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.

It has been debated that among all the renewable energy alternatives, only solar energy offers sufficient resources to meet energy demands. Silicon thin film solar cells are at the frontier of commercial solar technology. Hot wire chemical vapour deposition (HWCVD) is the technique of choice for silicon thin film deposition due to the absence of ion bombardment and its independence toward geometry or electromagnetic properties of the substrate, as seen by plasma enhanced chemical vapour deposition (PECVD). With the implementation of nanostructures in a multi-band gap tandem solar cell, considerable improvement has been achieved over the single junction solar cells. Defect assisted tunnelling processes at the junctions between individual solar cells in a tandem structure solar cell largely affect the efficiency of these solar cells. In this contribution, the investigation toward the improvement of silicon thin films for tandem solar cell application is initiated. This study reports on the effects of hydrogen dilution and deposition time on six silicon thin films deposited at six specific deposition regimes. The thin film properties are investigated via X-Ray diffraction analysis, Raman spectroscopy, Fourier transform infra-red spectroscopy, elastic recoil detection analysis, scanning and transmission electron microscopy and UV-visible spectroscopy. This investigation revealed the dominating etching effect of atomic hydrogen with the increase in hydrogen dilution and a bonded hydrogen content (CH) exceeding 10 at.% for each of the six thin films. The optically determined void volume fraction and static refractive index remain constant, for each thin film, with the change in CH. A new deposition procedure, utilising the deposition conditions of the previously investigated thin films, is performed by HWCVD to deposit two silicon thin films. This deposition procedure involved either increasing (protocol 1) or decreasing (protocol 2) hydrogen dilution during deposition. Structural and optical variation with depth was observed for the dynamically deposited silicon thin films, with nano-voids existing across the entire cross section and bond angle variations which are indicative of good structural order. The optical absorption curves differ for the two silicon thin films whereas the optical density remains constant for both. / >Magister Scientiae - MSc

>Magister Scientiae - MSc / This study reports on the effects of hydrogen dilution and deposition time on six silicon thin films deposited at six specific deposition regimes. The thin film properties are investigated via X-Ray diffraction analysis, raman spectroscopy, fourier transform infra-red spectroscopy, elastic recoil detection analysis, scanning and transmission electron microscopy and UV-visible spectroscopy. This investigation revealed the dominating etching effect of atomic hydrogen with the increase in hydrogen dilution and a bonded hydrogen content (CH) exceeding 10 at.% for each of the six thin films. The optically determined void volume fraction and static refractive index remain constant, for each thin film, with the change in CH

Cette thèse s’intéresse à l'intégration sur Si de cellules solaires III-V à simple et double jonction par épitaxie en phase vapeur aux organo-métalliques (MOVPE). Les dispositifs photovoltaïques ont été réalisés avec des matériaux accordés sur InP. L'objectif était d'abord d'obtenir des dispositifs performants sur des substrats InP, puis de les intégrer sur une structure avec un paramètre de maille différent, en évaluant les effets sur les performances photovoltaïques. Ceci a nécessité la réalisation et l'optimisation de plusieurs étapes de fabrication.Tout d'abord, nous avons réalisé une cellule InP à simple jonction, qui peut correspondre à la cellule top dans notre structure tandem. Cela était également nécessaire pour mettre en place un processus de fabrication pour toutes les cellules suivantes. Les conditions de croissance ont été optimisées en profitant des techniques de caractérisation des matériaux telles que la XRD, l’analyse C-V et le SIMS. En optimisant les épaisseurs et les niveaux de dopage des différentes couches du dispositif, ainsi que le procédé en salle blanche, nous avons obtenu une efficacité de conversion de 12.9%, avec un FF de 84.3%. Nous avons démontré que l'utilisation d'une couche fenêtre en AlInAs au lieu de l’InP peut augmenter l'efficacité à 13.5%, malgré une légère réduction du FF (81.4%). La même procédure a ensuite été étendue à la réalisation d'une cellule solaire InGaAs comme cellule bottom du dispositif tandem. Nous avons obtenu un rendement de 11.4% et un FF de 74.5%.En parallèle, des jonctions tunnels capables de relier électriquement les deux