No description available.

The naturally occurring mineral of Cu2ZnSnS4 (CZTS) is a promising alternative absorber layer for thin film based photovoltaic devices. It has the remarkable advantage that it consists of abundant, inexpensive and non-toxic elements compared to its crystallographically related and highly successful counterparts: the Cu(In,Ga)(S,Se)2 (CIGSSe) and CuIn(S, Se)2 (CISSe) material systems. Therefore, there is real commercial potential for reduced material costs and improved device efficiencies. A two-stage high throughput combinatorial process for the fabrication of Cu-Zn-Sn-S thin film libraries is presented, which consists of either sequentially stacking or co-depositing Cu,Sn and Zn precursor layers by DC magnetron sputtering followed by a sulphurisation process. Sputtering conditions and target-substrate geometry are developed to give compositionally graded Cu-Zn-Sn precursor layers spanning a wide spatial region around the point of stoichiometry. Conversion into Cu-Zn-Sn-S libraries is achieved by thermally evaporating a uniform layer of sulphur directly onto the metal alloy and annealing the sample at 500 °C in a furnace. Effects of the precursor composition on the structural properties of the films prior to the incorporation of sulphur are investigated. The sulphurised libraries are then studied by Scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy as a function of composition, to assess the effects on morphology and phase formation. Observations of changes in lattice parameters and crystallinity are clear. The opto-electronic and electrical properties of the CZTS film libraries are measured using photoconductivity and hot point probe techniques, respectively. Changes in the band gap and conductivity type are studied as a function of atomic ratios. Based on high performing compositions, devices have been fabricated with the highest achieving cell at 1.26 %. The observations are discussed in the context of the particular compositions and synthesis conditions, and recommendations are made for further work.

Theoretical considerations for the use of chalcopyrite ternary I-III-VI₂ compounds in heterojunction photovoltaic conversion devices are presented, followed by an in-depth study of the structural, optical, and electrical characteristics of multi-source evaporated CuGaSe₂ thin films as determined by processing. Film composition was identified as the primary variable for affecting the microstructure and optical-electrical behavior of the films. Film composition was in turn dependent upon elemental flux rates and substrate related effects. Films deposited on glass and bare alumina substrates were richer in selenium than films deposited on molybdenum coated substrates. Cu-poor, near stoichiometeric, and Cu-rich compositions were obtained by varying the Cu/Ga flux ratio. Cu-poor films deposited on bare ceramic substrates were characterized by secondary impurity phase content and a tendency for cubic CuGaSe₂ formation. The cubic nature of optically thin films deposited on glass was substantiated by a lack of crystal field splitting of the valence band as observed by optical absorption measurements. Cubic-tetragonal phase behavior was monitored on optically opaque samples by observation of intensity-independent (112)/(111) x-ray diffraction peak shifts. Cu-poor films on glass were also characterized by surfaces pitting at substrate temperatures in excess of 450°C which may be related to the high surface energy of gallium. Cu-poor films deposited on molybdenum coated alumina substrates exhibited less impurity phase formation and were largely single-phase tetragonal CuGaSe₂. Cu-rich films on all substrates contained CuₓSe impurities and tetragonal CuGaSe₂.

A one-dimensional analytical model of dark current has been developed to facilitate the investigation and analysis of dark current from gate-controlled photovoltaic InSb arrays. The applied gate voltage is an essential parameter in the model. The expressions relating this parameter to surface potential are derived separately for the cases of accumulation and depletion at the surface of n-type InSb material under the gate. In addition, the measured dark current is compared with that from the analytical model, and the discrepancy is discussed in terms of the intrinsic carrier concentration, surface recombination velocity, and geometry of the array. The components of dark current are mainly associated with surface state generation-recombination, field induced tunneling, and the depletion region from the bulk and surface. The experimental results are obtained at temperatures between 30K and 40K.

No description available.

