Dans une cellule solaire, il existe un compromis entre l’efficacité d’absorption des photons et le rendement quantique de collection des charges électriques. Dans les semi-conducteurs organiques, la longueur de diffusion des porteurs est limitée à une centaine de nanomètres, si bien qu’il est nécessaire de travailler avec des couches photo-actives ultraminces (< 100 nm). Pour limiter l’épaisseur physique des matériaux utilisés tout en maintenant une absorption élevée, il est possible d’utiliser les propriétés des cristaux photoniques (CP), pour allonger la durée d’interaction des photons avec le milieu absorbant. Cela consiste à former un CP dans la couche active ou à son voisinage et d’exciter des modes résonants de la structure. Ce travail de thèse est divisé en plusieurs parties. Dans un premier temps, à l’aide d’outils numériques, nous nous intéressons aux phénomènes qui régissent le gain d’absorption lors du couplage d’une onde plane avec un mode résonant d’une membrane à CP. Ensuite, nous étudions une cellule à CP, où l’électrode d’ITO est nano-structurée, et nous optimisons le gain d’absorption d’une couche photo-active ultramince (50 nm). Enfin, dans un travail expérimental, nous fabriquons des cristaux colloïdaux bidimensionnels à base de microsphères diélectriques par différentes méthodes d’auto assemblage. / In a solar cell, there is a trade-off between light absorption capacity and internal quantum efficiency. In organic semi conductors, charge carrier diffusion is limited to a few hundred nanometers, which implies to work with very thin active layers (< 100 nm). In order to limit the thickness of the material while keeping high light absorption, it is possible to use the properties of photonic crystals (PC) to enhance light matter interaction duration. It consists in forming a PC in or around the active layer, and to excite a resonant mode of the formed photonic structure. The work of this thesis is divided into several parts. In a first approach, using numerical tools, we investigate the phenomena that give rise to absorption enhancement when a plane wave is coupled to a resonant mode of a PC membrane. We then study a nano-structured cell architecture, in which the ITO electrode is periodically patterned, and we optimize absorption enhancement in the thin active layer (50 nm). Finally, in an experimental work, we fabricate two dimensional colloidal crystals formed by dielectric microsphere self assembly.

La thèse a pour but d’élaborer et d’étudier les potentialités des semi-conducteurs organiques, transporteurs de trous (HTMs) pour l’application photovoltaïque à l’aide de cellules solaires à base de pérovskite (PSCs). Plusieurs familles de molécules HTM ont été préparées et déposées en solution pour l’élaboration des cellules solaires. L'objectif principal étant d'étudier et d’apporter des informations sur la relation entre la structure moléculaire des nouveaux matériaux de transport de trous et les performances photovoltaïques obtenues, cette étude contribue à une meilleure compréhension fondamentale des propriétés requises des matériaux de transport de trous pour de meilleures performances photovoltaïques.La première étude concerne l’élaboration d’une molécule de type p à base de thieno [3,2-b] thiophène comme élément central avec des dérivés de dimethoxytriphenylamine comme donneurs d’électrons aux extrémités. Différentes conformations sont proposées et révèlent des performances photovoltaïques significativement différentes dans les dispositifs PSC. Notons par exemple, qu’une conformation de structure planaire favorisent la conjugaison avec des valeurs élevées de mobilités et conductivités obtenues.Dans la seconde étude, des molécules donneur-accepteurs à base de dérivés d’acridone 9 (10H) comme accepteur ont été élaborés. En y associant différents fragments donneurs d'électrons, on obtient des structures présentant des caractéristiques favorables à la fois pour de bons transferts de charge intramoléculaire (ICT) et des niveaux d’énergie HOMO-LUMO adaptés et favorisant l’injection des trous de la pérovskite vers l’électrode métallique via le HTM. Des études similaires ont été effectuées avec la thioxanthone.A partir d’un précurseur bon marché et d’une préparation aisée, la troisième étude a permis de synthétiser un dérivé de 9,9’-biacridone, molécule push-pull de type p révélant une structure tridimensionnelle, similaire à celle du Spiro-OMeTAD, molécule référence pour les PSCs.Enfin, la dernière étude concerne l’élaboration de molécules donneur-accepteur à base de thiéno [3,4-c] pyrrole-4,6-dione (TPD). La motivation de cette partie est le développement de la molécule à structure planaire améliorant l’empilement π-π dans la fabrication de dispositifs sans joints de grains. Ces molécules possèdent également un fort caractère ICT, une conjugaison π étendue sur toute la structure et une bonne solubilité ce qui en fait un candidat