In this thesis, we use reactive RF magnetron sputtering to deposit zinc oxide (ZnO) buffer layer and main layer on SiO2/Si substrate at room temperature. After various annealing treatments, the ZnO nanowires can be obtained. The effects of buffer layer on the crystallization of ZnO main layer and the zinc-to-oxygen ratio in the main layer on the growth of the ZnO nanowires are analyzed by PL, SEM, XRD and EDS. Finally, the growth mechanism of the ZnO nanowires is investigated by various annealing temperatures. According to the experimental results, surplus zinc in the main layer is necessary for the ZnO nanowires growth. When the annealing temperature is higher than the melting point of zinc, it will melt and be extruded onto thin film surface as a result of the thermal stress. As soon as the melting zinc on the film surface reacts with the oxygen in the air, ZnO nanowires can be obtained. The optimum ZnO nanowires which possess better morphology and high density are revealed by conventional thermal annealing at 600¢J for 90 minutes.

Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The aim of this study was to develop a ZnO nanowire-array biosensor that would detect immunoglobulins and record changes in the concentration of an antibody. Early detection of disease-causing agents is essential for an early response. In contrast to conventional methods, biosensors may detect disease-associated agents much faster and more accurate, which holds specific benefits to rural communities. The development of such a biosensor would be favourable for diagnostics in underprivileged communities without infrastructure. The hypothesis was that binding of antibodies to the surface of ZnO nanowires would result in the generation of a piezoelectric potential that, when channelled through a Schottky barrier, would produce a constant voltage reading. Piezoelectricty would be generated due to the bending of the nanowires, or tensile stress applied to the nanowires due to binding of the antibodies. The performance of such a device largely depends on the methods used to construct the ZnO nanowires and methods used to funtionalize the sensor surface. The biggest challenge was thus to chemically modify the self-assembled monolayers (SAMs) and create intermediate monolayers that would react to primary amino groups of lysozyme and form a covalent amide bond. Lysozyme was selected as model antigen, since its structure and reaction with antibodies has been well studied. Alkanethiol and dialkyl disulphides were used to form SAMs. Different SAMs were compared to select the absorbate that would bind the highest concentration of lysozyme. Lysozyme was best immobilized onto Au film layers in the presence of SAM 3-mercaptopropionic acid. Weakest immobilization was in the presence of combined SAM 11-mercaptoundecanoic acid/1-nonanethiol. The sensitivity of the constructed ZnO nanowire biosensor was tested in vitro, in the presence of different concentrations of lysozyme antibodies. An increase in the dimension of the ZnO seed layer led to an increase in the mean diameter of the ZnO seed grains, and subsequently an increase in the mean diameter of the synthesized ZnO nanowires. Deposition of the ZnO seed layer, using the RF cylindrical magnetron sputtering technique, improved the c-axis alignment of the nanowires and produced nanowires with similar dimensions. However, deposition of the ZnO seed layer using the sol-gel spin coating technique, produced nanowires with irregular c-axis alignments and irregular diameters. An increase in the Au film thickness led to a decrease in the mean diameter of the synthesized ZnO nanowires and worsening of the c-axis alignment. In contrast to single crystalline Au (111) film layers, polycrystalline Au layers increased the mean diameter of the synthesized nanowires. The crystal orientation of the Au film layer had no effect on the c-axis alignment. Increased voltage readings were recorded with an increase in antibody binding, indicating that the ZnO nanosensor may be used to record changes in immunoglobulin levels. Antibody concentrations ranging from 10 ng/ml to 20 μg/ml were sensed. This is the first study showing that ZnO