J-V curves were analyzed for series resistance, diode ideality factor and reverse saturation current density. The devices were also characterized by SEM and XRD measurements.

The aim of this study was to understand the properties of glass/TCO/CdS/CdTe/metal solar cells, the CdS and CdTe being grown by aqueous electrodeposition. Deposited films and completed cells were characterised using electrical, structural and optical techniques. This report describes the production of well-formed polycrystalline CdS and CdTe with well defined XRD peaks and band gap. Experiments were performed to investigate the pre-conditioning of the CdTe bath on the overall cell performance. Pre-conditioning the CdTe deposition bath was found to improve the Voc value of the completed devices. It has been known for some time that treating the CdTe layer of a CdS/CdTe solar cell with chlorine brings about significant improvements in the efficiency of these devices. This report presents results on a systematic variation of the chlorine concentration within a CdTe deposition bath. Solar simulated I-V measurements of completed devices clearly show that the addition of CdCl[2] to the CdTe deposition bath significantly improved the efficiency values for the glass/TCO/CdS/CdTe/metal devices. The electrical parameter most significantly affected by the addition of chlorine is the J[sc] value. In terms of the Voc performance of the device, this investigation showed that there was a trend of improving Voc with increasing chlorine concentration. Addition of chlorine also produces improvements in the preferred orientation of CdTe films as measured by XRD. Optical absorption results showed a correlation that the minima of the band gap vs. chlorine concentration graph for annealed samples matches up with the maximum in the efficiency and J[sc] graphs. To investigate whether this phenomenon was specific to chlorine or was displayed by other elements, similar experiments were performed with no chlorine inclusion but varying the indium concentration in the deposition bath. Solar simulated I-V measurements of completed devices clearly show that the addition of In[2](SO[4])[3] to the CdTe deposition bath significantly reduced the efficiency values for the glass/TCO/CdS/CdTe/metal devices. The electrical parameter most significantly affected by the addition of indium is the J[sc] value. The addition of indium also had a detrimental effect on the preferred orientation measured by XRD.

Dye-sensitized solar cell (DSSC) has attracted increasing interest as a promising hybrid organic-inorganic solar cell. At the heart of the device is a photosensitizer, which is anchored onto a wide-bandgap semiconducting metal oxide. It harvests solar light and transfers the energy via electron transfer to a suitable material (e.g. TiO2) to produce electricityas opposed to chemical energy in plant. The topic of this thesis focuses on the design and synthesis of metal-free organic dyes for applications in DSSCs. Specific attention has been paid to the correlation between the molecular structures and physical properties, as well as their performances in DSSCs. Chapter 1 presents the major components and working principle of DSSC, following by a brief overview of the development of organic dyes and their application in DSSCs. In chapter 2, we have designed two types of new phenothiazine-based dyes to investigate the positioning effect a donor group on the cell performance. The structural features of a donor aryl group at the C(7) position of phenothiazine core extend the π-conjugation of the chromophore and efficiently suppress the dye aggregation on TiO2 film. As a result, Type 1 dyes have better light harvesting properties in contact with TiO2 films, and give much better photovoltaic performance than Type 2 dyes. Chapter 3 presents the synthesis and characterization of a series of simple phenothiazine-based dyes, in which, a linear electron-rich (4-hexyloxy)phenyl group at C(7) of the phenothiazine periphery as the donor, and an alkyl chain with different length at N(10). The dye molecules show a linear shape which is favorable for the formation of a compact dye layer on the TiO2 surface, while their butterfly conformations can sufficiently inhibit molecular aggregation. Moreover, the alkyl substituents with different chain length at N(10) could further optimize the performance through complete shielding the surface of TiO2 from the Iˉ/I3ˉ electrolyte. Under simulated AM 1.5G irradiation, the PT-C6 based DSSC produces a short-circuit photocurrent of 15.32 mAcm−2, an open-circuit photovoltage of 0.78 V, a fill factor of 0.69, corresponding to a power conversion efficiency (PCE) of 8.18%. Moreover, we designed a stepwise approach for co-adsorption of the organic dye PT-C6 with a porphyrin dye (ZnP) for DSSCs. Upon optimization, the device made of the PT-C6 + ZnP system yielded Jsc = 19.36 mA cm-2, Voc =0.735 V, FF = 0.71 and η = 10.10%. In chapter 4, we further developed five organic dyes appended with T, TT, E, ET, or EE (T and E denote thiophene and 3,4-ethylenedioxythiophene (EDOT), respectively) on the C(7) atom of phenothiazine core as electron donors. We have also analyzed the structure-performance corelations of dye molecules in the aspect of dye aggregation, electron injection, dye regeneration and interfacial charge recombination of electrons with electrolytes and/or oxidized dye molecules, through DFT calculation, impedance analysis and transient photovoltage studies. In chapter 5, we extended our studies by using phenothiazine as a building block to construct 3D bulky organic dyes. We systematically investigated the influence of 3D bulky substituents on dye aggregation and charge recombination, as well as photovoltaic performance of DSSCs. The molecular design strategy demonstrates that high Voc can be realized by employing 3D-phenothiazine dyes featuring a bulky substituent, such as, hexylcarbazole and dihexylfluorene units. Impressively, the co-adsorbent-free DSSCs based on dye TP3 exhibits a photovoltaic performance with efficiency up to 8.00 %. In order to realize a panchromatic absorption and further enhance the energy conversion efficiency of DSSCs, we also designed a stepwise approach for co-adsorption of the organic dye TP3 with a NIR dye YR6 for co-sensitized DSSCs. Upon optimization, the device made of the TP3 + YR6 system yielded Jsc = 19.18 mA cm-2, Voc =0.721 V, FF = 0.712 and η = 9.84 %. The power-conversion efficiency is the highest reported efficiency for a squaraine dye-based co-sensitized panchromatic DSSCs. From chapters 6 and 7, a series of new simple panchromatic dyes based on thiadiazolo[3,4-c]pyridine (PyT) have been designed for panchromatic DSSCs. These new organic dyes exhibit broad absorption spectrum in the range of 300~850 nm and high molar extinction coefficients. The electrochemical analyses demonstrate that the incorporation of the auxiliary electron-deficient thiadiazole[3,4-c]pyridine unit can fine-tune the HOMO and LUMO energy levels and red-shift the absorption spectra to NIR region. The overall conversion efficiencies of liquid-electrolyte DSSCs based on these sensitizers range from 0.46 to 6.30 %. We draw some conclusions in chapter 8 together with the outlooks in DSSCs

