abstract: Silicon photovoltaics (PV) is approaching its theoretical efficiency limit as a single-junction technology. To break this limit and further lower the PV-generated levelized cost of electricity, it is necessary to engineer a silicon-based “tandem” technology in which a solar cell of another material is stacked on top of silicon to make more efficient use of the full solar spectrum. This dissertation understands and develops four aspects of silicon-based tandem PV technology. First, a new “spectral efficiency” concept is proposed to understand how tandem cells should be designed and to identify the best tandem partners for silicon cells. Using spectral efficiency, a top-cell-design guide is constructed for silicon-based tandems that sets efficiency targets for top cells with various bandgaps to achieve targeted tandem efficiencies. Second, silicon heterojunction solar cells are tuned to the near-infrared spectrum to enable world-record perovskite/silicon tandems both in two- and four-terminal configurations. In particular, for the 23.6%-efficient two-terminal tandem, a single-side textured silicon bottom cell is fabricated with a low-refractive-index silicon nanoparticle layer as a rear reflector. This design boosts the current density to 18.5 mA/cm2; this value exceeds that of any other silicon bottom cell and matches that of the top cell. Third, “PVMirrors” are proposed as a novel tandem architecture to integrate silicon cells with various top cells. A strength of the design is that the PVMirror collects diffuse light as a concentrating technology. With this concept, a gallium-arsenide/silicon PVMirror tandem is demonstrated with an outdoor efficiency of 29.6%, with respect to the global irradiance. Finally, a simple and versatile analytical model is constructed to evaluate the cost competitiveness of an arbitrary tandem against its sub-cell alternatives. It indicates that tandems will become increasingly attractive in the market, as the ratio of sub-cell module cost to area-related balance-of-system cost—the key metric that will determine the market success or failure of tandems—is decreasing. As an evolution of silicon technology, silicon-based tandems are the future of PV. They will allow more people to have access to clean energy at ultra-low cost. This thesis defines both the technological and economic landscape of silicon-based tandems, and makes important contributions to this tandem future. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2018

In this thesis, research on a-Si:H Schottky diodes and a-Si:H/c-Si heterojunctions is presented with the focus on the capacitance spectroscopy and information on electronic properties that can be derived from this technique. Last years a-Si:H/c-Si heterojunctions (HJ) have received growing attention as an approach which combines wafer and thin film technologies due to their low material consumption and low temperature processing. HJ solar cells benefit from lower fabrication temperatures thus reduced costs, possibilities of large-scale deposition, better temperature coefficient and lower silicon consumption. The most recent record efficiency belongs to Panasonic with 24.7% for a cell of 100 cm² was obtained. The aim of this thesis is to provide a critical study of the capacitance spectroscopy as a technique that can provide information on both subjects: DOS in a-Si:H and band offset values in a-Si:H/c-Si heterojunctions.The first part of the manuscript is devoted to capacitance spectroscopy in a-Si:H Schottky diodes. The interest is concentrated on the simplified treatment of the temperature and frequency dependence of the capacitance that allows one to extract the density of states at the Fermi level in a-Si:H. We focus on the study of the reliability and validity of this approach applied to a-Si:H Schottky barriers with various magnitudes and shapes of the DOS. Several structures representing n-type and undoped hydrogenated amorphous silicon Schottky diodes are modeled with the help of numerical simulation softwares. We show that the reliability of the studied treatment drastically depends on the approximations used to obtain the explicit analytical expression of the capacitance in such an amorphous semiconductor.In the second part of the chapter, we study the possibility of fitting experimental capacitance data by numerical calculations with the input a-Si:H parameters obtained from other experimental techniques. We conclude that the simplified treatment of the experimentally obtained capacitance data together with numerical modeling can be a valuable tool to assess some important parameters of the material if one considers the results of numerical modeling and performs some adjustments. The second part is dedicated to capacitance spectroscopy of a-Si:H/c-Si heterojunctions with special emphasis on the influence of a strong inversion layer in c-Si at the interface. Firstly, we focus on the study of the frequency dependent low temperature range of capacitance-temperature dependencies of a-Si:H/c-Si heterojunctions. The theoretical analysis of the capacitance steps in calculated capacitance-temperature dependencies is presented by means of numerical modeling. It is shown that two steps can occur in the low temperature range, one being attributed to the activation of the response of the gap states in a-Si:H to the small signal modulation, the other one being related to the response of holes in the strong inversion layer in c-Si at the interface. The experimental behavior of C-T curves is discussed. The quasi-static regime of the capacitance is studied as well. We show that the depletion approximation fails to reproduce the experimental data obtained for (p) a-Si:H/(n) c-Si heterojunctions. Due to the existence of the strong inversion layer, the depletion approximation overestimates the potential drop in the depleted region in crystalline silicon and thus underestimates the capacitance and its increase with temperature. A complete analytical calculation of the heterojunction capacitance taking into account the hole inversion layer is developed. It is shown that within the complete analytical approach the inversion layer brings significant changes to the capacitance for large values of the valence band offset. The experimentally obtained C-T curves show a good agreement with the complete analytical calculation and the presence of the inversion layer in the studied samples is thus confirmed.

