This work is focused to study organic materials for solar energy conversion into electricity and characterization of conversion processes. Materials and their blends with semiconducting properties such as photoconductivity were studied. Thin films of organic materials and their blends were prepared by spin-coating method and characterized by optical methods (UV-VIS and photoluminiscence spectroscopy), by current-voltage characteristics, by impedance spectroscopy method, spectral response measurement of photocurrent and method of transient photoconductivity. Structural factors influences the conversion of solar energy into electricity were observed. Based no these results, the materials and their blends useful for photovoltaic applications were determined. The dependence between photoconductivity of thin films and theirs structure was also discussed.

This work deals with the advanced methods of contact’s fabrication for monocrystalline solar cells and the appropriate methods for the analysis of their properties with a focus on the study and realization the contact’s structures with low contact and sheet resistance fabricated by galvanic and electroless processes. In the first part of the work is discussed the theory of solar cells and buried contacts and in the second part of the work is an evaluation of practical realization.

This thesis deals with experimental measurement of angular distribution of electromagnetic radiation scattered from solar cells surfaces. The measuring apparatus is the second genaration of a scattermeter. This apparatus has been put into operation within the framework of this thesis. Results of the thesis are materials for numerical simulations aforementioned scattering and quantitative evaluation of scattering of electromagnetic waves from given surfaces.

Tato práce se zabývá optimalizací procedury měření optického záření rozptýleného pevnými tělesy prováděného pomocí scatterometru. V práci je popsáno několik metod použitelných k nalezení souboru pozic nepřekrývajících se kruhových detektorů na povrchu polokoule (i koule). Výsledky práce jsou aplikovány na samotný meřicí přístroj a je ukázána shoda experimentálních výsledku získaných před i po optimalizaci. Výhodu nového uspořádání lze nalézt především v převedení dřívejšího způsobu měření na soubor nezávislých měření, což má význam pro matematické zpracování výsledků.