This thesis describes the synthesis and characterization of a series of photosensitizers, transition metal-containing polymers and small organic molecules for dye-sensitized solar cells and organic solar cells. To begin with, a brief overview on the background of dye-sensitized solar cells (DSSCs) and organic solar cells was presented in Chapter 1. In Chapter 2, a series of novel donor-acceptor-π-acceptor bithiazole-based and fluorenone-based organic dyes for dye-sensitized solar cells were successfully synthesized and fully characterized. We discovered that the performance of the photovoltaic devices depends significantly on the nature and strength of the electron-donating end group along the conjugated main. Some of the materials have been found to show higher power conversion efficiency of 4.71% (Voc = 565 mV, Jsc = 11.71 mA cm–2, FF = 0.71) under AM 1.5 irradiation (100 mW cm–2). In Chapter 3, ten novel donor-donor-π-acceptor organic dyes for dye-sensitized solar cells have been synthesized and applied for the fabrication of DSSCs, including six dibenzothiophene-based photosensitizers and carbazole-based photosensitizers. All the dyes have efficient charge injection from the excited sensitizer molecule to TiO2 conduction band and can provide ample driving force for efficient dye regeneration best overall light to electricity conversion efficiency of 5.28% (Voc = 0.70 V, Jsc = 11.06 mA cm–2, FF = 0.68) under AM 1.5 irradiation, which reached 73% with respect to that of an N719-based device fabricated under similar fabrication conditions. Besides, nine novel di-anchoring organic sensitizers employing two different electron-donating cores, which are the fluorene and carbazole units, and two symmetrical anchoring cyanoacrylic acid (acceptor) termini have been synthesized and studied for their applications in DSSCs in Chapter 4. In Chapter 5, four new platinum polyyne polymers were prepared via the Sonogashira-type dehydrohalogenation reaction between the ethynyl precursor and trans-Pt(PBu3)2Cl2. All of the polymers are air-stable and well characterized by different spectroscopic methods and photophysical measurements. Their photovoltaic behaviors were fully investigated. Their model compounds were also prepared and studied. In Chapter 6, a series of new organic small molecules were designed and synthesized comprising head-to-head coupled heylthiophene, dithienosilole and dithienogermole units. They exhibited broad absorption peaks with favorable spectral overlap with the solar spectrum. These seven small molecules have been applied to presented. Among these molecules, the highest PCE of 4.93% was achieved with a Voc = 0.79 V, Jsc = 1.22 mA cm-2 and FF = 0.51 under illumination of an AM 1.5 solar cell simulator. Finally, Chapters 7 and 8 present the concluding remarks and the experimental details of the work described in Chapters 2−6

Philosophiae Doctor - PhD / Dye-sensitised solar cells (DSC) have attracted much attention during the last few years due to their high efficiencies and their potentially low production costs. The technology is based on a thin layer of nano sized, high band gap (3.2 eV) TiO2 film. A Ru containing dye (from hereon called the Ru dye) is chemisorbed onto the TiO2 film. This combination acts as the working electrode. The counter electrode consists of a platinum layer which is the catalyst for the regeneration of the Iodine/Iodide electrolyte. The work that is presented here is focused on the results that were obtained during studies of the performance of the DSC under certain reverse bias conditions. When one cell in the series connection in a module is shaded, the current will pass this cell in reverse bias. In such a case the shaded cell will be subjected to a voltage in the reverse direction coming from the other lit cells in the module. This reverse voltage could permanently modify or damage the cell if it is not properly protected. Although the work is focussed on the chemical stability of the dye, various techniques were employed to determine the physical changes in the cell. It was found that a cell that was subjected to a reverse bias of 2 V for 500 min showed a 58% recovery and a cell that was subjected to 4.5 V reverse bias was irreversibly damaged. The UV-vis spectra showed a blue shift (higher energy), the Raman showed no peak at 1713 cm-1 (which indicates the absence of free carboxylate groups) and the FT-IR showed the disappearance of the NC-S absorption band at 2100 cm-1. The combined conclusion is that the - NCS ligand has been depleted and replaced with I3- ions. When measuring the impedance, the Nyquist plots showed an increase in the charge transfer resistance at the counter electrode when subjected to a reverse bias potential of 2 V. This is confirmed by the Bode plots. This indicates a partial oxidation of the Pt catalyst on the counter electrode. It can therefore be stated with confidence that the changes in the cell after being subjected to a reverse bias potential of 2 V for 500 min are changes on the -NCS bonds on the Ru dye as well as the Pt in the counter electrode. / South Africa