A l’échelle mondiale, la part des énergies renouvelables dans le mix énergétique est de plus en plus importante. Basées sur le principe de la photosynthèse, les cellules solaires à colorant sont une des technologies émergentes viables pour une intégration en bâtiment. Ces cellules hybrides utilisent un oxyde semi-conducteur inorganique dont la surface est recouverte d’un colorant organique. L’absorption de la lumière incidente par ce colorant va provoquer l’injection d’un électron de l’état photo-excité de la molécule dans la bande de conduction de l’oxyde. Un médiateur rédox présent dans l’électrolyte va venir régénérer le colorant oxydé et générer un courant sous illumination. Les colorants déjà décrits dans la littérature présentent déjà des rendements de conversion pouvant atteindre 14 % mais très peu de ces matériaux peuvent absorber jusque dans la gamme proche infrarouge (700-1000 nm). Pourtant l’absorption des photons de cette gamme spectrale pourrait mener à une plus grande densité de courant générée et à de meilleures performances globales. Dans ce contexte, ce travail présente une étude complète de nouveaux colorants absorbeurs panchromatiques capable de collecter des photons jusque dans la gamme proche infrarouge. Pour cela, l’approche « donneur-accepteur » a été utilisée afin d’obtenir les propriétés optoélectroniques désirées. Une première famille à base de dérivés du benzothiadiazole a été développée conduisant à de très bonnes propriétés d’absorption dans la gamme proche infrarouge (absorption jusqu’à 925 nm). Les propriétés optiques, électrochimiques et photovoltaïques de ces matériaux ont été étudiées afin de comprendre les limitations de ces matériaux pour une application en cellules solaires. Suite à cela, une nouvelle famille de colorant à base de dérivés de l’isoindigo a été synthétisée et étudiée par spectroscopie UV-Visible, électrochimie et simulation DFT. Ces composés absorbent fortement dans la gamme UV-visible et proche infrarouge jusqu’à 848 nm. Après avoir optimisé les conditions d’imprégnation et de formulation de l’électrolyte, nous avons atteint un rendement de conversion en dispositif de 5,76%. Des mesures photophysiques nous ont permis d’avoir une compréhension fine des facteurs limitant l’efficacité de conversion de ces colorants. Fort de ce constat, nous avons amélioré la structure d’une des molécules pour atteindre un rendement de 7,0 %. Nous avons aussi de manière prospective testé différents matériaux alternatifs au système TiO2/iode classiquement utilisé. / On a global scale, the share of renewable energies in the energy mix is constantly increasing. Based on the principle of photosynthesis, Dye-Sensitized Solar Cells are an emerging technology for Building Integration Photovoltaic (BIPV). These hybrid cells use an inorganic semiconductor oxide whose surface is covered with an organic dye. The absorption of the incident light by this dye will cause the injection of an electron from the photo-excited state of the molecule into the conduction band of the oxide. A redox mediator present in the electrolyte will regenerate the oxidized dye and generate a current under illumination. The dyes already described in the literature shows efficiencies reaching 14%. On the other hand, very few of these materials can absorb up to the near infrared range (NIR) (700-1000 nm). Thereby, the absorption of the NIR spectral range could lead to a greater photo-generated current density. In this context, this work presents a complete study of new panchromatic dyes extending into the near infrared range. For this study, the "donor-acceptor" approach was used to obtain the desired optoelectronic properties. A first family based on benzothiadiazole derivatives has been developed leading to very good absorption properties in the NIR region (absorption up to 925 nm). The optical, electrochemical and photovoltaic properties of these materials have been studied in order to understand the limitations for solar cell applications. Following this, a new dye family based on isoindigo derivatives was synthesized and studied by UV-Visible spectroscopy, electrochemistry and DFT simulation. These compounds strongly absorbs in the UV-visible and NIR spectral range up to 848 nm. The dyeing bath composition and the electrolyte formulation were optimized in order to obtain a device conversion efficiency of 5.76%. Photophysical measurements have allowed us to have a fine understanding of the limiting factors of these dyes. On the basis of this observation, we improved the structure of one of the dye and witg this new molecule we reached a power conversion efficiency of 7.0% with a UV-Visible and near infrared absorption for the solar cell. In the last part of this work we have also obtained preliminary results employing various alternative materials to the TiO2/iodine system.