HTM idéal pour la réalisation d’un dispositif PSCs sans dopant. / The aim of the thesis is to develop and study the potential of organic hole transporting materials (HTMs) for photovoltaic applications using perovskite-based solar cells (PSCs). Several families of HTM molecules have been prepared and deposited in solution for the fabrication of solar cells. Since the main objective is to study and provide information on the relationship between the molecular structure of new hole transport materials and the photovoltaic performances obtained, this study contributes to a better fundamental understanding of the required properties of hole transport materials for better photovoltaic performance.The first study concerns the development of p-type molecules based on Thieno [3,2-b] thiophene as a central unit and π-linker with dimethoxytriphenylamine as end-capping electron donors. Different configurations are designed and revealed significantly different photovoltaic performances in the PSC devices. Remarkable, a planar structure with linear conjugation shows higher values of mobility and conductivity than others, thus it improved device performances.In the second study, donor-acceptor molecules based on 9(10H)Acridone derivatives as an acceptor were developed. By incorporating different electron-donating fragments, we obtain structures with favorable characteristics for both good intramolecular charge transfer (ICT) character and adequate HOMO-LUMO energy levels. Their energy levels are suitable for collecting and injecting the holes from perovskite to the metal electrode through the HTM. Similar studies have been done with Thioxanthone.Using a cheap precursor and facile preparation, the third study synthesized a 9.9'-biacridone derivative. These p-type molecules possess a three-dimensional structure which is similar to that of Spiro-OMeTAD, state-of-the-art molecule for PSCs.Finally, the last study focus on the development of donor-acceptor molecules based on thieno [3,4-c] pyrrole-4,6-dione (TPD). The objective is elaboration of the planar structure molecule which could be improved the π-π stacking effect in the device fabrication without grain boundaries. These molecules also own a strong ICT character, an extended π-conjugation on the whole structure and a good solubility which makes it an ideal candidate for the dopant-free HTM in PSCs.

Thin film silicon on low temperature glass substrates is currently seen as the best path toreduce the $/W cost of photovoltaic (PV) modules. However, producing thin film polysilicon, on glass, is an ongoing research challenge. Laser crystallisation of a-Si is one of the possible methods. Typically excimer (XMR) lasers are used for laser crystallisation. This thesis introduces the copper vapour laser (CVL) as a viable alternative for thin film photovoltaic applications. The CVL, like the XMR, is a high powered, pulsed laser. However, the CVL has higher pulse rates (4-20kHz), better beam quality and a visible wavelength output (578 & 511nm). Preliminary experiments, using 600K-heated silicon-on-quartz samples, confirmed that CVL crystallisation can produce area weighted average grain size of 0.1-0.15??m, which is comparable to results reported for XMR??? s. Importantly, the CVL results used thicker films (1??m), which is more applicable to thin photovoltaic devices that need 1-10??m of silicon to be viable. The CVL??? s longer wavelength and therefore longer penetration depth (1/alpha) are proffered as the main reason for this result. Extensive laser-thermal modelling highlighted further opportunities specific to CVL crystallisation. Through-the-glass doublesided irradiation was shown in simulations to reduce thermal gradients, which would enhance crystal growth. The simulations also produced deeper melts at lower surface temperatures, reducing the thermal stress on the sample. Subsequent experiments, using silicon-on-glass, confirmed the benefit of through-the-glass doublesided irradiation by maintaining grain sizes without the usual need for substrate heating. Furthermore, Raman analysis showed that doublesided crystallisation achieved full depth crystallisation, unlike single side irradiation which produced partial crystallisation. A new mode of crystallisation, stepwise crystallisation, was also postulated whereby a series of CVL pulses could be used to incrementally increase the crystallisation depth into the silicon. Simulations confirmed the theoretical basis of the concept, with HeNe Raman spectroscopy and analysis of surface grain sizes providing indirect experimental support. The CVL??? s ability to crystallise thicker films more directly applicable to photovoltaic devices secures its viability as an alternative laser for photovoltaic applications. The through-the-glass doublesided irradiation and the stepwise crystallisation provide additional potential for increased process flexibility over XMR???s.