M.Sc. / Current solar cell research programmes in general aim to develop a high conversion efficiency photovoltaic (PV) module from high quality thin films. In this study, Cu (In,Ga)Se2 (CIGS) thin films were grown and characterized. These films were grown by selenization of Cu-In-Ga precursors. These precursors were prepared by co-sputtering In and (Cu, Ga). All the precursors were grown on Mo coated soda lime glass substrates. The selenization was conducted under different conditions in Ar/H2Se atmosphere, i.e. taking different values of flow rate of H2Se (5.00, 1.00, 0.25 mol%) in Ar, temperature (350, 450, 550 ºC) and time (10, 20, 30, 40, 50, 60 min). At each selenization condition, two samples were placed at different positions in the chamber. The structural properties of the produced films were analyzed by the techniques of X-ray Diffraction (XRD) for phases, Scanning Electron Microscopy (SEM) for morphology and Energy Dispersive Spectroscopy (EDS) for the bulk composition. The effect of temperature variation, the effect of flow rate variation and the effect of time variation were analyzed by comparing the structural properties as analyzed by the techniques mentioned. All in all this specific study delivers important information about the sensitivity of Cu(In,Ga)Se2 (CIGS) thin films to the temperature, gas flow rate and exposure time of the selenization step. / Doctor C.A. Engelbrecht Professor Vivian Alberts

Organic semiconducting materials have been attracted considerable attention as a promising technology for the next generation flexible electronic devices, such as solar cells and field-effect transistors because of their advantages of low-cost, structural versatility and flexibility. Many organic semiconducting materials have been developed in recent years. In this thesis, four pi-conjugated building blocks based on benzodithiophene and quinoxalinedithienothiophene were applied to develop novel photovoltaic materials, including donor-acceptor alternating copolymers as a donor material for polymer solar cells, photosensitizers for dye sensitized solar cells, small molecule hole transporting materials for perovskite solar cells and small molecule acceptors for organic solar cells. A comprehensive review of current development of organic photovoltaic materials was presented in Chapter 1. In Chapter 2, a series of D-A copolymers (PBB-n) based on 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole and 4,5-bis((2-ethylhexyl)oxy)benzo[2,1-b:3,4-b'] dithiophene attached with different solubilizing side-chains were designed, synthesised and characterized. In general, PBB-n polymers showed good absorption in the region of visible light and UV region, indicating such polymers are a promising light harvester. Also, PBB-n exhibited suitable energy levels, suggesting that they could be applied as the donor materials in polymer solar cells. PBB-n also exhibited various extent of aggregation behaviour. Chapter 3 described syntheses and the fluorination effect of two series of fluoro-substituted PBB-n copolymers, namely PfBB-n and PffBB-n on optical, electrochemical, and optoelectronic properties. Among them, PfBB-n series was characterized with photovoltaic performance. The champion devices fabricated from PfBB-12 showed a PCE as high as 9.7%, with a Voc of 0.92 V, a Jsc of 16.60 mA/cm-2 and a FF of 63.49%. Cells fabricated from other PfBB-n copolymers also exhibited good PV performance with PCE ranging from 7.4 - 8.5%. For PffBB-n polymers, temperature-dependent aggregation behaviour was exploited by modulating the coating temperature during device fabrication. PSC devices based on PffBB-n exhibited good PV performance with PCE ranging from 7.4% to 9.9%. Among which, PffBB-14 provided the most promising PV performance with PCE of 9.9%, a Voc of 0.92 V, a Jsc of 16.8 mA/cm-2 and a FF of 64.36%. Electron deficient conjugated structure was seldom used as the π-bridge in metal-free photosensitizers. In Chapter 4, four novel organic photosensitizers, namely QC5-m and PC5-n were designed with an electron deficient π-bridge. Typical sandwich-structured DSSCs based on the newly developed photosensitizers exhibited promising photovoltaic performance with PCE ranging from 5.23 - 7.77 %, with a maximum Jsc as high as 15.63 mA cm-2. These results suggest that the use of electron deficient π-bridge provides alternative approach to construct efficient organic photosensitizers. Chapter 5 and Chapter 6 described the design, synthesis and investigation of novel hole-transporting materials and electron acceptor materials based on benzo[2,1-b:3,4-b']dithiophene-4,5-dione derived building blocks as potential organic photovoltaic materials for solar cell applications. Keywords: organic photovoltaic materials, photosensitizers, polymer solar cell, electron acceptor, hole-transporting materials.