nanowires, conformed into piezoelectric transducers, may be used in the detection of antibodies. The current size of the chip with ZnO nanowires is approximately 1 cm², which is too big to incorporate into a compact monitoring device. Apart from the challenge to produce smaller nanowire-arrays, highly sensitive sensors and miniature amplifiers will have to be developed to increase the strength of the signals generated by the nanowires. The biosensor will also have to be optimised to detect a variety of immunoglobulins. / AFRIKAANSE OPSOMMING: Die doel van hierdie studie was om ‘n ZnO nanodraad biosensor te ontwikkel wat immunoglobuliene kan opspoor en veranderinge in konsentrasies van die teenliggaampies sal reflekteer. Vroë deteksie van siekte veroorsaakende agente is belangrik vir n vroeg tydige respons. In teenstelling tot konvensionele metodes, kan biosensors siekte veroorsaakende agente vining en akkuraat opspoor, wat veral voordele vir gemeenskappe in landelike gebiede inhou. Die hipotese was dat binding van teenliggaampies aan die ZnO nanodrade ‘n piëzo-elektriese potensiaal sal skep, wat dan ‘n konstante leesbare spanningspotensiaal sal lewer nadat dit deur ‘n Schottky versperring gestuur is. Piëzo-elektrisiteit word gegenereer deur die buiging van die nanodrade, of deur spanning wat op die nanodrade geplaas word deur binding van die teenliggaampies. Die sukses van die ontwerp hang grootliks af van die metode wat gebruik word om die ZnO nanodrade te konstrueer en metodes wat gebruik word om die sensor oppervlak te funksionaliseer. Die grootste uitdaging was dus om die monolae wat outomaties saam groepeer (SAMs) chemies so te verander dat intermediêre monolae vorm wat aan primêre aminogroepe van lisosiem bind ten einde kovalente amied-bindings te vorm. Lisosiem is as model antigeen geselekteer omdat die struktuur en reaksie daarvan met teenliggaampies reeds goed bestudeer is. Alkaantiol en di-alkiel disulfied is gebruik om SAMs te vorm. ‘n Verskeidenheid SAMs is vergelyk ten einde die anker te selekteer waaraan die hoogste konsentrasie lisosiem sal bind. Lisosiem is die effektiefste aan Au film lae ge-immobiliseer in die teenwoordigheid van SAM 3-merkapto-propanoësuur. Die swakste immobilisasie is in die teenwoordigheid van kombineerde SAM 11-merkapto-dekanoësuur/1-nanotiol waargeneem. Die sensitiwiteit van die ZnO nanodrade is in vitro getoets, in die teenwoordigheid van verskillende konsentrasies van lisosiem teenliggaampies. ‘n Toename in die dimensie van die ZnO grondlaag het die gemiddelde deursnit van die ZnO grein verhoog en so ook die gemiddelde deursnit van die gesintetiseerde ZnO nanodrade. Toediening van die ZnO grondlaag deur gebruik te maak van die RF silindriese mikrogolf-verstuiwings tegniek het die orientasie van die c-aslyn van die nanodrade verbeter. Toediening met die sol-gel draai-bedekkings tegniek het ‘n onreëlmatige orientasie van die c-aslyn teweeg gebring, asook ‘n variasie in die afmetings van die nanodrade. ‘n Toename in die Au laag het ‘n afname in die gemiddelde afmetings van die nanodrade en ook ‘n onreelmatige oriëntasie van die c-aslyn veroorsaak. In teenstelling met enkel-kristallyne Au (111) het poli-kristallyne Au lagies ‘n toename in die gemiddelde deursnit van die nanodrade veroorsaak. Die kristal-oriëntasie van die Au laag het geen effek op die belyning van die nanodrade gehad nie. Die spanningspotensiaal het verhoog met ‘n toename in teenliggaampie binding. Hiervolgens kan die ZnO nanosensor gebruik word om veranderinge in immunoglobulien vlakke te monitor. Teenliggaampie konsentrasies wat wissel van 10 ng/ml tot 20 μg/ml is opgespoor. Hierdie is die eerste studie wat toon dat ZnO nanodrade, omskep tot piëzo-elektriese transduseerders, gebruik kan word in die opsporing van teenliggaampies. Die grootte van die skyfie met die ZnO nanodrade is tans ongeveer 1 cm² en is te groot om in ‘n kompakte biosensor in te bou. Benewens die uitdaging om kleiner nanodraad skyfies te ontwikkel, sal hoogs sensitiewe sensors en seinversterkers ontwikkel moet word om die sein afkomstig van die nanodrade te versterk. Die biosensor sal ook ge-optimiseer moet word om ‘n verskeidenheid immunoglobuliene op te spoor.