Ce travail traite de la croissance épitaxiale et de la caractérisation d’hétérostructures àbase de multi-puits quantiques (MPQ) pour des applications dans le photovoltaïque. Leséchantillons ont été obtenus par la technique d’épitaxie en phase vapeur aux organométalliques(EPVOM) sur des substrats de saphir (0001). La caractérisation structurale etoptique est réalisée par diffraction de rayons X, microscopie électronique en transmission,spectroscopie de photoluminescence et de transmission. Pour étudier la présence de l’effetphotovoltaïque et pour estimer la performance électrique des échantillons, les MPQ ont étéintégrés dans la géométrie de cellules solaires en utilisant de la photolithographie, desattaques réactives ioniques assistées par plasma inductif et des métallisations pour contacterles parties dopées n et p.Nous avons étudié l’influence de différents designs des régions actives InGaN/GaN surles propriétés optiques et électriques des échantillons, c’est-à-dire le nombre de puitsquantiques InGaN, les épaisseurs des puits et des barrières et la composition en indium dansles puits. Deux mécanismes principaux doivent être pris en compte pour une optimisationefficace de composants photovoltaïques: l’absorption des photons et la collections desporteurs. Nous avons montré qu’une augmentation du nombre de MPQ, de leur épaisseur etde la composition d’In améliorait l’absorption, mais causait aussi des pertes dans l’efficacitéde collection du fait de l’augmentation de l’épaisseur de la couche active (champ électriqueplus faible), de la difficulté des porteurs pour s’échapper de puits plus profonds et derelaxation des contraintes (création de défauts structuraux). La décroissance de l’épaisseur desbarrières peut résoudre les deux premiers points, mais le problème de la relaxation de lacontrainte reste entier. Pour notre meilleur design, nous obtenons une efficacité de conversionde 2 % pour des couches 15×In0.18Ga0.82N/GaN qui ont une réponse spectrale qui s’étendjusqu’à 465 nm. / In this work we report on epitaxial growth and characterization of InGaN/GaN multiquantumwells (MQWs) heterostructures for application in photovoltaic devices. The sampleswere grown by metal-organic vapor phase epitaxy (MOVPE) on (0001) sapphire substrate.The structural and optical characterization is performed by X-ray diffraction, transmissionelectron microscopy, photoluminescence spectroscopy and transmission measurements. Toinvestigate the presence of photovoltaic effect and estimate the electrical performance of thesamples, they were processed into solar cells by means of the photolithography, inductivelycoupled plasma reactive-ion etching and metallization to manage n and p contacts.We studied the influence of different InGaN/GaN active region designs on thestructural, optical and electrical properties of the samples, i.e. number of InGaN quantumwells, QW and quantum barrier thicknesses and indium composition in the wells. Two mainmechanisms have to be taken into account for an efficient optimization of photovoltaicdevices: photon absorption and carrier collection. We showed that an increase of the MQWsnumber, their thickness and the In-content allows absorption improvement, but causes lossesin the carrier collection efficiency due to: the increase of the active region thickness (lowerelectric field), the difficulty of the carrier to escape from deeper QWs and the strain relaxation(structural defect creation). The decrease of the barrier thickness can solve the first two issues,but the problem with strain relaxation remains. In the best design, we report the value of2.00% of conversion efficiency for 15×In0.18Ga0.82N/GaN samples with spectral responseextending to 465 nm.

My PhD thesis work is to design, synthesize, and characterize inexpensive and reliable nanocomposites for the photovoltaic (PV) devices. Photovoltaic materials utilized in our studies were synthesized using simple and inexpensive methods. The material properties were tailored and optimized to improve the optical absorption and charge transport properties. The PV cells fabricated with these materials exhibited improved power conversion efficiencies (PCE). The origin of charge generation and charge transfer was studied using different photoactive materials such as CdSe quantum dots (QDs), perylene-3, 4, 9, 10-tetracarboxylic-3, 4, 9, 10-dianhydride (PTCDA), poly(3-hexylthiophene) (P3HT), multiwalled carbon nanotubes (MWCNTs), multilayer graphene (MuLG), and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM).