Dans le contexte des cellules photovoltaïques (PV) à base de silicium cristallin (c-Si), le développement de structures de contacts dits « passivants », qui permettent de limiter les pertes par recombinaisons des porteurs de charge à l’interface entre le métal et le c-Si, est un des principaux leviers vers l’obtention de plus hauts rendements. Une approche de contacts passivés consiste à intégrer entre le métal et le c-Si une jonction composée d’une couche de silicium poly-cristallin (poly-Si) fortement dopée sur une mince couche d’oxyde de silicium (SiOx < 2 nm).Les objectifs de ce travail sont d’une part de développer une jonction poly-Si/SiOx compatible avec la fabrication industrielle des cellules PV, et d’autre part d’améliorer la compréhension des mécanismes de passivation et de transport des charges au niveau de la fine couche de SiOx située à l’interface entre le poly-Si et le c-Si.Dans ce travail, une jonction de poly-Si/SiOx dopée au bore a été développée, le dopage de la couche étant dans un premier temps réalisé in-situ pendant l’étape de dépôt chimique en phase vapeur assisté par plasma (PECVD) de la couche poly-Si. La méthode de dépôt PECVD est répandue dans l’industrie PV et permet la fabrication de la couche poly-Si d’un seul côté du substrat c-Si. Cependant, elle induit une forte concentration d’hydrogène dans la couche déposée, ce qui entraine la formation de cloques à l’interface avec le c-Si et tend à dégrader les propriétés de passivation de surface de la jonction après recuit de cristallisation. L’optimisation des conditions de dépôt (température de dépôt et ratio de gaz H2/SiH4) a permis d’obtenir des couches de poly-Si dopées in-situ intègres. Par la suite, une méthode de dopage alternative, par le biais du dépôt d’une couche diélectrique riche en bore sur le poly-Si, a été appliquée afin de réduire l’apport en hydrogène pendant le dépôt et d’obtenir des couches de poly-Si intègres plus épaisses. L’ajout d’une étape d’hydrogénation a permis d’obtenir des propriétés de passivation de surface au niveau de l’état de l’art pour les deux types de jonctions poly-Si/SiOx développées.A la suite du développement de la jonction poly-Si/SiOx, la caractérisation physico-chimique de la couche SiOx a été réalisée et a démontré une possible amélioration de la stœchiométrie de la couche vers SiO2 ainsi qu’une dégradation de son homogénéité en épaisseur sous l’effet du recuit de cristallisation à haute température. Ces phénomènes pourraient s’expliquer par une diffusion des atomes d’oxygène à l’interface. D’autre part, l’étude du transport des charges à travers le SiOx par C-AFM a mis en évidence les limites de cette technique quant à la détermination de nano-ouvertures au sein de la couche SiOx (qui favoriseraient le transport des charges). Enfin, une méthode de caractérisation des défauts recombinants à l’interface entre une jonction de poly-Si intrinsèque et le c-Si a été mise en œuvre. Cette méthode a permis de modéliser les recombinaisons à l’interface poly-Si/c-Si via deux défauts discrets apparents dont les niveaux d’énergie dans la bande interdite et les ratios de sections efficaces de capture des électrons et des trous ont été déterminés. / In the context of high efficiency solar cells (SCs) based on crystalline silicon (c-Si), the development of "passivating" contact structures to limit the recombination of charge carriers at the interface between the metal electrode and the c-Si has been identified as the next step to further improve the photovoltaic (PV) conversion efficiency. Passivating contacts consisting of a highly doped poly-crystalline silicon layer (poly-Si) on top of a thin layer of silicon oxide (SiOx ≤ 2 nm) are particularly sparking interest as they already demonstrated promising conversion efficiency when integrated in SCs.The objectives of this work are to develop a poly-Si/SiOx passivating contact compatible with the industrial production of c-Si SCs, and to investigate the passivation and charge transport mechanisms in the region of the thin SiOx layer located at the interface between the poly-Si and the c-Si.In this work, a boron-doped poly-Si/SiOx contact was fabricated. The doping of the layer was first performed in-situ during the deposition of a hydrogen-rich amorphous silicon (a-Si:H) layer by plasma-enhanced chemical vapor deposition (PECVD). The PECVD step was followed by an annealing step for crystallization of the poly-Si layer. The PECVD presents the advantages of being widespread in the PV industry and enabling the fabrication of the poly-Si contact on a single side of the c-Si substrate. However, it induces a high concentration of hydrogen in the deposited layer, which causes the formation of blisters at the interface with the c-Si and tends to degrade the surface passivation properties of the contact after annealing for crystallization. The optimization of the deposition conditions (temperature and H2/SiH4 gas ratio) enabled to obtain blister-free in-situ doped poly Si layers. An alternative doping method consisting of the deposition of a boron-rich dielectric layer on top of the poly-Si layer was applied to reduce the hydrogen content of the deposited layer. This approach enabled to obtain thicker blister-free poly-Si layers. The diffusion of hydrogen in the contact after annealing is known to provide a further chemical passivation of the poly-Si/c-Si interface. In this work, the addition of a hydrogenation step enabled to obtain state-of-the-art surface passivation properties for the two types of poly Si/SiOx contact fabricated.After developing the poly-Si/SiOx contact, a study of the effect of the annealing step on the chemical and structural properties of the SiOx layer was performed. Results indicated a possible improvement of the stoichiometry of the layer towards SiO2 as well as a degradation of its homogeneity at the poly-Si/c-Si interface after annealing at high temperature. These phenomena could be explained by a diffusion of the oxygen atoms content in the interfacial SiOx layer. The transport mechanism of charge carriers through the SiOx layer was conducted by C-AFM. This study revealed the limits of this technique to determine the presence of pinholes within the SiOx layer (that would help the transport of charge carriers). Finally, a method for characterizing recombinant defects at the interface between an intrinsic poly-Si junction and the c-Si has been developed. This method enabled to model the recombination phenomena at the poly-Si/c-Si interface via two apparent discrete defects. Their associated energy levels in the bandgap and ratios of electron and hole capture cross sections were estimated.