One-dimensional (1D) nanostructures have gained tremendous attention over the last decade due to their wide range of potential applications. Particularly, ZnO 1D nanostructures have been investigated with great interest due to their versatility in synthesis with potential applications in electronics, optics, optoelectronics, sensors, photocatalysts and nanogenerators. The thesis deals with the challenges and the answer to grow ZnO 1D nanostructure by vapor phase transport (VPT) continuously without any length limitation. The conventional VPT technique has been modified for the non-catalytic growth of ultralong ZnO 1D nanostructures and branched structures in large area with controllable aspect ratio. It has been shown that the aspect ratio can be controlled both by thermodynamically (temperature) and kinetically (vapour flux). The thesis also deals with the fabrication of carbon nanotube (CNT) -ZnO based multifunctional devices and the field emission performance of ZnO nanowires by employing various strategies. The entire thesis has been organised as follows: Chapter 1 deals with Introduction. In this chapter, importance of ultralong nanowires and significance of ultralong ZnO nanowires has been discussed. Various efforts to grow ultralong ZnO nanowire with their advantages and disadvantages have been summarised. Lastly the significance of forming ZnO nanowires based nano hybrid structures and importance of doping in ZnO nanowires and has also been discussed. Chapter 2 deals with experimental procedure and characterization. In this chapter, a single step VPT method for the growth of ultralong ZnO nanowires that incorporates local oxidation barrier for the source has been described. The synthesized nanowires were characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman & photoluminescence. Chapter 3 deals with growth of ZnO nanowires, controlling the aspect ratio of ZnO nanowires, and role of other experimental aspects. In this chapter, a way to grow nanowires continuously without any apparent length limitation, a way to control the diameter of the nanowires kinetically without catalyst particle or seed layer and obtaining smaller diameter of the nanowires by non-catalytic growth as compared to that set by the thermodynamic limit has been discussed. Furthermore, the significance and importance of local oxidation barrier on source for protecting them from degradation, ensuring the continuous supply of vapour and enabling the thermodynamically and kinetically controlled growth of nanowires has been discussed. Lastly, the scheme for large area deposition and a method to use same source material for several depositions has been presented. Chapter 4 deals with multifunctional device based on CNT -ZnO Nanowire Hybrid Architectures same device can be used as a rectifier, a transistor and a photodetector. In this chapter, the fabrication of CNT arrays-ZnO nanowires based hybrid architectures that exhibit excellent high current Schottky like behavior with p-type conductivity of ZnO has been discussed. CNT-ZnO hybrid structures that can be used as high current p-type field effect transistors (FETs) and deliver currents of the order of milliamperes has been presented. Furthermore, the p-type nature of ZnO and possible mechanism for the rectifying characteristics of CNT-ZnO has been discussed. Lastly, the use of hybrid structures as ultraviolet detectors where the current on-off ratio and the response time can be controlled by the gate voltage has been presented and also an explanation for photoresponse behaviour has been provided. Chapter 5 deals with the substrate-assisted doping of ZnO nanowires grown by this technique. In this chapter, the non-catalytic growth of ZnO nanowires on multiwalled carbon nanotubes (MWCNTs) and soda lime glass (SLG) with controlled aspect ratio has been presented. The elemental mapping to confirm the presence and distribution of carbon and sodium in ZnO nanowires and the transport studies on both carbon and sodium doped ZnO has also been presented. Furthermore the stability of carbon doped ZnO has also been presented. Lastly, the advantage of growing ZnO nanowires on MWCNTs and overall advantage associated with this technique has been discussed. Chapter 6 deals with formation of ZnO nanowire branched structures. In this chapter, a possibility to grow ZnO nanowires on already grown ZnO nanowires has been demonstrated. The formation of branched structure during multiple growth of ZnO nanowire on ZnO nanowire has been presented and evolution of aspect ratio in these branched structures has been discussed. Furthermore, the advantage of using ZnO branched structures and also the ZnO nanoneedles on MWCNT mat for field emission has been presented. Chapter 7 summarizes all the findings of the thesis.