Multiscale computational simulations are performed to investigate how electronic structure and optical absorption characteristics of recently reported nanostructured III-nitride core-shell MQW solar cells are governed by an intricate coupling of size-quantization, atomicity, and built-in structural and polarization fields. The core computational framework, as available in our in-house QuADS 3-D simulator, is divided into four coupled phases: 1) Geometry construction for the wurtzite lattice having hexagonal crystal symmetry and non-conventional crystal orientations; 2) Structural relaxation and calculation of atomistic strain distributions using the VFF Keating molecular-mechanics model, which employs a conjugate gradient energy minimization scheme; 3) Obtaining the induced polarization and internal potential distributions using a 3-D atomistic Poisson solver; 4) Computing the single-particle electronic structure and optical transition rates using a 10- band sp3 s*-spin tight-binding framework; and 5) Using a TCAD toolkit, study the carrier transport and obtain the device terminal characteristics. Special care was taken in incorporating the nonpolar m-plane crystallographic orientation within the simulator via appropriate lattice vectors, rotational matrices, neighboring atom co-ordinates and sp3-hybridized passivation scheme. Numerical calculations of electronic structure properties are generally based on non-primitive rectangular unit cell. The rectangular geometry approximation is still valid and can be considered even in the presence of strain in nanostructures such as quantum wells, nanowires, and even in self-assembled quantum dots with varying composition. With this approximation, atoms are grouped into traditional unit cells resulting in simpler analysis and better storage scheme, which results in more dynamic and easily debugged algorithms. Note that the contribution of the second-order piezoelectric polarization is small in the nonpolar m-plane structure (as compared to the polar c-plane counterpart) and was neglected in this study. Besides, the spontaneous polarization is non-existent in m-plane structure. The polarization fields are incorporated in the Hamiltonian as an external potential within a non-self-consistent approximation. From the simulations, it is found that, even without the inclusion of any internal fields, the crystal symmetry is lowered compared to ideal geometries, which is due mainly to the fundamental atomicity and interface discontinuities. However, with the inclusion of internal polarization fields, although the symmetry is lowered further, the m-plane structure exhibits a stronger overlap and localization of the wavefunctions, as compared to the c-plane counterpart. Importantly, strain, in the m-plane structure, causes a larger splitting of the topmost valence band and the interband transition probability involving the 4th valence band was found to be highest. Overall, the m-plane structure offers higher spontaneous emission rate and internal quantum efficiency (IQE) as well as an improved fill-factor.

abstract: A single solar cell provides close to 0.5 V output at its maximum power point, which is very low for any electronic circuit to operate. To get rid of this problem, traditionally multiple solar cells are connected in series to get higher voltage. The disadvantage of this approach is the efficiency loss for partial shading or mismatch. Even as low as 6-7% of shading can result in more than 90% power loss. Therefore, Maximum Power Point Tracking (MPPT) at single solar cell level is the most efficient way to extract power from solar cell. Power Management IC (MPIC) used to extract power from single solar cell, needs to start at 0.3 V input. MPPT circuitry should be implemented with minimal power and area overhead. To start the PMIC at 0.3 V, a switch capacitor charge pump is utilized as an auxiliary start up circuit for generating a regulated 1.8 V auxiliary supply from 0.3 V input. The auxiliary supply powers up a MPPT converter followed by a regulated converter. At the start up both the converters operate at 100 kHz clock with 80% duty cycle and system output voltage starts rising. When the system output crosses 2.7 V, the auxiliary start up circuit is turned off and the supply voltage for both the converters is derived from the system output itself. In steady-state condition the system output is regulated to 3.0 V. A fully integrated analog MPPT technique is proposed to extract maximum power from the solar cell. This technique does not require Analog to Digital Converter (ADC) and Digital Signal Processor (DSP), thus reduces area and power overhead. The proposed MPPT techniques includes a switch capacitor based power sensor which senses current of boost converter without using any sense resistor. A complete system is designed which starts from 0.3 V solar cell voltage and provides regulated 3.0 V system output. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2015