A Thesis submitted to the Faculty of Science, School of Chemistry at University of the Witwatersrand, in fulfilment of the requirements for the degree of Doctor of Philosophy. Johannesburg, 2015. / Photovoltaic cells offer a good alternative to the fossil fuels. Several approaches are being analysed in order to have solar cells that are capable to conquer the energy market all around the world. Quantum dots (QDs) have already proven features that can be taken into account to improve the properties of solar cells. Metal selenide nanoparticles (NPs) possess semiconducting behaviours that can vary with their structural and optical properties evolving from their synthesis. The reaction parameters such as the method, time, solvent and precursors can affect the growth and nucleation of particles and thus impose on the properties of the synthesized materials. The performance of solar cells made of the synthesized metal selenides will then be dependent upon the properties of the NPs used as active layer. Furthermore, the electrical current generation also depends on the structure of the deposited active layer and its interface with other films to be assembled for the device. The binary copper selenide, ternary copper indium selenide (CISe), quaternary copper indium gallium selenide (CIGSe) and quinary copper zinc tin sulphur selenide (CZTSSe) NPs were synthesized via conventional colloidal method (CCM) and microwave assisted method (MAM). The MAM has a particular interest as it is less time consuming and can easily be a large scale synthesis. Photovoltaic devices were fabricated from the synthesized materials as proof of concept for photovoltaic activities. The CCM was used to optimize various parameters for the synthesis of each type of the chalcogenide materials as this is easily controllable than the ones from the sealed vessel from MAM. The dependency of properties of all copper chalcogenide NPs on the time, precursor concentration, temperature and solvent of synthesis have been demonstrated via various characterization techniques including ultraviolet-visible-near infrared spectroscopy, photoluminescence spectroscopy, X-ray diffractometry and transmission electron microscopy. The binary copper selenide was first synthesized and considered as a template for evaluation of the use of copper chalcogenide materials in solar cells. Relatively smaller copper selenide NPs with average sizes of 4.5 and 6.0 nm were obtained from conventional colloidal and microwave assisted methods respectively. The sample yielded from the microwave assisted method possessed less polydispersed NPs. The later had better crystallinity in which prevailed a single cubic Cu2Se phase. To the best of our knowledge this is the first evidence of defined shapes and nearly single phase of small sized copper selenide NPs synthesized by mean of the MAM. The copper selenide particles synthesized via this method were used to fabricate a Schottky device. The conditions of copper selenide synthesis were optimized to 250 oC, 30 min of CCM synthesis using oleylamine (OLA) and a Cu/Se ratio of 1:1. Nearly hexagonal facets with blue-shifted absorption band edge of monodispersed NPs sizing 4-8 nm in diameter were obtained. The synthesized copper selenide showed better crystallinity with a single cubic Cu2Se phase. A Schottky device using MAM synthesized copper selenide NPs as the semiconducting layer was fabricated at room temperature. The diode effect was demonstrated with the electrical parameters such as the ideality factor, barrier height and the series resistances extracted from the experimental current-voltage data using the thermionic theory and Cheung’s modification. The thermionic theory resulted in the ideality factor of 4.35 and the barrier height of 0.895 eV whilst the Cheung’s method resulted in the ideality factor, barrier height and series resistance of 1.04, 2.59 10-3 eV and 0.870 Ω respectively. The ternary copper indium selenide NPs showed that the MAM allowed the formation of copper rich NPs alongside secondary products. The synthesis of the ternary sample via CCM was optimized using uncapped precursors (no TOP was added) in OLA at 220 oC for 30 min. The synthesized CuInSe2 NPs possessed a large blue-shift in their absorption band edges and emission peaks. The nearly stoichiometric CuInSe2 particles with diameter sizes of 5-9 nm were found in tetragonal crystalline orientation. The