Les travaux développés dans cette thèse sont dédiés à l’étude des propriétés électroniques de diodes Schottky de silicium amorphe hydrogéné (a-Si:H) et d'hétérojonctions entre silicium amorphe hydrogéné et silicium cristallin, a-Si:H/c-Si au moyen de spectroscopies de capacité de jonctions.Lors de la fabrication des cellules solaires à haut rendement plusieurs paramètres d’une hétérojonction a-Si:H/c-Si doivent être considérés. Premièrement, la densité d’états dans le gap du a-Si:H est d’une grande importance car il s’agit de défauts qui favorisent le piégeage et la recombinaison de porteurs. Deuxièmement, la détermination des désaccords des bandes entre la couche amorphe et la couche cristalline est indispensable puisque ceux-ci contrôlent le transport à travers la jonction et déterminent la courbure des bandes dans c-Si, ce qui va notamment influencer la recombinaison des porteurs sous lumière, donc la tension de circuit ouvert des cellules. Cette thèse a pour but d’étudier la spectroscopie de capacité comme technique d'analyse de paramètres clés pour les dispositifs à hétérojonctions de silicium : la densité d’états dans le a-Si:H et les désaccords des bandes entre a-Si:H et c-Si.La première partie est dédiée à l’étude de la capacité de diodes Schottky. Nous nous concentrons sur un traitement simplifié de la capacité en fonction de la température et de la fréquence reposant sur une expression analytique obtenue par une résolution approchée de l'équation de Poisson. Ce traitement permet en principe d’extraire la densité d’états au niveau de Fermi dans le a-Si:H et la fréquence de saut des électrons depuis un état localisé au niveau de Fermi vers la bande de conduction. En appliquant ce traitement simplifié à la capacité calculée sans approximation à l'aide de deux logiciels de simulation numérique, nous montrons que sa fiabilité et sa validité dépendent fortement de la distribution des états localisés dans la bande interdite du a-Si:H et de la position du niveau de Fermi. Puis nous abordons l’étude de la capacité des hétérojonctions entre a-Si:H de type p et c-Si de type n, et nous mettons particulièrement en avant l’existence d'une couche d’inversion forte à l’interface dans le c-Si, formant un gaz bidimensionnel de trous. Dans une première partie, nous présentons une étude par simulation numérique de la dépendance de la capacité en fonction de la température, pour laquelle un ou deux échelons peuvent être mis en évidence à basse température. Leur analyse montre qu’un des ces échelons est attribué à l’activation de la réponse de la charge dans le a-Si:H, alors que l’autre, présentant une énergie d'activation plus grande, est lié à la modulation de la concentration des trous dans la couche d’inversion forte, lorsque celle-ci existe. On présente ensuite une discussion de résultats expérimentaux. Le régime quasi-statique de la capacité fait ainsi l’objet d’une discussion. Nous mettons en relief le fait que l’approximation de la zone de déplétion ne permet pas de reproduire cette augmentation de la capacité en fonction de la température. Du fait de l’existence de la couche d’inversion forte, la chute de potentiel dans la zone de déplétion du c-Si est plus faible que la valeur déterminée par le calcul attribuant toute la chute de potentiel à la zone de déplétion. Par conséquent, cette approximation conduit à sous-estimer la capacité ainsi que son augmentation avec la température. Nous présentons alors un calcul analytique complet qui tient compte à la fois de la distribution particulière du potentiel dans le a-Si:H, et des trous dans le c-Si dont la contribution à la concentration totale de charges n'est pas négligeable dans la couche d’inversion forte. Le calcul analytique complet permet de bien reproduire les résultats expérimentaux de capacité en fonction de la température; ceci confirme la présence de la couche d’inversion forte dans les échantillons étudiés. / In this thesis, research on a-Si:H Schottky diodes and a-Si:H/c-Si heterojunctions is presented with the focus on the capacitance spectroscopy and information on electronic properties that can be derived from this technique. Last years a-Si:H/c-Si heterojunctions (HJ) have received growing attention as an approach which combines wafer and thin film technologies due to their low material consumption and low temperature processing. HJ solar cells benefit from lower fabrication temperatures thus reduced costs, possibilities of large-scale deposition, better temperature coefficient and lower silicon consumption. The most recent record efficiency belongs to Panasonic with 24.7% for a cell of 100 cm² was obtained. The aim of this thesis is to provide a critical study of the capacitance spectroscopy as a technique that can provide information on both subjects: DOS in a-Si:H and band offset values in a-Si:H/c-Si heterojunctions.The first part of the manuscript is devoted to capacitance spectroscopy in a-Si:H Schottky diodes. The interest is concentrated on the simplified treatment of the temperature and frequency dependence of the capacitance that allows one to extract the density of states at the Fermi level in a-Si:H. We focus on the study of the reliability and validity of this approach applied to a-Si:H Schottky barriers with various magnitudes and shapes of the DOS. Several structures representing n-type and undoped hydrogenated amorphous silicon Schottky diodes are modeled with the help of numerical simulation softwares. We show that the reliability of the studied treatment drastically depends on the approximations used to obtain the explicit analytical expression of the capacitance in such an amorphous semiconductor.In the second part of the chapter, we study the possibility of fitting experimental capacitance data by numerical calculations with the input a-Si:H parameters obtained from other experimental techniques. We conclude that the simplified treatment of