abstract: Thin films have been widely used in various applications. This research focuses on the characterization of novel thin films in the integrated circuits and photovoltaic techniques. The ion implanted layer in silicon can be treated as ion implanted thin film, which plays an essential role in the integrated circuits fabrication. Novel rapid annealing methods, i.e. microwave annealing and laser annealing, are conducted to activate ion dopants and repair the damages, and then are compared with the conventional rapid thermal annealing (RTA). In terms of As+ and P+ implanted Si, the electrical and structural characterization confirms that the microwave and laser annealing can achieve more efficient dopant activation and recrystallization than conventional RTA. The efficient dopant activation in microwave annealing is attributed to ion hopping under microwave field, while the liquid phase growth in laser annealing provides its efficient dopant activation. The characterization of dopants diffusion shows no visible diffusion after microwave annealing, some extent of end range of diffusion after RTA, and significant dopant diffusion after laser annealing. For photovoltaic applications, an indium-free novel three-layer thin-film structure (transparent composited electrode (TCE)) is demonstrated as a promising transparent conductive electrode for solar cells. The characterization of TCE mainly focuses on its optical and electrical properties. Transfer matrix method for optical transmittance calculation is validated and proved to be a desirable method for predicting transmittance of TCE containing continuous metal layer, and can estimate the trend of transmittance as the layer thickness changes. TiO2/Ag/TiO2 (TAgT) electrode for organic solar cells (OSCs) is then designed using numerical simulation and shows much higher Haacke figure of merit than indium tin oxide (ITO). In addition, TAgT based OSC shows better performance than ITO based OSC when compatible hole transfer layer is employed. The electrical and structural characterization of hole transfer layers (HTLs) in OSCs reveals MoO3 is the compatible HTL for TAgT anode. In the end, the reactive ink printed Ag film for solar cell contact application is studied by characterizing its electromigration lifetime. A percolative model is proposed and validated for predicting the resistivity and lifetime of printed Ag thin films containing porous structure. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2017

L'objectif principal de cette thèse est dirigé vers l'établissement et l'explication des relations entre les conditions de synthèse des couches minces de CZTSSe, ses propriétés physiques et les performances des dispositifs photovoltaïques. Pour faire face à cette tâche la première approche était de comprendre le mécanisme de formation de la matière par rapport aux conditions de croissance du matériau. Le CZTSSe est synthétisé par un processus de sélénisation en deux étapes, où une première étape de dépôt par PVD de précurseurs est nécessaire, suivie d'une seconde étape de recuit sous atmosphère de sélénium. Différents ordres d'empilement de précurseurs ont été étudiés afin de comprendre la séquence de réactions qui, à partir de leur dépôt, conduise à la couche finale de CZTSSe. Cette étude, fait en plusieurs étapes, a nécessité de un effort important sur la caractérisation du matériau à chaque étape de la synthèse. Le résultat a montré que dans le cas du procédé en deux étapes, le matériau final est indépendant du dépôt de précurseurs. Les possibles implications bénéfiques en raison de l'incorporation de sodium dans le CZTSSe sont également décrites. Cette étude est réalisée en synthétisant la couche de CZTSSe sur différents substrats contenant diffèrent taux de sodium: de cette manière, pendant la synthèse, le sodium migre de substrats vers l'absorbeur. Après quantification du Na dans le CZTSSe juste après la croissance, le matériau est caractérise afin d'évaluer sa qualité. Ensuite il est employé dans une cellule solaire complète pour vérifier ses propriétés photovoltaïques. Les résultats ont montré que, comme pour la technologie CIGS, le sodium est bénéfique pour le CZTSSe, permettant l'augmentation de la tension à circuit ouvert et le rendement de cellule. Le molybdène est le contact arrière le plus utilisé pour les cellules solaires à base CZTSSe. Cependant, il a été suggéré récemment que le Mo n'est pas stable à l'interface avec le CZTSSe. En outre, à ma connaissance, aucune étude expérimentale n'a