ZnO is a promising semiconducting material for manufacturing optoelectronic devices. Its most important properties are its wide and direct band gap and its high electron-hole binding energy. Synthesis of ZnO in bulk and thin film form has been investigated intensively over recent decades. Likewise, nanomaterials have been in the point of focus for their different properties compared to their bulk form. The vastly increased ratio of surface area to volume and change in electronic properties with great reduction in particle size enable improved performance in conventional applications where their bulk counterparts have been used for decades. As a result of this trend, research on synthesis of ZnO nanowires and their incorporation in prototype optoelectronic devices has been intensive in recent years. Therefore, synthesis of ZnO nanowires in a cost effective way and understanding the factors influencing the ZnO nanowire growth is essential for contribution to ongoing research. V In this thesis, hydrothermal synthesis of ZnO nanowires, which is a solution based method enabling vertically aligned ZnO nanowire array fabrication over large areas, is investigated. In the first part of this thesis, the effect of using various zinc salts as zinc sources on ZnO nanowires is investigated by monitoring pH, temperature and light transmittance of growth solutions. In the second part, a detailed parametric study on the use of zinc acetate dihydrate salt is provided with regard to the existence of its unique properties compared to other two zinc salts. The effect of growth time, temperature, ratio of concentration of precursor chemicals and precursor chemical concentrations is investigated. The results show that hydrothermal synthesis method could replace the conventional ZnO nanowire fabrication methods. It was shown that specific nanowire lengths for any application can be obtained simply by adjusting the parameters of hydrothermal growth system.

Το οξείδιο του ψευδαργύρου είναι ένας ημιαγωγός της ομάδας II-VI και έχει μεγάλη ποικιλία σε τεχνολογικές εφαρμογές όπως οι αισθητήρες διαφόρων χημικών αερίων, τα lasers, οι δίοδοι εκπομπής φωτός, οι νανο-γεννήτριες, τα ηλιακά κύτταρα και πολλές άλλες. Το ευρύ του ενεργειακό κενό (3.445 eV) το καθιστά ένα πολλά υποσχόμενο υλικό για φωτονικές εφαρμογές στην περιοχή του UV ή του ιώδους, ενώ ταυτόχρονα η υψηλή ενέργεια συνοχής του εξιτονίου που το χαρακτηρίζει (περίπου στα 60 meV) επιτρέπει την αποτελεσματική εξιτονική εκπομπή σε θερμοκρασία δωματίου. Οι πιο πρόσφατες εξελίξεις στον τομέα του νανοδομημένου ZnO είναι οι νανοδρόμοι, οι νανογέφυρες, οι νανοπροπέλες, οι νανοδακτύλιοι, τα νανονήματα κ.α. Στην παρούσα διπλωματική εργασία μελετώνται οι ηλεκτρονιακές και οπτικές ιδιότητες νανονημάτων οξειδίου του ψευδαργύρου (ZnO) για ένα εύρος διαμέτρων από 2 έως 6 nm και με την βοήθεια της εμπειρικής μεθόδου των ψευδοδυναμικών και της Configuration Interaction (CI). Μια ανασκόπηση των ιδιοτήτων και χαρακτηριστικών του bulk ZnO, όπως η κρυσταλλική και η ενεργειακή του δομή, κάποιες τεχνολογικές εφαρμογές και μέθοδοι ανάπτυξης δίνονται στο πρώτο κεφάλαιο. Το δεύτερο κεφάλαιο περιέχει την περιγραφή διαφόρων υπολογιστικών μεθόδων όπως της προσέγγισης ενεργούς μάζας ( Effective Mass Approximation), της θεωρίας του συναρτησιακού της πυκνότητας (Density Functional Theory) και τέλος, της εμπειρικής μεθόδου των ψευδοδυναμικών που χρησιμοποιείται στους υπολογισμούς των ηλεκτρονιακών και οπτικών ιδιοτήτων των νανοδομών που μελετάμε. Στο τρίτο και τελευταίο κεφάλαιο, παρατίθενται τα αριθμητικά αποτελέσματα . Αυτά, αφορούν στο εξαρτώμενο από το μέγεθος, οπτικό ενεργειακό κενό, το Stokes shift, και το φάσμα φωτοφωταύγειας. Στο τέλος του κεφαλαίου περιγράφονται τα συμπεράσματα. / Zinc oxide (ZnO), a typical group II-VI compound, has a great variety of device applications, such as chemical sensors, lasers, light-emitting diodes, nanogenerators, solar cells and so forth. The wide band gap (3.445 eV) makes it a promising material for photonic applications in the UV or the blue range, while the high exciton binding energy (around 60 meV at room temperature) allows efficient excitonic emission at room temperature. The most recent developments are towards the nanostructured ZnO, such as nanorods, nanobridges, nanopropellers, nanorings, nanowires, et al. In the present master thesis, the electronic and optical properties of ZnO nanowires within the range of 2-6 nm in diameter are studied by means of atomistic empirical pseudopotential method and configuration interaction. A review of the bulk ZnO, such as the crystal and band structures, technological applications and synthesis methods, is presented in chapter one. The second chapter is devoted to the discussion of various types of methods, e.g., effective-mass approximation, density-functional theory (DFT), and especially the empirical pseudopotential method used herein, for the calculations of the electronic and optical properties of nanostructured ZnO. The numerical results, based on the empirical pseudopotential methods and configuration interaction approach, are present in the following chapter. These results cover the size-dependent optical band gap, Stokes shift and photoluminescence spectrum. A summarization of the results is given in the last chapter.