cyclic voltametry (CV) and the absorption spectra showed a large blue-shifted energy gap, about 0.95 eV, an increase from the bulk, proving the quantum confinement effects of synthesized copper indium selenide quantum dots. The CuInSe2 NPs were thus used as absorbing materials in the quantum dot sensitized solar cell devices (QDSSCs). The QDSSC devices were assembled via treatment of the titanium oxide, quantum dot layers and their interface. This was done by the treatment of copper indium selenide surface with mercapto-propionic acid (MPA) and ethanedithiol (EDT) during the deposition of the quantum dots onto TiO2 films. The MPA treatment did not reveal positive effects on copper indium selenide thin film and the assembled device under our optimized working conditions. However the use of EDT allowed the improvement of electron transport. The short circuit current (Jsc), open circuit voltage (Voc) and fill factor (FF) obtained from the current-voltage (J-V) curves reached the values of 324 μA cm-2, 487 mV and 43% respectively, indicating that the investigated quantum dots possess electrical properties. For the quaternary copper indium gallium selenide, relatively small sized NPs were synthesized via CCM and MAM. The CCM synthesized CIGSe NPs were less agglomerated with a shorter tailing in absorption than those from MAM. The stoichiometric CuIn0.75Ga0.25Se2 showed less agglomerated and highly crystalline particles with a large blueshifted absorption band edge and a smaller full width at halth maximum (FWHM) of the emission peak compared to CuIn0.5Ga0.5Se2 and CuIn0.25Ga0.75Se2. The use of OLA as solvent of synthesis improved the growth and dispersivity of copper indium gallium selenide NPs. The particles with a large blue-shifted absorption band edge, a lattice of tetragonal phase, more monodispersed CIGSe and possessing an average size of 6.5 nm were obtained from CCM synthesis using OLA. The OLA as-synthesized CIGSe NPs were used in thin film for the assembly of QDSSC. The device exhibited electrical properties with the Jsc, Voc and FF of 168 μA cm-2, 162 mV and 33% respectively. The overall device performance was poor but may further be improved for further photovoltaic application. The quinary CZTSSe NPs possessed large blue-shifted absorption band edges of 450-460 nm than the bulk material (827 nm). The emission peak at 532 nm and similar FWHM of less than 50 nm were observed in samples from both CCM and MAM. More monodispersed crystals were obtained with both methods whilst the average particle sizes of 10 and 9 nm were yielded from MAM and CCM respectively. The nanoparticles crystallized in tetragonal lattices between copper zinc tin sulphide and copper zinc tin selenide crystals. However, the MAM gave more crystalline phases. The CV and the absorption spectra showed a blue shifted energy gap, about 0.21 eV increase from the buk which is located at 1.51 eV. This is indicative of the quantum confinement effects of synthesized NPs. The evidence of electrical properties was also shown in the QDSSCs fabricated using the MAM synthesized quinary QDs. This was done following the same treatments as for copper indium selenide devices. The Jsc, Voc and FF were found at the maxima of 258 μA cm-2, 395 mV and 38% respectively. The MPA and EDT treatments did not improve the device performance under our working conditions. Nevertheless, the electrical properties observed in the assembled device were indicative of promising efficient solar cells from synthesized CZTSSe NPs.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of requirements for the degree of Master of Science. Johannesburg, 2015. / Organic Photovoltaic (OPVs) is a promising alternative technology to provide clean and inexhaustible energy due to their excellent optoelectronic properties of the active polymer blends. The organic polymers have low weight, tunable electrical and optical properties besides being relatively insensitive to film imperfections which in the long run enable low-cost high-throughput roll-to-roll processing. However, their photo-conversion efficiency (PCE) and instability to air remains their greatest drawback as these preclude their commercialization. Indeed the highest power-conversion efficiency reported in literature is between 10-12 % compared to their inorganic counterparts (40 %). Therefore there is great need for improvement to make them competitive with grid parity. In