the experimentally obtained capacitance data together with numerical modeling can be a valuable tool to assess some important parameters of the material if one considers the results of numerical modeling and performs some adjustments. The second part is dedicated to capacitance spectroscopy of a-Si:H/c-Si heterojunctions with special emphasis on the influence of a strong inversion layer in c-Si at the interface. Firstly, we focus on the study of the frequency dependent low temperature range of capacitance-temperature dependencies of a-Si:H/c-Si heterojunctions. The theoretical analysis of the capacitance steps in calculated capacitance-temperature dependencies is presented by means of numerical modeling. It is shown that two steps can occur in the low temperature range, one being attributed to the activation of the response of the gap states in a-Si:H to the small signal modulation, the other one being related to the response of holes in the strong inversion layer in c-Si at the interface. The experimental behavior of C-T curves is discussed. The quasi-static regime of the capacitance is studied as well. We show that the depletion approximation fails to reproduce the experimental data obtained for (p) a-Si:H/(n) c-Si heterojunctions. Due to the existence of the strong inversion layer, the depletion approximation overestimates the potential drop in the depleted region in crystalline silicon and thus underestimates the capacitance and its increase with temperature. A complete analytical calculation of the heterojunction capacitance taking into account the hole inversion layer is developed. It is shown that within the complete analytical approach the inversion layer brings significant changes to the capacitance for large values of the valence band offset. The experimentally obtained C-T curves show a good agreement with the complete analytical calculation and the presence of the inversion layer in the studied samples is thus confirmed.

In this thesis, research on a-Si:H Schottky diodes and a-Si:H/c-Si heterojunctions is presented with the focus on the capacitance spectroscopy and information on electronic properties that can be derived from this technique. Last years a-Si:H/c-Si heterojunctions (HJ) have received growing attention as an approach which combines wafer and thin film technologies due to their low material consumption and low temperature processing. HJ solar cells benefit from lower fabrication temperatures thus reduced costs, possibilities of large-scale deposition, better temperature coefficient and lower silicon consumption. The most recent record efficiency belongs to Panasonic with 24.7% for a cell of 100 cm² was obtained. The aim of this thesis is to provide a critical study of the capacitance spectroscopy as a technique that can provide information on both subjects: DOS in a-Si:H and band offset values in a-Si:H/c-Si heterojunctions.The first part of the manuscript is devoted to capacitance spectroscopy in a-Si:H Schottky diodes. The interest is concentrated on the simplified treatment of the temperature and frequency dependence of the capacitance that allows one to extract the density of states at the Fermi level in a-Si:H. We focus on the study of the reliability and validity of this approach applied to a-Si:H Schottky barriers with various magnitudes and shapes of the DOS. Several structures representing n-type and undoped hydrogenated amorphous silicon Schottky diodes are modeled with the help of numerical simulation softwares. We show that the reliability of the studied treatment drastically depends on the approximations used to obtain the explicit analytical expression of the capacitance in such an amorphous semiconductor.In the second part of the chapter, we study the possibility of fitting experimental capacitance data by numerical calculations with the input a-Si:H parameters obtained from other experimental techniques. We conclude that the simplified treatment of the experimentally obtained capacitance data together with numerical modeling can be a valuable tool to assess some important parameters of the material if one considers the results of numerical modeling and performs some adjustments. The second part is dedicated to capacitance spectroscopy of a-Si:H/c-Si heterojunctions with special emphasis on the influence of a strong inversion layer in c-Si at the interface. Firstly, we focus on the study of the frequency dependent low temperature range of capacitance-temperature dependencies of a-Si:H/c-Si heterojunctions. The theoretical analysis of the capacitance steps in calculated capacitance-temperature dependencies is presented by means of numerical modeling. It is shown that two steps can occur in the low temperature range, one being attributed to the activation of the response of the gap states in a-Si:H to the small signal modulation, the other one being related to the response of holes in the strong inversion layer in c-Si at the interface. The experimental behavior of C-T curves is discussed. The quasi-static regime of the capacitance is studied as well. We show that the depletion approximation fails to reproduce the experimental data obtained for (p) a-Si:H/(n) c-Si heterojunctions. Due to the existence of the strong inversion layer, the depletion approximation overestimates the potential drop in the depleted region in crystalline silicon and thus underestimates the capacitance and its increase with temperature. A complete analytical calculation of the heterojunction capacitance taking into account the hole inversion layer is developed. It is shown that within the complete analytical approach the inversion layer brings significant changes to the capacitance for large values of the valence band offset. The experimentally obtained C-T curves show a good agreement with the complete analytical calculation and the presence of the inversion layer in the studied samples is thus confirmed.