sous-cellules dans un dispositif tandem ont été étudiées. En particulier, nous avons concentré notre attention sur les conditions de croissance de l'anode de la jonction, qui a été fabriquée en AlInAs et dopée avec le précurseur CBr4. Les réactions chimiques d’un tel précurseur avec le précurseur de l’Al et l’In nécessitaient une importante réduction de la température de croissance à 540 °C. En déterminant les effets des flux sur la composition et les niveaux de dopage du composé, nous avons obtenu un dopage élevé de +4x1019 cm-3. En obtenant un niveau équivalent pour la cathode InP:S, nous avons réalisé un dispositif présentant un Jp de 1570 A/cm2, capable de fonctionner dans des conditions de concentration solaire élevée. En combinant finalement les trois dispositifs présentés dans une cellule tandem, nous avons pu obtenir un rendement global de conversion de 18.3%, avec un FF de 83.9%.Un template approprié pour l'intégration III-V/Si a été déterminé en testant plusieurs possibilités fournies par différents partenaires. Les caractérisations XRD et AFM ont démontré qu'un template InP/GaP/Si fourni par la société NAsP était la meilleure option. Ceci a été confirmé par la croissance d'une cellule InP à simple jonction sur le template. La techno sur un substrat Si a été rendu possible en déplaçant le contact arrière de la cellule sur la face avant du dispositif, ce qui a nécessité la mise au point d'un ensemble approprié de masques photolithographiques. La réussite de l’intégration des cellules solaires III-V sur Si a été confirmée par le photocourant produit. Celui-ci correspond à environ 60% de la valeur obtenue sur les substrats InP. De plus, les caractéristiques J-V mesurées donnent une tendance de type diode, démontrant la validité de l'approche proposée. / This thesis focuses on III-V/Si integration of single- and dual-junction solar cells by Metalorganic Vapor Phase Epitaxy (MOVPE). The photovoltaic devices were made with materials lattice matched to InP. The goal was to firstly obtain efficient devices on InP substrates and then to integrate them on a structure with a different lattice parameter, by evaluating the effects on the photovoltaic performances. This required the realization and the optimization of several manufacturing steps.Firstly, we realized an InP single junction device, which may correspond to the top cell of our tandem structure. This was also necessary to set up a manufacturing process for all the next cells. The growth conditions were optimized by taking advantage of material characterization techniques such as XRD, C-V profiling and SIMS. By optimizing thicknesses and doping levels of the various layers of the device, as well as the clean room process, we obtained a conversion efficiency of 12.9%, with a FF of 84.3%. We demonstrated that the use of an AlInAs window layer instead of InP may increase the efficiency to 13.5%, despite a slight reduction in FF (81.4%). The same procedure was then extended to the realization of an InGaAs solar cell as the bottom component of the tandem device. We obtained an efficiency of 11.4% and a FF of 74.5%.In parallel, tunnel junctions able to electrically connect the two subcells in a tandem device were studied. In particular, we focused our attention on the growth conditions of the junction anode, which was made in AlInAs and doped with CBr4 precursor. The particular chemical interactions that such a precursor has with Al precursor and In required a relevant reduction of growth temperature to 540 °C. By determining the effects of the flows on composition and doping levels of the compound, we obtained a high doping of +4x1019 cm-3. By obtaining an equivalent level for the InP:S cathode, we realized a device presenting a Jp of 1570 A/cm2, able to work under high solar concentration conditions. By finally combining the three presented devices in a tandem cell, we could obtain an overall conversion efficiency of 18.3%, with a FF of 83.9%.A proper template for III-V/Si integration was determined by testing several possibilities provided by different partners. XRD and AFM characterizations demonstrated that an InP/GaP/Si template provided by NAsP Company was the best option. This was confirmed by the growth of an InP single junction cell over the template. The processing over a Si substrate was made possible by shifting the rear contact of the cell on the front side of the device, which required the development of a proper set of photolithographic masks. The successful integration of the III-V solar cells on Si was confirmed by the relevant produced photocurrent. This corresponds to around 60% of the value obtained on InP substrates. Furthermore, the measured J-V characteristics show a diode-like trend, which demonstrates the validity of the proposed approach.