Les cellules solaires à multi-jonctions de type III-V possèdent des rendements de conversion de l'énergie très élevés (46%). Cependant, les méthodes de fabrication généralement utilisées sont complexes et coûteuses, notamment pour les cellules solaires non monolithiques associées par des techniques de collage et à structure inversée. Cette thèse vise à augmenter les rendements de conversion des cellules solaires monolithiques à l'aide de méthodes prospectives. Le travail est focalisé sur l'étude des défauts électroniquement actifs dans les matériaux constituant les cellules solaires au moyen de techniques photoélectriques et capacitives, et il peut être scindé en trois parties. La première partie traite des cellules solaires à simple jonction avec des couches absorbantes non dopées d'alliages InGaAsN de 1 eV de bande interdite de différentes épaisseurs obtenues sous forme de super-réseaux (InAS / GaAsN) par épitaxie à jets moléculaires (MBE) sur des substrats de GaAs. Pour des épaisseurs inférieures à 1200 nm, la concentration de défauts est négligeable et n'affecte pas fortement les propriétés photoélectriques, tandis que que pour une épaisseur de 1600 nm, la forte concentration de défauts détectés réduit la durée de vie des porteurs photogénérés, et conduit à une baisse significative du rendement quantique externe et des performances de la cellule. La deuxième partie du travail est consacrée à l'étude de cellules solaires à une et plusieurs jonctions avec des couches actives de (In)GaP(As)N obtenues par MBE sur des substrats respectifs de GaP et de Si. Nous avons trouvé que les cellules solaires de type p-i-n avec des couches actives de GaPAsN non dopé présentaient de meilleures performances que les cellules solaires de type p-n avec des couches actives de GaPAsN dopé n. De plus, les cellules solaires avec une couche d'absorbeur en GaPAsN non dopé présentent de meilleures propriétés photoélectriques et des concentrations de défauts plus faibles que celles avec un absorbeur obtenu à partir de super-réseaux InP / GaPN. Plusieurs niveaux de défauts ont été détectés dans la bande interdite de ces matériaux et leurs paramètres ont été décrits en détail. Nous avons montré qu'un traitement de post-croissance approprié pouvait améliorer la qualité électronique des couches et des cellules solaires. Une cellule solaire à triple jonction a été fabriquée avec des couches actives d'absorbeurs de GaPAsN et de GaPN non dopées. La valeur élevée de la tension de circuit ouvert (>2,2V) atteste du fonctionnement des 3 sous-cellules, mais la performance globale est limitée par les faibles épaisseurs de couches d'absorbeurs. Enfin, la troisième partie du travail est consacrée à l'étude de couches de GaP obtenues sur des substrats de Si à des températures inférieures à 400 ° C par une méthode originale de dépôt de couches atomiques assistée par plasma (PE-ALD). En effet, celle-ci utilise un équipement de dépôt chimique en phase vapeur assisté par plasma et elle repose sur l'interaction de la surface avec les atomes de Ga et P provenant respectivement du triméthylgallium et de la phosphine qui sont injectés alternativement. Nous avons également fait croître des couches en utilisant un processus continu (fournissant simultanément les atomes P et Ga) et observé que leurs propriétés électriques et structurelles étaient moins bonnes que celles obtenues par la méthode PE-ALD proposée. Nous avons exploré l'influence des conditions de croissance sur les hétérostructures GaP / Si. Nous avons constaté qu'une faible puissance de plasma RF conduit à de meilleures propriétés photoélectriques, structurelles et à moins de défauts, grâce à une meilleure passivation du substrat de silicium. En outre, nous avons démontré que, contrairement à des résultats de la littérature utilisant des procédés MBE, la technique PE-ALD n'affecte pas ou très peu les propriétés électroniques des substrats de silicium et aucune désactivation des dopants n'a été observée. / Multi-junction solar cells based on III-V compounds have reached very high power conversion efficiencies (46%). However, the fabrication methods that are generally used are complex and expensive for non-monolithic bonded and inverted solar cells. This thesis is devoted to the study of prospective methods to increase the efficiency of monolithic solar cells. The work is focused on the study of electronically active defects in the materials constituting the solar cells by means of photoelectric and capacitance techniques (admittance spectroscopy, DLTS,…) and it can be divided into three parts. The first part deals with single-junction solar cells wherein the absorber is made of i-layers of 1 eV bandgap InGaAsN compounds with various thicknesses grown as sub-monolayer digital alloys (SDA) of InAs/GaAsN by molecular-beam epitaxy (MBE) on GaAs wafers. The cell with 900 nm thick InGaAsN exhibits the best photovoltaic performance and no defects could be evidenced from capacitance techniques. When the thickness is increased to 1200 nm, defects were detected, but their concentration is low so it did not strongly affect the photoelectric properties. Further increase to 1600 nm of the layer thickness was shown to lead to a higher defect concentration causing a change in the band diagram of the structure and lowering the lifetime of photogenerated carriers. This could explain the drastic drop of the external quantum efficiency, and the overall poor performance of the solar cell. The second part is devoted to the study of single- and multi-junction solar cells with active layers of (In)GaP(As)N grown by molecular beam epitaxy (MBE) on GaP and Si wafers, respectively. More precisely, the active layers were either quaternary alloys of GaPAsN or SDAs of InP/GaPN. We found that p-i-n type solar cells with active layers of i-GaPAsN showed better performance than p-n type solar cells with active layers of n-GaPAsN due to higher EQE values. Moreover, solar cells with an i-GaPAsN absorber layer show better photoelectric properties and lower defect concentrations, than those with an SDA InP/GaPN absorber layer. Different defect levels were detected by capacitance methods in these materials and their parameters were described in detail. We showed that a suitable post-growth treatment could improve the electronic quality of the GaPAsN layer and the solar cell properties. Also, a triple-junction solar cell was fabricated with active layers of i-GaPAsN and i-GaPN. All subcells were found to be operating, leading to a large open circuit voltage (>2.2 V), but the overall performance is limited by the low value of the quantum efficiency due to low thicknesses of i-layers that should be increased for better absorption. Finally, the third part is devoted to the study of GaP layers grown on Si wafers at temperatures below 400 °C using an original method called plasma-enhanced atomic-layer deposition (PE-ALD). Indeed, it uses a plasma-enhanced chemical vapor deposition equipment and it is based on the alternate interaction of the wafer surface with Ga and P atoms coming from injected trimethylgallium and phosphine, respectively. We also grew layers using a continuous process (providing simultaneously the P and Ga atoms) and observed that their electric and structural properties were poorer than that grown by the proposed PE-ALD method. The influence of growth conditions on the GaP/Si heterostructures was explored. We found that low RF-plasma power leads to better photoelectric, structural and defect-related properties, due to a better passivation of the silicon wafer. In addition, we demonstrated that, contrary to results reported in the literature using MBE processes, our growth process does not affect the electronic properties of phosphorous doped n-Si wafers, while slight changes were observed in boron-doped p-Si wafers containing Fe-related defects, however without deactivation of the doping nor strong degradation of the electronic properties.