abstract: It has been a long-standing goal to epitaxially integrate III-V alloys with Si substrates which can enable low-cost microelectronic and optoelectronic systems. Among the III-V alloys, gallium phosphide (GaP) is a strong candidate, especially for solar cells applications. Gallium phosphide with small lattice mismatch (~0.4%) to Si enables coherent/pseudomorphic epitaxial growth with little crystalline defect creation. The band offset between Si and GaP suggests that GaP can function as an electron-selective contact, and it has been theoretically shown that GaP/Si integrated solar cells have the potential to overcome the limitations of common a-Si based heterojunction (SHJ) solar cells. Despite the promising potential of GaP/Si heterojunction solar cells, there are two main obstacles to realize high performance photovoltaic devices from this structure. First, the growth of the polar material (GaP) on the non-polar material (Si) is a challenge in how to suppress the formation of structural defects, such as anti-phase domains (APD). Further, it is widely observed that the minority-carrier lifetime of the Si substrates is significantly decreased during epitaxially growth of GaP on Si. In this dissertation, two different GaP growth methods were compared and analyzed, including migration-enhanced epitaxy (MEE) and traditional molecular beam epitaxy (MBE). High quality GaP can be realized on precisely oriented (001) Si substrates by MBE growth, and the investigation of structural defect creation in the GaP/Si epitaxial structures was conducted using high resolution X-ray diffraction (HRXRD) and high resolution transmission electron microscopy (HRTEM). The mechanisms responsible for lifetime degradation were further investigated, and it was found that external fast diffusors are the origin for the degradation. Two practical approaches including the use of both a SiNx diffusion barrier layer and P-diffused layers, to suppress the Si minority-carrier lifetime degradation during GaP epitaxial growth on Si by MBE were proposed. To achieve high performance of GaP/Si solar cells, different GaP/Si structures were designed, fabricated and compared, including GaP as a hetero-emitter, GaP as a heterojunction on the rear side, inserting passivation membrane layers at the GaP/Si interface, and GaP/wet-oxide functioning as a passivation contact. A designed of a-Si free carrier-selective contact MoOx/Si/GaP solar cells demonstrated 14.1% power conversion efficiency. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2017

Die vorliegende Arbeit beschäftigt sich mit Ätzprozessen von alkalischen und insbesondere HF/HNO3-basierten Ätzmedien an Silicium (Si). Es wurden Ätzprozesse an kristallinen (c-Si) und besonders an amorph/kristallinen (a-Si:H/c-Si) Silicium-Strukturen mit Hilfe von in situ Photolumineszenz(PL)-Messungen untersucht. Diese ermöglichen eine Verfolgung der Veränderung der Grenzflächendefektdichte an der c-Si-Grenzfläche während der Ätzprozesse. Es wurde erstmals beobachtet, dass der über Ladungsträgerinjektion von Löchern in das Si ablaufende Ätzprozess in HNO3-reichen, HF/HNO3-basierten Ätzmedien eine temporäre Feldeffektpassivierung an der geätzten Grenzfläche verursacht, welche zu einer Verzögerung des eigentlichen Auflöseprozesses des Si führt. Die Anwendung dieser Ätzmedien erfolgte im Rahmen der Strukturierung von a-Si:H-Schichten auf c-Si zur Realisierung von interdigitierenden Kontaktstrukturen rückseitenkontaktierter a-Si:H/c-Si-Heterosolarzellen. Für diese Ätzprozesse konnte mit Hilfe von in situ PL-Messungen erstmalig eine in situ Prozesskontrolle etabliert werden. Der Ätzprozess kann exakt bei Erreichen der a-Si:H/c-Si-Grenzfläche gestoppt werden, wodurch die ätzbedingte Defektbildung an der resultierenden c-Si-Oberfläche minimiert wird. Als weiterer Themenschwerpunkt wurde eine Photolithographie-freie Nanostrukturierung von a-Si:H/c-Si-Strukturen durch metallkatalysiertes Ätzen (MAE) vorgestellt, wobei MAE erstmals auf a-Si:H angewandt wurde. Anhand von in situ PL-Messungen konnte ebenfalls eine, wenn auch geringere, Feldeffektpassivierung an der geätzten Grenzfläche im Zuge der Injektion von Löchern in das Si durch die katalytisch aktiven Ag Nanopartikel (AgNP) beobachtet werden. Mit den so steuerbaren MAE-Prozessen können a-Si:H-Schichten exakt bis zur a-Si:H/c-Si-Grenzfläche punktuell geöffnet werden. Auf diese Weise wurden p-Typ a-Si:H/c-Si-Heterosolarzellen mit einem punktförmigen Absorberkontakt erfolgreich realisiert. / This dissertation is concerned with wet chemical etching processes of silicon (Si) by alkaline and especially HF/HNO3 based etchants. The etching processes are applied to crystalline (c-Si) and amorphous/crystalline (a-Si:H/c-Si) samples and analyzed by in situ photoluminescence (PL) measurements. These measurements enable a monitoring of changes in the defect density at the c-Si interface during the etching processes. By etching of Si in HNO3-rich HF/HNO3 based etchants, a temporary field effect passivation at the etched c-Si surface by hole injection was established. It was detected by in situ PL measurements for the first time. This effect causes a delay of the actual dissolution of the Si. These etching processes were applied to structure a-Si:H layers on c-Si in order to establish interdigitated contacts for back contacted a-Si:H/c-Si heterojunction solar cells. A process control for that kind of etch back processes was developed for the first time by in situ PL measurements. This method enables an exact termination of the etching processes with the arrival of the etching front at the a-Si:H/c-Si interface. Thus, etching induced defects at the resulting c-Si surface can be reduced. Finally this thesis focuses on the development of a photolithography-free approach for nanostructuring of a-Si:H/c-Si samples using metal assisted etching (MAE). In this context, MAE was applied to a-Si:H for the first time. In situ PL measurements also showed a temporary field effect passivation during MAE due to hole injection by the catalytically active Ag nanoparticles (AgNP). Here, this effect was less distinct because of only punctual etching by the AgNP. These designed MAE processes are used to selectively etch a-Si:H layers exactly down to the a-Si:H/c-Si interface. This process opens new doors to a novel fabrication technique for point contacted heterojunction solar cells. P-type a-Si:H/c-Si heterojunction solar cells with point contacted back surface field are presented.