One of the poly-Si thin-film cells developed at the University of New South Wales (UNSW) is the EVA cell. In this work, SiN films for EVA cells as an antireflection/barrier coating were investigated. In addition, the effect of hydrogenation pre-treatment of solid phase crystallisation (SPC) on grain size and open-circuit voltage (Voc) was investigated. The SiN films deposited by PECVD were examined for uniformity of the thickness and the refractive index of the films across the position of the samples in the PECVD deposition system. A spectrophotometric analysis was used to determine these film properties. It was found that these properties were very uniform over the deposition area. Good repeatability of the depositions was also observed. A series of SiN film depositions by reactive sputtering were also performed to optimize the deposition process. Parameters adjusted during the deposition were nitrogen flow rate, substrate bias, and substrate temperature. By investigating the deposition rate, refractive index, and surface roughness of the films, the three deposition parameters were optimised. The effects of post SiN deposition treatments (a-Si deposition, SPC, RTA, and hydrogenation) on thickness and refractive index of both SiN films deposited by PECVD and reactive sputtering were investigated by using samples which have the same structure as the EVA cells. The thickness of the PECVD SiN films decreased about 6 % after all the treatments. On the other hand, the thickness reductions of the reactively sputtered SiN films were very small. The refractive index of the PECVD SiN films increased about 0.6 % after the treatments, whereas that of the reactively sputtered SiN films decreased 1.3 % after the treatments. As a possible method to improve the performance of EVA cells, hydrogenation of a-Si was investigated as a pre-treatment of SPC process. There were no obvious differences in the grainsize and the Voc of the EVA cells with and without the hydrogenation. Therefore it is likely that the hydrogenation pre-treatment of SPC does not have a beneficial effect on the performance of EVA cells.

The cost of photovoltaic electricity needs to be significantly reduced in order to achieve a high electricity market penetration. Thin-film solar cells have good potential to achieve such cost savings though (i) large-area deposition onto low-cost foreign substrates, (ii) more streamlined processing, (iii) monolithic cell interconnection, and very efficient use of the expensive semiconductor material. Polycrystalline silicon (poly-Si) on glass is a promising technology for the cost-effective large volume production of PV modules since it (i) makes use of an abundant raw material, (ii) is non-toxic, (iii) does not suffer from light-induced degradation, and (iv) does not rely on TCO layers. Usually plasma enhanced chemical vapour deposition (PECVD) is used for the layer formation. This thesis explores the use of e-beam evaporation as deposition method since it is potentially much faster and cheaper than PECVD. The resulting solar cells are referred to as EVA (from EVAporation). Two inherent shunting mechanisms in EVA cells are demonstrated to be shunting through sub-micron sized pinholes when the back electrode is deposited and shunting between the emitter and the absorber layer at the glass-side electrode. Through the improved understanding of these shunting mechanisms it was possible to develop a suitable metallisation scheme for EVA cells using an aligned deposition of emitter and back surface field line contacts and a specially developed shunt mitigation etching technique. For the first time appreciable efficiencies of up to 5.2% were demonstrated on this material. It was also shown that only very lightly doped absorber layers can lead to the required high short-circuit currents in EVA cells. The resulting cells are currently completely limited by space charge region recombination occurring with comparatively low ideality factors of only ~ 1.4 This thesis also demonstrates the usefulness of Jsc-Suns measurements and investigates optical loss mechanisms in the current devices. Advanced modelling of distributed series resistance effects, influencing Suns-Voc, m-Voc and Jsc-Suns curves, is employed. PC1D modelling is used to extract relevant device parameters. In this work it was found that the diffusion length in the best EVA cells is longer than the absorber layer and that insufficient light trapping is currently the major hurdle to higher cell efficiencies. From the obtained results it can be concluded that EVA solar cells are promising candidates for the low-cost and high-volume production of solar modules.