Philosophiae Doctor - PhD / The main aim of this study was to prepare band gap-engineered graphene quantum dot (GQD) structures which match the different energies of the visible region in the solar spectrum. These band gap-engineered graphene quantum dot structures were used as donor materials in rainbow Schottky junction solar cells, targeting all the energies in the visible region of the solar spectrum for improved solar-to-electricity power conversion efficiency. Structural characterisation of the prepared nanomaterials under solid-state nuclear magnetic resonance spectroscopy (SS-NMR) showed appearance of bands at 40 ppm due to the presence of sp3 hybridised carbon atoms from the peripheral region of the GQD structures. Other bands were observed at 130 ppm due to the presence of polycyclic aromatic carbon atoms from the benzene rings of the GQD backbone, and around 180 ppm due to the presence of carboxylic acid carbons from oxidation due to moisture. Fourier-transform infrared resonance (FTIR) spectroscopy further confirmed the presence of aromatic carbon atoms and oxidised carbons due to the presence of C=O, C=C and -OH functional groups, concurrent with SS-NMR results. / 2023-12-01

abstract: The emergence of perovskite and practical efficiency limit to silicon solar cells has opened door for perovskite and silicon based tandems with the possibility to achieve >30% efficiency. However, there are material and optical challenges that have to be overcome for the success of these tandems. In this work the aim is to understand and improve the light management issues in silicon and perovskite based tandems through comprehensive optical modeling and simulation of current state of the art tandems and by characterizing the optical properties of new top and bottom cell materials. Moreover, to propose practical solutions to mitigate some of the optical losses. Highest efficiency single-junction silicon and bottom silicon sub-cell in silicon based tandems employ monocrystalline silicon wafer textured with random pyramids. Therefore, the light trapping performance of random pyramids in silicon solar cells is established. An accurate three-dimensional height map of random pyramids is captured and ray-traced to record the angular distribution of light inside the wafer which shows random pyramids trap light as well as Lambertian scatterer. Second, the problem of front-surface reflectance common to all modules, planar solar cells and to silicon and perovskite based tandems is dealt. A nano-imprint lithography procedure is developed to fabricate polydimethylsiloxane (PDMS) scattering layer carrying random pyramids that effectively reduces the reflectance. Results show it increased the efficiency of planar semi-transparent perovskite solar cell by 10.6% relative. Next a detailed assessment of light-management in practical two-terminal perovskite/silicon and perovskite/perovskite tandems is performed to quantify reflectance, parasitic and light-trapping losses. For this first a methodology based on spectroscopic ellipsometry is developed to characterize new absorber materials employed in tandems. Characterized materials include wide-bandgap (CH3NH3I3, CsyFA1-yPb(BrxI1-x)3) and low-bandgap (Cs0.05FA0.5MA0.45(Pb0.5Sn0.5)I3) perovskites and wide-bandgap CdTe alloys (CdZnSeTe). Using this information rigorous optical modeling of two-terminal perovskite/silicon and perovskite/perovskite tandems with varying light management schemes is performed. Thus providing a guideline for further development. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2019