La technologie des cellules photovoltaïques silicium à hétérojonction (HET) a montré un intérêt croissant ces dernières années. En alliant les avantages des technologies couches minces et silicium cristallin (c-Si), elle permet un meilleur compromis coûts-performances que les cellules purement c-Si. Cette thèse a pour but d'améliorer la compréhension des mécanismes physiques qui régissent les performances de ces cellules, en mettant à profit des compétences spécifiques de caractérisation et de simulation issues de la microélectronique. Nos travaux se focalisent sur l'étude de la face avant de la cellule HET de type n, composée d'un empilement de couches minces d'oxyde d'indium dopé à l'étain (ITO) et de silicium amorphe hydrogéné (a-Si:H). Nous commençons par une étude théorique et expérimentale de la conduction des couches d'a-Si:H en fonction de la température, du dopage et des défauts qu'elles contiennent. Prendre en compte l'équilibre dopant/défaut de ces couches est primordial mais nous montrons aussi que le travail de sortie des électrodes en contact, comme l'ITO, peut influer fortement sur la position du niveau de Fermi dans les films nanométriques d'a-Si:H. Nous présentons ensuite une évaluation de sept techniques de caractérisation du travail de sortie afin d'identifier les plus adaptées à l'étude de semiconducteurs dégénérés tels que l'ITO. Nous montrons notamment l'intérêt de techniques originales de la microélectronique comme les mesures de capacité C(V), de courant de fuite I(V) et de photoémission interne (IPE) sur des empilements ITO/biseau d'oxyde/silicium. Nous mettons clairement en évidence que les propriétés volumiques de l'ITO peuvent être optimisées, mais que les interfaces ont un effet prépondérant sur les valeurs de travaux de sortie effectifs (EWF) extraits. Une bonne cohérence globale a été obtenue pour les techniques C(V), I(V) et IPE sur biseau de silice (SiO2) ; les valeurs extraites ont notamment permis d'expliquer des résultats expérimentaux d'optimisation des cellules. Nous montrons que la tension de circuit ouvert (Voc) des cellules est finalement peu sensible au travail de sortie, contrairement au Facteur de Forme (FF), grâce à la couche d'a-Si:H. Plus cette dernière est dopée, défectueuse et épaisse, plus elle est capable d'écranter les variations électrostatiques d'EWF. Aussi, le travail de sortie doit être suffisamment élevé pour pouvoir réduire les épaisseurs de couche p d'a-Si:H et ainsi gagner en courant de court-circuit (Jsc) sans perdre en FF ni Voc. Enfin, il nous a été possible d'appliquer cette méthodologie à d'autres oxydes transparents conducteurs (TCO) que l'ITO. Le meilleur candidat de remplacement de l'ITO doit non seulement présenter une transparence optique élevée, être un bon conducteur et avoir un fort travail de sortie effectif, mais il faut également prêter une attention particulière à la dégradation éventuelle des interfaces causée par les techniques de dépôt. / By combining the advantages of thin-films and crystalline silicon (c-Si), the silicon heterojunction solar cell technology (HET) achieves a better cost-performance compromise than the technology based only on c-Si. The aim of this thesis is to improve the understanding of the physical mechanisms which govern the performance of these cells by taking advantage of specific characterization and simulation skills taken from microelectronics. Our study focuses on the front-stack of the n type cell composed of thin layers of indium tin oxide (ITO) and hydrogenated amorphous silicon (a-Si:H). We begin with a theoretical and experimental study of the conductivity of a-Si:H layers as a function of temperature, doping concentration and bulk defects density. It is important to properly take into account the dopant/defect equilibrium of these layers but we also show that the work function of the electrodes in contact, such as the ITO, can strongly influence the Fermi level in the nano-films of a-Si:H. Then, we evaluate seven characterization techniques dedicated to the work function extraction in order to identify the most suitable one for studying degenerate semiconductors such as the ITO. We particularly show the interest of using original microelectronics techniques such as capacitance C(V), leakage current I(V) and internal photoemission (IPE) measurements on ITO/bevel oxide/silicon test structures. We clearly demonstrate that the ITO bulk properties can be optimized, yet the interfaces have a major influence on the extracted values of the effective work function (EWF). A good overall consistency has been obtained for C(V), I(V) and IPE measurements on a silicon dioxide bevel (SiO2) ; the extracted values enabled us to explain experimental results concerning the optimization of HET cells. We show that the open circuit voltage (Voc) of these devices is finally barely sensitive to work function, unlike the Fill Factor (FF). This is due to the a-Si:H layer. The more it is doped, defective and thick, the more it is able to screen the electrostatic variations of EWF. Thus, EWF must be sufficiently high to be able to reduce the p a-Si:H layer thickness and, in turn, to gain in short-circuit current (Jsc) without losing either in FF or Voc. Finally, we successfully applied this methodology to other types of transparent conductive oxides (TCO) differing from ITO. The best candidate to replace ITO must not only have a high optical transparency, be a good conductor and have a high EWF, but we must also pay close attention to the possible interface degradations caused by the deposition techniques.