In polycrystalline silicon (pc-Si) thin-film solar cells, defect passivation is critical to device performance. Isoelectronic or covalently bonded impurities, hydrogenic, extended defects and defects with localized levels in the bandgap (deep level defects) are typically introduced during the fabrication of, and/or are inherent to, pc-Si thin-film solar cells. These defects dramatically affect minority carrier lifetimes. Removing and/or passivating these defects is required to maximize minority carrier lifetimes and is typically done through thermal annealing and passivation techniques. For pc-Si thin-film solar cells on low temperature glass superstrates, rapid thermal annealing (RTA) and hydrogen plasma passivation (hydrogenation) are powerful techniques to achieve effective removal and passivation of these defects. In this thesis, three silicon thin-film solar cells structures on low-temperature glass are subjected to variations in RTA high-temperature plateaus, RTA plateau times, and hydrogen plasma passivation parameters. These solar cells are referred to as ALICIA, EVA and PLASMA. By varying the RTA plateau temperature and time at plateau, the trade-off between extensive dopant diffusion and maximum defect removal is optimized. To reduce the density of point defects and to electrically activate the majority of dopants, an RTA process is shown to be essential. For all three of the thin-film solar cell structures investigated in this thesis, a shorter, higher-temperature RTA process provides the best open-circuit voltage (Voc). Extensive RTA plateau times cause excessive dopant smearing, increasing n = 2 recombination and shunt resistance losses. Hydrogenation is shown to be an essential step to achieve maximum device performance by `healing' the defects inherent to pc-Si thin-film solar cells. If the hydrogen concentration is about 1-2 times the density of oxygen in the cells as measured by secondary ion mass spectroscopy (SIMS), the cells seem to respond best to hydrogenation, with good resultant Voc and short-circuit for all cells investigated in this thesis. The effect of hydrogen passivation on the Voc is spectacular, typically increasing it by a factor of 2 to 3.5. Hydrogen de-bonding from repeated thermal treatments at increasing temperature provides a deeper understanding of what defects exist and the nature of the defects that limit the cell voltage. The variation in RTA and hydrogenation process parameters produces significant empirical insight into the effectiveness of RTA processes for point defect removal, dopant activation, point defect and grain boundary passivation, and impurity passivation. SIMS measurements are used to determine the impurities present in the cells' bulk and the amount of hydrogen available to passivate defects. From the results presented it appears that pc-Si thin-film solar cells on low-temperature glass are a promising, and potentially lower-cost, alternative to Si wafer based cells.