We have performed a first principles density functional theory (DFT) calculations to study the thermal conductivity in ZnO nanotubes, ZnO nanowires, and Si/Ge shell-core nanowires. We found the equilibrium configuration and the electric band structure of each nanostructure using DFT, the interatomic force constants and the phonon dispersion relations were calculated using DFPT as implemented in Quantum Espresso. In order to fundamentally understand the effect of atomic arrangements, we calculated the phonon conductance in a ballistic approach using a Green's function method. All ZnO nanostructures studied exhibit semiconducting behavior, with direct bandgap at the Gamma point. The calculated values for the bandgaps were larger than the value of the bandgap of the bulk ZnO. We were able to identify phonon modes in which the motion of Zn atoms is significant when it is compared with the motion of oxygen atoms. The thermal conductivity depends on the diameter of the nanowires and nanotubes and it is dramatically affected when the nanowire or nanotube is doped with Ga. For Si/Ge nanowires, the slope and the curvature of acoustic modes in the phonon dispersion relation increases when the diameter increases. For nanowires with the same number of atoms, the slope and curvature of acoustic modes depends on the concentration of Si atoms. We were able to identify phonon modes in which the motion of core atoms is significant when it is compared with motion of atoms on the nanowire's shell. The thermal conductivity in these nanostructures depends on the nanowire's diameter and on the Si atoms concentration.

This thesis deals with one-dimensional (1D) and two-dimensional nanomaterials (2D) in terms of their utilization for new types of gas sensors. Thesis focuses on study of sensing elements for gas sensors based on semiconductor metal oxide materials (MOX) and their manufacturing technology. The objective of the thesis is the design and implementation of a sensing elements formed by selected nanomaterials based on the structure of interdigital electrodes. The result of the practical part of the thesis is the characterization and comparison of materials in terms of their detection parameters in the presence of selected test gases. The first part of thesis hierarchically defines chemoresistive gas sensor, characterizes and explains its operation principle. Second part studies 1D and 2D nanomaterials of sensing elements for MOX chemoresistive gas sensors, contains a research of their properties and describes their methods of manufacturing and implementation. The last part deals with the implementation of the sensitive layer of the sensor with selected nanomaterials, characterizes and compares their detection properties.

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.

Ce projet de thèse aborde la question de l’intégration hétérogène de nanofils interconnectés sur des puces microélectroniques à destination de dispositifs de type MEMS et NEMS. Ces dispositifs visent à adresser la problématique globale qu’est le « More than Moore », c’est-à-dire la transformation des filières CMOS classiques pour permettre le développement de nouveaux micro et nano-composants intégrés.En particulier, ces dernières années, une variété de dispositifs à base de nanomatériaux ont vu le jour, conférant à des dispositifs de type micro-actionneurs et micro-capteurs de nouvelles fonctionnalités et/ou des performances accrues, e.g. en termes de résolution, sensibilité, sélectivité. Nous nous intéresserons ici à un certain type de nanostructures, les nanofils d’oxyde de zinc (ZnO), qui ont surtout été utilisés pour concevoir des dispositifs dont le principe de fonctionnement exploite l’effet piézoélectrique, souvent astucieusement combiné avec leurs propriétés semiconductrices. En effet, sous l’effet d’une contrainte mécanique ou d’un déplacement, les nanofils piézoélectriques génèrent un potentiel électrique (piézopotentiel). Si, en outre, les nanofils sont semiconducteurs, le piézopotentiel peut être utilisé pour contrôler un courant externe en fonction de la contrainte mécanique imposée au nanofil (effet piézotronique). L’avantage d’utiliser des nanostructures unidimensionnelles réside dans la modularité de leurs propriétés mécaniques et piézoélectriques en comparaison avec le matériau massif. Par ailleurs, leur intégration est aujourd’hui possible par des voies de croissance compatibles avec les procédés microélectroniques (CMOS/MEMS). Toutes ces considérations rendent possibles la conception de dispositifs très haute performance combinant la faible dimension des éléments fonctionnels (et donc une forte densité d’intégration