The present work focuses on the growth and characterizations of GaN and InN layers and nanostructures on p-Si(100) and p-Si(111) substrates by plasma-assisted molecular beam epitaxy and the studies of GaN/p-Si and InN/p-Si heterojunctions properties. The thesis is divided in to seven different chapters. Chapter 1 gives a brief introduction on III-nitride materials, growth systems, substrates, possible device applications and technical background. Chapter 2 deals with experimental techniques including the details of PAMBE system used in the present work and characterization tools for III-nitride epitaxial layers as well as nanostructures. Chapter 3 involves the growth of GaN films on p-Si(100) and p-Si(111) substrates. Phase pure wurtzite GaN films are grown on Si (100) substrates by introducing a silicon nitride layer followed by low temperature GaN growth as buffer layers. GaN films grown directly on Si (100) are found to be phase mixtured, containing both cubic and hexagonal modifications. The x-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy studies reveal that the significant enhancement in the structural and optical properties of GaN films grown with silicon nitride buffer layer grown at 800 oC, when compared to the samples grown in the absence of silicon nitride buffer layer and with silicon nitride buffer layer grown at 600 oC. Core-level photoelectron spectroscopy of SixNy layers reveals the sources for superior qualities of GaN epilayers grown with the high temperature substrate nitridation process. The discussion has been carried out on the typical inverted rectification behavior exhibited by n-GaN/p-Si heterojunctions. Considerable modulation in the transport mechanism is observed with the nitridation conditions. The heterojunction fabricated with the sample of substrate nitridation at high temperature exhibites superior rectifying nature with reduced trap concentrations. Lowest ideality factors (~1.5) are observed in the heterojunctions grown with high temperature substrate nitridation which is attributed to the recombination tunneling at the space charge region transport mechanism at lower voltages and at higher voltages space charge limited current conduction is the dominating transport mechanism. Whereas, thermally generated carrier tunneling and recombination tunneling are the dominating transport mechanisms in the heterojunctions grown without substrate nitridation and low temperature substrate nitridation, respectively. A brief comparison of the structural, optical and heterojunction properties of GaN grown on Si(100) and Si(111) has been carried out. Chapter 4 involves the growth and characterizations of InN nanostructures and thinfilms on p-Si(100) and p-Si(111) substrates. InN QDs are grown on Si(100) at different densities. The PL characteristics of InN QDs are studied. A deterioration process of InN QDs, caused by the oxygen incorporation into the InN lattice and formation of In2O3/InN composite structures was established from the results of TEM, XPS and PL studies. The results confirm the partial oxidation of the outer shell of the InN QDs, while the inner core of the QDs remains unoxidized. InN nanorods are grown on p-Si(100), structural characterizations are carried out by SEM, and TEM. InN nanodots are grown on p-Si(100), structural characterizations are performed. InN films were grown on Si(100) and Si(111) substrates and structural characterizations are carried out. Chapter 5 deals with the the heterojunction properties of InN/p-Si(100) and InN/p-Si(111).The transport behavior of the InN NDs/p-Si(100) diodes is studied at various bias voltages and temperatures. The temperature dependent ZB BH and ideality factors of the forward I-V data are observed, while it is governed through the modified Richardson’s plot. The difference in FB BH and C-V BH and the deviation of ideality factor from unity indicate the presence of inhomogeneities at the interface. The band offsets derived from C-V measurements are found to be Δ EC=1.8 eV and Δ EV =1.3 eV, which are in close agreement with Anderson’s model. The band offsets of InN/p-Si heterojunctions are estimated using XPS data. A type-III band alignment with a valence band offset of Δ EV =1.39 eV and conduction band offset of ΔEC=1.81 eV is identified. The charge neutrality level model provides a reasonable description of the band alignment of the InN/p-Si interface. The interface dipole deduced by comparison with the electron affinity model is 0.06 eV. The transport studies of InN NR/p-Si(100) heterojunctions have been carried out by conductive atomic force microscopy (CAFM) as well as conventional large area contacts. Discussion of the electrical properties has been carried out based on local current-voltage (I-V) curves, as well as on the 2D conductance maps. The comparative studies on transport properties of diodes fabricated with InN NRs and NDs grown on p-Si(100) substrates and InN thin films grown on p-Si(111) substrates have also been carried out. Chapter 6 deals with the growth and characterizations of