this thesis, the major factors limiting the efficiency of organic solar cells such as light absorption, exciton diffusion and dissociation as well as charge collection are investigated and discussed. Despite the high thickness dependent absorption coefficients (>105 cm-1) within the visible spectrum the materials exhibit short exciton diffusion lengths (10-20 nm) which limit the optimal active layer thickness to a few nanometers. Improving optical absorption within this thickness forms the basis of this project. We report the use of surface Plasmons synthesized by both thermal evaporation and Radio Frequency (RF) magnetron sputtering system to tune and enhance optical absorption and scattering using the surface Plasmon resonance effect. The NPs were annealed at various temperatures and for different times to reconstruct and modify their shapes, sizes as well as the inter-particle distance (coverage). Stability is of paramount importance in organic semiconductor devices. Serious degradation in air constrains their applications potential. The study further investigates the mechanisms that determine the stability of organic photovoltaic devices. Our results depict the degradation mechanisms and their circumvention through the use of high mobility pentacene to improve stability.

A Thesis submitted for the faculty of Science at the University of Witwatersrand Johannesburg, in the fulfilment for the degree of Doctor of Philosophy in Chemistry. Johannesburg, November 2016. / The synthesis of carbon spheres (solid and hollow) for application in organic photovoltaics and chemical sensors is a means of using inexpensive and readily processable carbons to eliminate global warming and to monitor harmful gases. The synthesis conditions used to make solid carbon spheres can also be used to tailor their structural, paramagnetic and thermal properties. More so, the ability to tailor the morphology, surface, structural and electronic properties of the hollow carbon spheres by a templating method is an added advantage to their applicability in electronic devices. Solid carbon spheres were synthesized by a vertically oriented chemical vapor deposition (CVD) reactor using acetylene as a carbon source and argon or hydrogen as the carrier gas. The flow rates of the acetylene or carrier gases determined the particle sizes of the carbon spheres. Annealing of carbon spheres in hydrogen resulted in an increase in thermal stability, fewer defects and narrower paramagnetic signals relative to the carbon spheres annealed in argon gas. In contrast, carbon spheres annealed in argon exhibited an increase in the number of defects, a decrease in thermal stability and broader paramagnetic signals. Doped carbon spheres portrayed an increase in ID/IG ratios, a decrease in thermal stability and stronger paramagnetic signals due to the presence of defects induced by nitrogen. The N doped carbon spheres synthesized in H2 comprised of 48% pyridinic-N, 22% pyrrolic-N and 24% quaternary -N while the N doped spheres obtained in the presence of Ar had 17% pyridinic- N, 20% pyrrolic-N and 49% quaternary-N. The presence of a higher percentage of pyridinic- N confirms the presence of more edge defects in carbon spheres synthesized under H2 gas corroborating with the stronger paramagnetic signal observed from the ESR spectra. Consequently, a higher N/C ratio was exhibited in the N doped CSs obtained in the presence of H2 (4.96) than in the presence of Ar (3.68). This could be attributed to the presence of edge defects in carbon spheres synthesized in the presence of H2 gas. The induction of edge defects in carbon spheres in the presence of H2 gas without the aid of a metal catalyst opens a platform for regulating surface and catalytic reactions using H2 gas. Pristine and mesoporous SiO2 spheres were synthesized using a modified Stober method. Carbonization of the pristine SiO2, pristine SiO2@PVP, mesoporous SiO2 and mesoporous SiO2@PVP spheres was carried out using a bubbling method with toluene as the carbon source and argon as the carrier gas in a CVD reactor for 1 h. Upon SiO2 removal, hollow carbon nanostructures of varying morphologies were obtained. The polyvinylpyrrolidone (PVP) adsorption time, PVP concentration, SiO2 mesoporosity, SiO2 particle size dispersion, and carbonization time played a role in the formation of unique hollow carbon nanostructures; complete HCSs, broken HCSs, deformed