été effectuée à ce jour pour tester si les cellules solaires construites sur un autre contact arrière pourraient présenter de meilleures propriétés photovoltaïques. A cet effet, divers métaux (Au, W, Pd, Pt et Ni) sont déposées sur le dessus de Mo et testés comme contacts arrières dans les cellules solaire à base de CZTSSe. Il est démontré qu'il est possible synthétiser de films minces de CZTSSe de qualité quand le tungstène, l'or et le platine sont employé comme contacts arrière. Il est démontré que les contacts en W et Au permettent d'augmenter le courant photogénéré, mais aussi que le Mo reste le meilleur contact arrière en termes d'efficacité de conversion. Les effets de la variation du rapport [S]/([S]+[Se]) sur les performances des cellules solaires à base CZTSSe ont été étudiés. Cette étude a été faite par simulations des cellules solaires à base de CZTSSe, où le taux de chalcogènes dans l'absorbeur est varié, avec l'objective de trouver la composition optimale de l'absorbeur. Deux types d'approche différente ont été étudiés: la variation linéaire du rapport des chalcogènes, et une variation parabolique. Les simulations conduisent à un rendement de 16,5% (avec une tension en circuit ouvert de 0,56 V, courant de court-circuit de 37,0 mA/cm2 et un facteur de forme de 79,0%) lorsque la teneur en soufre est diminué linéairement à partir du contact arrière en direction de la couche tampon. Sur la base de ces résultats, nous proposons que l'ingénierie de bande interdite sur la base de la variation du taux [S]/([S]+[Se]) dans l'absorbeur est un outil puissant qui permet d'augmenter les performances des cellules solaires à base CZTSSe sans changer la qualité de l'absorbeur en lui-même. / The main objective of this PhD thesis was directed toward establishing and explaining the relationships between synthesis conditions of CZTSSe, its physical properties and performance of photovoltaic devices. To tackle on this task the first approach was to understand the formation mechanism of the material in relation to the growth conditions. CZTSSe is synthesized by two-step selenization process, where a first step of precursor deposition by PVD is required, followed by a second step of annealing. Different precursor stacking orders have been studied in order to understand the sequence of reactions that, starting from their deposition, lead to the final CZTSSe layer. This study made step-by-step has required a strong effort on the material characterization at each step of the synthesis. The result demonstrated that in the case of two-step process, the final material is independent of the precursor deposition. The possible beneficial involvements due to incorporation of sodium in CZTSSe are also disclosed. This study is carried out by synthesizing CZTSSe on different sodium-containing substrates: in this way sodium migrates from the substrates to the absorber. After quantification of Na in CZTSSe right after growth, the latter is characterized to evaluate its quality and employed in a full solar cell to check on its photovoltaic properties. Results demonstrated that, as for CIGS technology, sodium is beneficial for CZTSSe allowing increasing the open circuit voltage and efficiency. Molybdenum is the most used back contact in CZTSSe based solar cells. However, it has been suggested recently that Mo is not stable at the interface with CZTSSe. In addition, to the best of our knowledge, no experimental study has been carried out so far to test whether solar cells built on another back contact could exhibit better photovoltaic properties. For this purpose, various metals (Au, W, Pd, Pt, and Ni) are deposited on top of Mo, and it is demonstrated that it is possible to synthesize device-quality CZTSSe thin films on W, Au, and Pt back contacts. It is shown that that W and Au back contacts allow enhancing the photogenerated current, but that Mo remains the best back contact in terms of power conversion efficiency. The effects of [S]/([S]+[Se]) ratio tuning on CZTSSe based solar cell performances have been studied by solar cell capacitance simulator (SCAPS) to find out the optimum absorber composition. Two different kind of approach have been studied: linear variation of the chalcogens ratio, and a parabolic variation. The simulations lead to an efficiency of 16.5% (with open-circuit voltage of 0.56 V, short-circuit current of 37.0 mA/cm2 and fill factor of 79.0%) when the sulfur content is linearly decreased from the back contact towards the buffer layer. Based on these results, we propose that bandgap engineering based on the control of [S]/([S]+[Se]) ratio in the absorber is a powerful tool which allows increasing the performances of CZTSSe based solar cells without changing the absorber material quality.