InN/GaN heterostructures on p-Si(100) and p-Si(111) substarets and also on the InN/GaN/p-Si heterojunction properties. The X-ray diffraction (XRD), scanning electron microscopy (SEM) studies reveal a considerable variation in crystalline quality of InN with grown parameters. Deterioration in the rectifying nature is observed in the case of InN/GaN/p-Si(100) heterojunction substrate when compared to InN/GaN/p-Si (111) due to the defect mediated tunneling effect, caused by the high defect concentration in the GaN and InN films grown on Si(100) and also due to the trap centers exist in the interfaces. Reduction in ideality factor is also observed in the case of n-InN/n-GaN/p–Si(111) when compared to n-InN/n-GaN/p–Si(100) heterojunction. The sum of the ideality factors of individual diodes is consistent with experimentally observed high ideality factors of n-InN/n-GaN/p–Si double heterojunctions due to double rectifying heterojunctions and metal semiconductor junctions. Variation of effective barrier heights and ideality factors with temperature are confirmed, which indicate the inhomogeneity in barrier height, might be due to various types of defects present at the GaN/Si and InN/GaN interfaces. The dependence of forward currents on both the voltage and temperatures are explained by multi step tunneling model and the activation energis were estimated to be 25meV and 100meV for n-InN/n-GaN/p–Si(100) and n-InN/n-GaN/p–Si(111) heterojunctions, respectively. Chapter 7 gives the summary of the present study and also discusses about future research directions in this area.

Les cellules solaires à hétérojonction a-Si:H/c-Si atteignent un rendement record de 24.7% en laboratoire. La passivation de la surface du c-Si est la clé pour obtenir de hauts rendements. En effet, la brusque discontinuité de la structure cristalline à l'interface amorphe/cristal induit une forte densité de liaisons pendantes créant une grande densité de défauts dans la bande interdite. Ces défauts sont des centres de recombinaison pour les paires électron-trou photogénérées dans le c-Si. Différentes couches diélectriques peuvent être utilisées pour passiver les wafers dopés n et dopés p : (i) le SiO₂ réalisé par croissance thermique, (ii) l’Al₂O₃ déposé par ALD, (iii) le a-SiNₓ:H et l’a-Si:H déposés par PECVD. La couche de passivation la plus polyvalente est a Si:H puisqu’elle peut passiver aussi bien les wafers dopés n que ceux dopés p. De plus sa production est peu coûteuse en énergie car sa croissance est réalisée à une température d’environ 200°C. L’inconvénient de cette couche de passivation est que lorsqu’elle est dopée p elle ne supporte pas des températures supérieures à 200°C, en raison de l’exodiffusion des atomes d’hydrogène qu’elle contient. Cependant, afin d'avoir un bon contact électrique, TCO et électrodes métalliques, il est souhaitable de recuire à plus haute température (entre 300°C et 500°C). Nous avons implanté des ions Argon de façon contrôlée dans des précurseurs de cellules solaires à des énergies comprises entre 1 et 30 keV, pour contrôler la profondeur à laquelle nous créons les défauts. En variant la fluence entre 10¹² Ar.cm⁻² et 10¹⁵ Ar.cm⁻² nous contrôlons la concentration de défauts créés. Nous montrons qu’une implantation à une énergie de 5 keV avec une fluence de 10¹⁵ Ar.cm⁻² n’est pas suffisante pour endommager l’interface a-Si:H/c-Si. La durée de vie effective des porteurs minoritaires mesurée par photoconductance (temps de décroissance de la photoconductivité) passe de 3 ms à 2,9 ms après implantation. En revanche les implantations à 10 keV, 10¹⁴ Ar.cm⁻² ou à 17 keV, 10¹² Ar.cm⁻² sont suffisantes pour dégrader la durée de vie effective de plus de 85%. Suite aux implantations les cellules solaires ont subi des recuits sous atmosphère contrôlée à différentes températures et ce jusqu’à 420°C. Nous avons découvert que le recuit permet de guérir les défauts introduits par l’implantation. Mais surtout, dans certains cas, d’obtenir des durées de vie après implantation et recuit supérieures aux durées de vies initiales. En combinant l’implantation ionique et les recuits, nous conservons de bonnes durées de vies effectives des porteurs de charges (supérieures à 2 ms) même avec des recuits jusqu’à 380°C. Nous avons utilisé une grande variété de techniques telles que la photoconductance, la photoluminescence, l’ellipsométrie spectroscopique, la microscopie électronique en transmission, la Spectroscopie de Masse d’Ions Secondaires, la spectroscopie Raman et l’exodiffusion de l’hydrogène pour caractériser et analyser l’ensemble des résultats et phénomènes physico-chimique intervenant dans la modification des précurseur de cellules solaires. Nous discutons ici de plusieurs effets tels que l’augmentation de la durée de vie et la tenue en température par la conservation de l’hydrogène dans la couche de silicium amorphe et ceci même après les recuits. Cette conservation peut s’expliquer par l’augmentation du nombre de liaisons Si-H au sein du silicium amorphe et par la formation de cavités lors de