Innovation in photovoltaic technology may offer cost competitive options to other energy sources and become a viable solution for the energy and environmental challenges of the 21st century. One proposed innovative technology is based on all-silicon tandem cells, which are constructed using superlattices consisting of environmental friendly Si and its compounds. The well and barrier materials in superlattices are restricted to silicon and silicon oxide during the present study. Single crystalline Si/SiO2 quantum wells (QWs) have been fabricated by thermal oxidation of silicon-on-insulator (SOI) wafers. It is found that oxide properties in QWs are important for SOI wafers prepared by the SIMOX (Separation by Implantation of Oxygen) technique. However, QWs fabricated from SOI wafers prepared by the ELTRAN (Epitaxial Layer TRANsfer) approach show the effect of quantum confinement without evidence of strong oxide interfacial transitions. In these wafers, evidence for an apparently ordered silicon oxide was found with 1.92?atomic fringe spacing along the (110) direction of the Si structure and with the thickness about 17?along the (100) direction of the Si structure. Luminescence wavelength ranges are from 700nm to 918nm depending on the Si thickness. The luminescence measurements on other positions of the sample show peak and shoulder spectra, which are explained by monolayer fluctuations in QW thicknesses, previously observed in III-V QWs and II-VI QWs. Si/SiO2 superlattices are fabricated by RF magnetron sputtering. Si density is the key issue in crystallizing the superlattice. High-density Si layers crystallize either under high temperature furnace annealing or rapid thermal process annealing. However, low density Si would not crystallize even at high temperature. Crystallized nanocrystals in the Si layers are observed by high resolution transmission electron microscopy (HRTEM) when the Si layer is thicker than 3nm. When Si layers are thinner than 3nm, the Si layers are discontinuous and finally deteriorate into small nanocrystals. The suitability of such superlattices for surface passivation and antireflection coatings is reviewed. Initial attempts to fabricate heterojunctions between Si wafers and Si/SiO2 superlattices resulted in open circuit voltage of 252mV. However, it is expected that better results would be obtained if Si/SiO2 superlattices were fully crystallized.

The cost of crystalline silicon solar cells must be reduced in order for photovoltaics to be widely accepted as an economically viable means of electricity generation and be used on a larger scale across the world. There are several ways to achieve cost reduction, such as using thinner silicon substrates, lowering the thermal budget of the processes, and improving the efficiency of solar cells. This thesis examines the use of plasma enhanced chemical vapour deposited silicon nitride to address the criteria of cost reduction for n-type crystalline silicon solar cells. It focuses on the surface passivation quality of silicon nitride on n-type silicon, and injection-level dependent lifetime data is used extensively in this thesis to evaluate the surface passivation quality of the silicon nitride films. The thesis covers several aspects, spanning from characterisation and modelling, to process development, to device integration. The thesis begins with a review on the advantages of using n-type silicon for solar cells applications, with some recent efficiency results on n-type silicon solar cells and a review on various interdigitated backside contact structures, and key results of surface passivation for n-type silicon solar cells. It then presents an analysis of the influence of various parasitic effects on lifetime data, highlighting how these parasitic effects could affect the results of experiments that use lifetime data extensively. A plasma enhanced chemical vapour deposition process for depositing silicon nitride films is developed to passivate both diffused and non-diffused surfaces for n-type silicon solar cells application. Photoluminescence imaging, lifetime measurements, and optical microscopy are used to assess the quality of the silicon nitride films. An open circuit voltage of 719 mV is measured on an n-type, 1 Ω.cm, FZ, voltage test structure that has direct passivation by silicon nitride. Dark saturation current densities of 5 to 15 fA/cm2 are achieved on SiN-passivated boron emitters that have sheet resistances ranging from 60 to 240 Ω/□ after thermal annealing. Using the process developed, a more profound study on surface passivation by silicon nitride is conducted, where the relationship between the surface passivation quality and the film composition is investigated. It is demonstrated that the silicon-nitrogen bond density is an important parameter to achieve good surface pas-sivation and thermal stability. With the developed process and deeper understanding on the surface passivation of silicon nitride, attempts of integrating the process into the fab-rication of all-SiN passivated n-type IBC solar cells and laser doped n-type IBC solar cells are presented. Some of the limitations, inter-relationships, requirements, and challenges of novel integration of SiN into these solar cell devices are identified. Finally, a novel metallisation scheme that takes advantages of the different etching and electroless plating properties of different PECVD SiN films is described, and a preliminary evalua-tion is presented. This metallisation scheme increases the metal finger width without increasing the metal contact area with the underlying silicon, and also enables optimal distance between point contacts for point contact solar cells. It is concluded in this thesis that plasma enhanced chemical vapour deposited silicon nitride is well-suited for n-type silicon solar cells.

