Στην διατριβή αυτή μελετήθηκαν και εξακριβώθηκαν θεωρητικά όλες οι φυσικές διεργασίες που υπεισέρχονται στις μετρήσεις του διαμορφωμένου φωτορεύματος. Με βάση αυτές δείξαμε ότι μπορούμε να εξάγουμε όλες τις πιθανές διεργασίες παγίδευσης και επανασύνδεσης σε διάφορες κατηγορίες ανόργανων ημιαγωγών. Σαν μελλοντική μελέτη μπορεί να γίνει η επέκταση της θεωρητικής ανάλυσης για υλικά όπου έχουμε ατέλειες που μπορούν να βρεθούν σε περισσότερες από δύο καταστάσεις φορτίου όπως είναι οι αιωρούμενοι δεσμοί του άμορφου . Επίσης η ανάλυση που προτείνουμε μπορεί να εφαρμοστεί και στην κατηγορία των οργανικών ημιαγωγών. / In this thesis we studied and verified theoretically, all the physical processes involved in modulated photocurrent measurements. Based on these measurements, we show that we can extract all possible trapping and recombination processes in different classes of inorganic semiconductors. As future study, we can extend the theoretical analysis for materials which have defects that may be found in more than two charge states such as the dangling bonds in amorphous silicon. Also, the analysis we propose can be applied to the class of organic semiconductors.

Yes / The application of photoelectrochemical methods presents the researcher with a powerful set of versatile tools by which photoactive materials, such as semiconductor quantum dots, at conductive interfaces may be interrogated. While the range of photoelectrochemical techniques available is quite large, it is surprising that very few have found their way into common usage within the nanoparticle community. Here a number of photoelectrochemical techniques and the principles upon which they are based are introduced. A short discussion on the criticality of ensuring the nanoparticles are reliably anchored to the substrate is followed by an introduction to the basic set of equipment required in order to enable the investigator to undertake such experiments. Subsequently the four techniques of transient photocurrent response to square wave illumination, photocurrent spectroscopy, intensity modulated photocurrent spectroscopy (IMPS) and intensity modulated photovoltage spectroscopy (IMVS) are introduced. Finally, the information that can be acquired using such techniques is provided with emphasis being placed on a number of case studies exemplifying the application of photoelectrochemical techniques to nanoparticles at interfaces, in particular optically transparent electrodes.

Dans le contexte de la recherche sur l’amélioration des performances et la réduction des coûts des cellules solaires à base de silicium, nous nous sommes intéréssés dans cette thèse aux hétérojonctions entre le silicium amorphe hydrogéné (a-Si:H) et le silicium cristallin (c-Si). Nous avons étudié d’une part l’application de la technique de mesure du PhotoCourant Modulé (MPC) comme outil de caractérisation de l’interface a-Si:H/c-Si et que nous avons couplé à la technique de mesure de PhotoLuminescence Modulée (MPL) déjà largement utilisée pour étudier la qualité de passivation de l’interface. Nous avons alors caractérisé par ces deux techniques une série d'échantillons composées de (p)a-Si:H/(i)a-Si:H/(n)c-Si d'épaisseur de (i)a-Si:H allant de 2 à 50 nm. Une partie importante de cette étude a été réalisée par simulations numériques en 2D afin d’interpréter nos résultats expérimentaux. Une cohérence dans l'estimation de la densité d'état de défauts à l'interface a-Si:H/c-Si a été obtenue par les deux techniques. Nous avons conçu d’autre part un outil de couplage des simulations électriques et optiques pour le design de cellules à base de nanofils à hétérojonction. Grâce à cet outil nous avons réalisé une étude plus réaliste et plus complète qu'auparavant où ces deux simulations étaient effectuées de manière séparée. Nous montrons notamment comment les conditions sur les contacts électriques des nanofils affectent les performances de la cellule solaire. / In the context of the research on improving performances and reducing costs of silicon-based solar cells, we focused on heterojunctions between hydrogenated amorphous silicon (a-Si:H) and crystalline silicon (c-Si). On the one hand, we studied the application of the Modulated PhotoCurrent technique (MPC) as a tool for characterizing the a-Si:H/c-Si interface and which we coupled to the Modulated PhotoLuminescence technique (MPL) widely used to study the quality of interface passivation. We characterized by these two techiques a serie of samples composed of (p)a-Si:H/(i)a-Si:H/(n)c-Si with a thickness of (i)a-Si:H going from 2 to 50 nm. An important part of this study was made by 2D numerical simulations in order to interpret our experimental results. We showed that both techniques give the same estimation of the density of interface defects between (i)a-Si:H and (n)c-Si. On the other hand, we developped a tool for coupling electrical and optical simulations for the design of nanowire-based solar cells with a radial heterojunction. Formerly, these simulations were most of the time performed separately and therefore were not allowing for a complete study of these kind of structures. We then made a study showing how the conditions of electrical contacts of nanowires affect the performances of these solar cells.

No / The objective of this review is to provide an overview concerning what the authors believe to be the most important photoelectrochemical techniques for the study of semiconductor nanoparticles. After a short historical background and a brief introduction to the area of photoelectrochemistry, the working principles and experimental setups of the various static and dynamic techniques are presented. Experimental details which are of crucial importance for their correct execution are emphasized, and applications of the techniques as found in the recent research literature as applied to semiconductor nanoparticles are illustrated.