l’implantation. Durant les recuits l’hydrogène qui diffuse est piégé puis libéré par les cavités et/ou les liaisons pendantes, ce qui limite son exo-diffusion et le rend de nouveau disponible pour la passivation des liaisons pendantes. / A-Si:H/c-Si heterojunction solar cells have reached record efficiencies of 24.7%. The passivation of c-Si is the key to achieve a high-efficiency. Indeed, the abrupt discontinuity in the crystal structure at the amorphous/crystal interface induces a high density of dangling bonds creating a high density of defects in the band gap. These defects act as recombination centers for electron-hole pairs photogenerated in c-Si. Several dielectric layers can be used to passivate n-type and p-type wafers: (i) SiO₂ produced by thermal growth, (ii) Al₂O₃ deposited by ALD, (iii) a-SiNₓ:H and a-Si:H deposited by PECVD. The most versatile passivation layer is a-Si: H because it is effective for both p-type and n-type wafers. In addition, this process has a low thermal budget since the deposition is made at 200°C. The drawback of this passivation layer, in particular when p-type doped, is that it does not withstand temperatures above 200°C. However, in order to have a good electrical contact, TCO and metal electrodes require high temperature annealing (between 300°C and 500°C).We implanted Argon ions in solar cell precursors with energies between 1 and 30 keV, which allows to control the depth to which we are creating defects. By varying the fluence between 10¹² Ar.cm⁻² and 10¹⁵ Ar.cm⁻² we control the concentration of defects. We show that implantation with an energy of 5 keV and a fluence of 10¹⁵ Ar.cm⁻² is not sufficient to damage the a-Si:H/c-Si interface. The effective lifetime of the minority charge carriers, measured using a photoconductance technique (decay time of photoconductivity), decreases only from 3 ms to 2.9 ms after implantation. On the other hand the implantations at 10 keV, 10¹⁴ Ar.cm⁻² or at 17 keV, 10¹² Ar.cm⁻² are sufficient to degrade the effective lifetime by more than 85%.Following implantation the solar cells have been annealed in a controlled atmosphere at different temperatures and this up to 420°C. We show that annealing can heal the implantation defects. Moreover, under certain conditions, we obtain lifetimes after implantation and annealing greater than the initial effective lifetime. Combining ion implantation and annealing leads to robust passivation with effective carrier lifetimes above 2 ms even after annealing our solar cell precursors at 380°C. We used a large variety of techniques such as photoconductance, photoluminescence, spectroscopic ellipsometry, Transmission Electron Microscopy, Secondary Ion Mass Spectrometry, Raman spectroscopy and hydrogen exodiffusion to characterize and analyze the physico-chemical phenomena involved in the modification of solar cells precursors. We discuss here several effects such as the increase of the effective lifetime and the temperature robustness by the preservation of hydrogen in amorphous silicon layer and this even after annealing. This hydrogen preservation can be explained by the increase of the number of Si–H bonds in amorphous silicon and the formation of cavities during implantation. In the course of annealing the hydrogen which diffuses is trapped and then released by cavities and dangling bonds, which limits its exodiffusion and makes it available for dangling bonds passivation.

Les cellules à hétérojonctions de silicium fabriquées par croissance de couches minces de silicium amorphe hydrogéné (a-Si :H) à basse température sur des substrats de silicium cristallin (c-Si) peuvent atteindre des rendements de conversion photovoltaïque élevés (η=23 % démontré). Les efforts de recherche ayant principalement été orientés vers le cristallin de type p jusqu'à présent en France, ce travail s'attache à l'étude du type n pour d'une part déterminer les performances auxquelles s'attendre avec cette nouvelle filière et d'autre part les améliorer. Pour cela, nous avons mis en œuvre des techniques de caractérisation des matériaux composant la structure et de l’interface (a-Si :H/c-Si) couplées à des outils de simulations numériques afin mieux comprendre les phénomènes de transport électronique. Nous nous sommes également intéressés aux cellules à hétérojonctions avec substrats de silicium multicristallin de type n, le silicium multicristallin étant le matériau le plus répandu actuellement dans la fabrication des cellules photovoltaïques. / In this thesis we focus on the silicon heterostructure combining thin films amorphous silicon (a-Si :H) deposited at low temperature on crystalline silicon (c-Si) substrates. We study the different materials and the interface between them through both characterizations, modelling and numerical simulations. The goal is to better understand the influence of the different parameters (doping level, defects density, band offset, ...) on the photovoltaic solar cell's performances in order to get them improved. Structures with multicrystalline silicon substrates are also studied.