Thin-film solar cells on glass substrates are likely to have a bright future due to the potentially low costs and the short energy payback times. Polycrystalline silicon (poly-Si, grain size &gt 1 pm) has the advantage of being non-toxic, abundant, and long-term stable. Glass as a substrate, however, limits the processing temperatures to ~600??C for longer process steps. Films with large grain size can be achieved by solid phase crystallisation (SPC), and especially by solid phase epitaxy (SPE) on seed layers, using amorphous silicon deposited at low temperatures as a precursor film. With SPC and SPE, the amorphous silicon film is typically crystallised at ~600??C over hours. During this anneal at atmospheric pressure -depending on the properties of the amorphous silicon film- ambient gas can percolate the film and can negatively affect the crystallisation. In this work, a high-vacuum anneal chamber was designed and built to allow the in-situ crystallisation of amorphous silicon films deposited on glass in a PECVD cluster tool. An important aspect of the design was the comfortable and safe operation of the vacuum anneal chamber to enable unattended operation. This was realised by means of a state-of-the-art, programmable temperature controller and a control circuit design that incorporates various safety interlocks. The chamber interior was optimised such that a temperature uniformity of 2-3K across the sample area was achieved. The chamber was calibrated and tested, and SPC and SPE samples were successfully crystallised. In initial SPC crystallisation experiments with solar cell structures, after post-deposition treatments, a 1 -sun open-circuit voltage of 465 mV was obtained, similar to furnace-annealed samples. In initial experiments with SPE solar cell structures, difficulties regarding the characterisation of the unmetallised solar cells with the quasi-steady-state open-circuit voltage method (QSSVOC) were encountered after post-deposition hydrogen treatment. A possible explanation for these difficulties is the contact formation with the metal probes. Furthermore, limiting factors of the QSSVOC method for the characterisation of unmetallised cells with high contact resistance values were investigated and, additionally, the accuracyof the QSSVOC setup was improved in the low light intensity range.

Photovoltaics (PV) is fast emerging as an attractive renewable energy technology due to concerns of global warming, pollution and scarcity of fossil fuel supplies. However to compete in the global energy market, solar cells need to be cheaper and more energy efficient. Silicon is the favorite semiconductor used in solar photovoltaic cells because of its ubiquity and established technology, but due to its indirect bandgap silicon is a poor absorber and light emitter. Thin film cells play an important role in low cost photovoltaics, but at the cost of reduced efficiencies when compared to wafer based cells. There remains much untapped potential in thin-film solar cells which this work has attempted to exploit through exploring novel approaches of enhancing the efficiency of thin film cells using the optical properties of sub-wavelength metal nanoparticles. Metals are considered as strong absorbers of light because of their large free-electron density. How can metals improve light trapping in solar cells? This question has raised several eyebrows and this thesis is an attempt to show that metal nanoparticles can be useful in producing efficient solar cells. Subwavelength metal particles support surface modes called surface plasmons when light is incident on them, which cause the particles to strongly scatter light into the underlying waveguide or substrate, enhancing absorption. The process of coupling thin film silicon waveguide modes to plasmonic metals using unpolarised light at normal incidence is applied to silicon-based solar cells and light emitting diodes, and enhanced photocurrent and electroluminescence is realized with potential for further optimisation and improvement. The results from this study correspond to a current increase of up to 19% from planar wafer based cells and up to 33% increase from 1.25 micron thin-film silicon-on-insulator structures for the AM1.5 global spectrum. We also report for the first time an up to twelve fold increase in electroluminescence signal from 95nm thick light-emitting diodes. From the results we conclude that this method which involves simple techniques of nanoparticle deposition and characterization could hold important implications in the improvement of thin-film silicon cell absorption / emission efficiencies where conventional methods of light trapping are not feasible, resulting in promising near-term applications of surface plasmons in photovoltaics and optoelectronics.