ITO is widely regarded as the optimal TCO for serving as front window layer in PSK/c-Si tandem solar cells. It is known to effectively mitigate several stability issues present in perovskite solar cells while demonstrating excellent lateral conductivities and optical transparency across the entire solar spectrum. However, due to the damaging effects of traditional magnetron sputtering methods on the underlying cell precursor and the limited range of annealing temperatures viable for maintaining the stability of Perovskite Solar cells, realizing the full capability of ITO layer is constrained. This investigation focuses on developing and optimizing the front Indium Tin Oxide (ITO) layer properties for high-efficiency monolithic Perovskite/PERC tandem solarcells. The study employs two widely employed industrial techniques, Magnetron Sputtering and Screen Printing for the deposition of ITO thin-films and subsequent metallization of Ag front contacts. The sputtering process parameters, namely the carrier speed, O2 : Ar ratio, and the sputter power were varied to obtain an optimized ITO layer, which exhibited a thickness of 53nm, Rsheet of 107 ohm/□, mobility of 37 cm2/V s, and 90 % average optical transparency between 400−1200nm. A low contact resistivity of 5.4mΩ·cm2 was achieved between the ITO and metal contacts which is the lowest reported value for ITO annealed at low temperature (140 °C). Champion cells, featuring Perovskite on Ohmic substrate and 2T perovskite/PERC tandem cells, exhibited high VOC values of 1.116 V and 1.75 V on 0.97 cm2 cell aperture areas and cell efficiencies of 17.2 % and 23.85 %. Additionally, a large area (158.7 cm2) tandem cell was also fabricated which demonstrated an excellent VOC of 1.75 V . The results of this investigation demonstrates the versatility of ITO layer properties achievable at low-temperatures through Magnetron sputtering and underscores the potential of existing commercialized technologies for the fabrication of high-efficiency tandem solar cells. / ITO anses allmänt vara den optimala TCO för användning som frontfönsterskikt i PSK/c-Si tandemsolceller. Den är känd för att effektivt mildra flera stabilitetsproblem som finns i perovskitsolceller samtidigt som den uppvisar utmärkt lateral konduktivitet och optisk transparens över hela solspektrumet. På grund av de skadliga effekterna av traditionella magnetronförstoftningsmetoder på den underliggande cellprekursorn och det begränsade intervallet av glödgningstemperaturer som är användbara för att upprätthålla stabiliteten hos perovskitsolceller, begränsas dock ITO-skiktens fulla kapacitet. Denna undersökning fokuserar på att utveckla och optimera egenskaperna hos det främre Indium Tin Oxide (ITO)-skiktet för högeffektiva monolitiska Perovskite/PERC tandemsolceller. I studien används två allmänt använda industriella tekniker, magnetronförstoftning och screentryckning, fördeponering av ITO-tunnfilmer och efterföljande metallisering av Ag-frontkontakter. Parametrarna för sputteringsprocessen, nämligen bärarhastigheten, förhållandet O2 : Ar och sputterkraften varierades för att få ett optimerat ITO-lager, som uppvisade en tjocklek på 53nm, Rsheet på 107 ohm/□, rörlighet på 37 cm2/V s och 90 % genomsnittlig optisk transparens mellan 400 − 1200 nm. En låg kontaktresistivitet på 5.4mΩ.cm2 uppnåddes mellan ITO och metallkontakterna, vilket är de lägstarapporterade värdena för ITO glödgat vid låg temperatur (140 °C). Champion-cellerna, med perovskit på ohmskt substrat och 2T perovskit/PERC tandemkonfigurationer, uppvisade höga VOC-värden på 1.116 V och 1.75 V på 0.97 cm2 cellaperturområden och cellverkningsgrader på 17.2 % och 23.85 %. Dessutom tillverkades en tandemcell med stor area (158.7 cm2) som uppvisade en utmärkt VOC på 1.75 V . Resultaten av denna undersökning visar mångsidigheten hos ITO-skiktets egenskaper som kan uppnås vid låga temperaturer genom magnetronförstoftning och understryker potentialen hos befintliga kommersialiserade tekniker för tillverkning av högeffektiva tandemsolceller.