The market for renewable energy sources, and solar cells in particular is growing year by year, as a result there is a large interest in research on new materials and new technologies for solar power applications. In this thesis the photovoltaic properties of cubic silicon carbide (3C-SiC) has been investigated. The research includes material growth using the sublimation epitaxy method, both n-type and p-type SiC have been investigated. 3C-SiC pn junctions have been produced and their electrical properties have been characterized, this is the first time 3C-SiC pn junctions have been studied in the research group. Photoresponse has been demonstrated from a 3C-SiC pn junction with Al and N used as p- and ntype dopants. This is the first demonstrated solar cell performance using 3C-SiC, to our knowledge.

abstract: Zinc oxide (ZnO) has attracted much interest during last decades as a functional material. Furthermore, ZnO is a potential material for transparent conducting oxide material competing with indium tin oxide (ITO), graphene, and carbon nanotube film. It has been known as a conductive material when doped with elements such as indium, gallium and aluminum. The solubility of those dopant elements in ZnO is still debatable; but, it is necessary to find alternative conducting materials when their form is film or nanostructure for display devices. This is a consequence of the ever increasing price of indium. In addition, a new generation solar cell (nanostructured or hybrid photovoltaics) requires compatible materials which are capable of free standing on substrates without seed or buffer layers and have the ability introduce electrons or holes pathway without blocking towards electrodes. The nanostructures for solar cells using inorganic materials such as silicon (Si), titanium oxide (TiO2), and ZnO have been an interesting topic for research in solar cell community in order to overcome the limitation of efficiency for organic solar cells. This dissertation is a study of the rational solution-based synthesis of 1-dimentional ZnO nanomaterial and its solar cell applications. These results have implications in cost effective and uniform nanomanufacturing for the next generation solar cells application by controlling growth condition and by doping transition metal element in solution. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2012

abstract: Silicon (Si) solar cells are the dominant technology used in the Photovoltaics industry. Field-effect passivation by means of electrostatic charges stored in an overlying insulator on a silicon solar cell has been proven to be a significantly efficient way to reduce effective surface recombination velocity and increase minority carrier lifetime. Silicon nitride (SiNx) films have been extensively used as passivation layers. The capability to store charges makes SiNx a promising material for excellent feild effect passivation. In this work, symmetrical Si/SiO2/SiNx stacks are developed to study the effect of charges in SiNx films. SiO2 films work as barrier layers. Corona charging technique showed the ability to inject charges into the SiNx films in a short time. Minority carrier lifetimes of the Czochralski (CZ) Si wafers increased significantly after either positive or negative charging. A fast and contactless method to characterize the charged overlying insulators on Si wafer through lifetime measurements is proposed and studied in this work, to overcome the drawbacks of capacitance-voltage (CV) measurements such as time consuming, induction of contanmination and hysteresis effect, etc. Analytical simulations showed behaviors of inverse lifetime (Auger corrected) vs. minority carrier density curves depend on insulator charge densities (Nf). From the curve behavior, the Si surface condition and region of Nf can be estimated. When the silicon surface is at high strong inversion or high accumulation, insulator charge density (Nf) or surface recombination velocity parameters (Sn0 and Sp0) can be determined from the slope of inverse lifetime curves, if the other variable is known. If Sn0 and Sp0 are unknown, Nf values of different samples can be compared as long as all have similar Sn0 and Sp0 values. Using the saturation current density (J0) and intercept fit extracted from the lifetime measurement, the bulk lifetime can be calculated. Therefore, this method is feasible and promising for charged insulator characterization. / Dissertation/Thesis / M.S. Electrical Engineering 2014