HCSs, edge connected, open ended, wormlike and bubble-like HCSs. The mesoporous broken HCSs and open ended HCSs portrayed a hierarchical structure with a bimodal pore size distribution. The surface area properties of these materials and the ease of control of the carbon morphology gives an insight into the application of these materials as dye adsorbents. The effect of the size dispersion of Au@SiO2 sphere templates for the synthesis of hollow carbon structures was evaluated using a CVD nanocasting method. The diameter of the template, the presence of the gold nanoparticles and the amount of PVP determined the size, thickness and shape of the synthesized carbon nanostructures. Carbonization (and SiO2 removal) of Au@polydispersed silica spheres for 1 h gave a graphene-like HCS layer while longer times (2-4 h) gave nanotube like (or worm like) HCSs. These results highlight the potential use of Au@carbon core shell structures for the generation of few layered graphene-like unusual nanostructures. As a proof of concept, the wormlike carbon structures were incorporated in organic solar cells and found to give a measurable photovoltaic response. The incorporation of Au nanospheres and nanorods in a hole transport layer (PEDOT:PSS) of a solar cell device increased the current density and the photo-conversion efficiency of the device due to the local surface plasmon resonance and enhanced light scattering effects of gold. However, high series resistance and leakage currents were obtained due to barrier centres created by uneven dispersion of Au nanaorods within the polymer matrix. The performance of bulk heterojunction organic photovoltaic cells based on poly(3-hexylthiophene- 2,5-diyl) (P3HT) and 6,6-phenyl-C61-butyric acid methyl ester (PCBM) processed from chlorobenzene solution can be enhanced by solution heat treatment of the blend. The morphology of films spin coated from the heat treated blend solution reveals a more favourable diffusion of PCBM into the P3HT matrix than heating of the individual solutions separately. The films obtained from heat treated P3HT and PCBM solutions had a more homogeneous dispersion and enhanced light absorption than those obtained from solutions heat treated separately. There was a significant improvement in the performance for devices made from a solution heat treated blends relative to the non-treated blend; a maximum power conversion efficiency of 3.5% and a fill factor up to 43% was achieved under Air Mass 1.5 at 100 mW/cm2 illumination. This study also reports on the sensing characteristics of ammonia in humid environment by hollow carbon spheres, hollow carbon spheres-polyvinylpyrrolidone composite and annealed hollow carbon spheres, at 20°C and 40°C. For device fabrication, a surfactant assisted method was used to homogeneously disperse the hollow carbon spheres, allowing their deposition onto an interdigitated electrode by casting. An enhanced response and recovery time of the devices was observed at the higher working temperature. Annealing of the hollow carbon spheres resulted in a tremendous decrease in the humidity dependent ammonia sensing due to a decrease in the number of the oxygenated groups and defects in their structure. The presence of hydroxyl groups on the pristine hollow carbon sphere surface resulted in an enhanced proton conductivity. However, the ammonia sensitivity at high relative humidity in the pristine hollow carbon spheres is negligible due to the inhibition of ammonia adsorption sites by the high concentration of water molecules. The sensor response was investigated by varying both ammonia concentration and relative humidity, determining the topology of the response as a function of these two variables, and applying a tristimulus analysis in an attempt to determine the ammonia concentration independently of the relative humidity. This study demonstrates the critical role played by humidity and surface chemistry in the ammonia sensing properties of hollow carbon spheres. The studies reveal the day to day application of ammonia sensors, with temperature and humidity playing a critical role in the carbon based sensor response and recovery of the materials. These carbon based sensors that simultaneously measure ammonia and relative humidity could be applied in agricultural industries to monitor ammonia concentration in soils, fishponds and in food industries to monitor meat spoilage. / LG2017