Organic solar cell (OSC) has been an active research field over the past decades, due to their intrinsic advantages, such as low consumption of materials and energy, the applicability on flexible substrates and the degradability of the organic components. Compared with the solution processing technology using polymers as electron donor materials, small molecule vacuum deposition is regarded as a promising fabrication method, avoiding the use of toxic aromatic solvents and guaranteeing constant batch-to-batch performance. Moreover, it is much easier to realize multi-junction tandem solar cells (TSCs) by thermal deposition, and the leading power conversion efficiency (PCE) of 13.2% was achieved using three different absorbers by vacuum deposition (“Heliatek sets new organic photovoltaic world record efficiency of 13.2%” 2016). In this dissertation, novel electron donor materials are synthesized based on the molecular skeleton of a famous chromophore, boron dipyrromethene (BODIPY), and chemical modifications are carried out to tune the intense absorption bands of these dyes to near infrared (NIR, λ>750,nm) region. Efficient small molecule NIR absorbers are highly required for TSCs, because they can construct a complementary absorption over the visible and NIR spectral region in cooperation with a wide bandgap material. Three β-fused aza-BODIPY molecules with heterocyclic substituents on α-positions are prepared using organolithium reagents and phthalonitrile as the starting materials. The organolithium reagents, namely N-methylpyrrole, N-methylindole and 2-trimethylsilylthiophene, are used instead of commonly used Grignard reagents. Moreover, three corresponding aza-BODIPY derivatives are obtained by replacing one fluorine atom in the BF_{2} moiety by a cyano group. UV-vis absorption spectra reveal that all these materials are strong NIR absorbers, and their abortion in solid state cover a wide range from 600 to 1000,nm. OSCs with these aza-BODIPY donors give a best PCE of 3.0%, which is a reasonable value for the NIR devices with the maximum and the onset of the EQE spectrum around 850 and 950,nm respectively. A series of furan-fused BODIPYs with a electron withdrawing CF_{3} group on the meso-C are synthesized, and the photophysical/electrochemical properties can be tuned easily by the electronic properties of the substituents on the peripheral aromatic rings. The most promising candidate gives a high PCE of 6.1% in a single junction OSC with a J_{sc} of 13.3,mA/cm^{2}, a V_{oc} of 0.73,V, and a FF of 62.7%. A serial connected TSC is fabricated using this BODIPY as the low bandgap donor and a “green” donor, and its EQE spectrum covers a wide range from 400 to 900,nm. The PCE reaches 9.9% with a J_{sc} of 9.9,mA/cm^{2}, a V_{oc} of 1.70,V, and a FF of 59.0%. Based on the general structure of furan-fused BODIPY, alkyl or fluorinated alkyl substituents with larger volume is introduced on either peripheral aromatic rings or the meso-C. The variations that caused by these substituents on the photophysical and electrochemical properties are negligible. The investigations on the OSCs demonstrate that the introduction of these alkyl chain substituents have positive influence on the PCE values, which benefit mainly from the increased photocurrent. However, there is no positive relationship between the device performance and the volume of the alkyl chain substituents. BODIPY molecules have been demonstrated as efficient and promising NIR electron donor materials for vacuum-deposited OSCs. Taking advantages of facile molecular modification, oustanding photophysical behaviors and tunable electrochemical properties, this series of dyes are also intereting for other semiconductor devices.

Philosophiae Doctor - PhD / The commercial need to improve the performance of low-cost organic solar cells has led to the idea for this research. The study discusses the synthesis of one dimensional TiO2 and ZnO nanowire arrays synthesised using a hydrothermal autoclave method and their application in bulk heterojunction inverted organic solar cells. Previous literature has shown that the precise manipulation, positioning and assembly of 1D nanostructures remain one of the greatest challenges in the field of nanotechnology, with much of the difficulty arising primarily from the lack of size and scale of the materials as well as the inability to visualise the nanostructures. In particular, one dimensional metal-oxides such as TiO2, ZnO and Fe2O3 have emerged as attractive alternatives to traditional semiconductor structures such as Si and GaAs as they are simple and inexpensive to manufacture, with research showing that application of ZnO nano-cones yield efficiencies of 8.4%, which is very attractive given the scope that exists in optimising the metal-oxide architecture. Much is still to be learned from the precise structural features of these materials and their influence on device performance. In this regard, this work largely focuses on this aspect of metal-oxide nanowires prior their application in organic solar cells.