synonyme de haute résolution spatiale) et leur sensibilité à des phénomènes d’échelle nanoscopique.Dans ce projet de thèse, on adoptera une vision très technologique de la conception de capteurs matriciels à base de nanofils piézoélectriques verticaux en ZnO. S’appuyant sur la prédiction des performances théoriques et la levée des verrous technologiques associés à la conception et la fabrication du capteur, cette étude s’attache à fournir des prototypes faisant la preuve de concept de ces dispositifs haute performance. Dans un premier temps, la réflexion s’articule autour de modèles multi-physiques par éléments finis (FEM) de la réponse piézoélectrique d’un seul nanofil en flexion, modèle que nous avons fait évoluer vers des pixels complets représentatifs d’un nanofil interconnecté dans une matrice. Sur la base de ces considérations, nous avons imaginé des moyens de caractérisation de la réponse piézoélectrique d’un fil, puis d’un pixel. Le banc de caractérisation mis en place a mis en évidence la complexité d’une mesure piézoélectrique systématique, calibrée et décorrélée des éléments environnants du pixel. Des solutions technologiques adéquates ont pu être imaginées et mises en œuvre à travers la réalisation de pixels élémentaires caractérisables et dont la réponse piézoélectrique peut être prédite théoriquement.Cette réalisation a fait appel à un développement en plusieurs étapes, incluant la croissance par voie chimique des nanofils en ZnO, puis la conception de la matrice d’électrodes contactant individuellement les nanofils. La première se découpe en deux étapes : d’abord le choix d’une couche de germination favorisant la croissance sur puce silicium et compatible avec les procédés de salle blanche ; ensuite le développement d’un procédé de croissance permettant la localisation des nanofils au sein d’une matrice d’électrodes. La seconde moitié du travail de fabrication a consisté à définir et à optimiser l’empilement technologique respectant toutes les considérations abordées jusqu’alors, et à définir les procédés technologiques aboutissant à la fabrication de la matrice finale. / This thesis project deals with the question of heterogeneous integration of interconnected nanowires on microelectronics chips in a view to MEMS and NEMS type devices. These devices aim to address the global problematic of “More than Moore”, that is the transformation of classical CMOS microelectronics processes to enable the development of new integrated micro and nanocomponents.In particular, over the past few years, a variety of nanomaterial-based devices have arisen, revealing micro-actuators and micro-sensors with new functionalities and/or improved performances, e.g. in terms of resolution, sensitivity, selectivity. Here we will focus on a certain type of nanostructures, Zinc Oxide (ZnO) nanowires, which have mostly been used so far to design devices whose working principle exploits the piezoelectric effect, often judiciously combined with their semiconducting properties. Indeed, when submitted to a mechanical constraint or displacement, piezoelectric nanowires generate an electrical potential (piezopotential). If, in addition to this, nanowires are also semiconducting, the piezopotential can be exploited to control an external current as a function of the mechanical constraint imposed to the nanowire (piezotronic effect). The advantage of using one-dimensional nanostructures lies into the modularity of both their mechanical and piezoelectric properties, in comparison with the bulk material. Moreover, their integration is now possible thanks to growth processes compatible with microelectronic processes (CMOS/MEMS). All these considerations make it possible to design very high performance devices combining the very small dimension of their functional unit elements (hence a high integration density which implies a high spatial resolution) and their sensitivity to nanoscale phenomena.In this project, we will adopt a very technology-oriented vision of the design of vertically-aligned ZnO-piezoelectric-nanowire matrix-type sensors. Relying on theoretical performance predictions and technological choices to solve device design and fabrication issues, this study aims to produce proof-of-concept prototypes of these high performance devices. First of all, the design process is elaborated based on finite element multiphysics models (FEM) of the piezoelectric response of a single bent nanowire, which we upgraded towards complete pixels, representative of an interconnected nanowire within a matrix. Following these considerations, we have imagined means of characterization of the piezoelectric response of a wire, then of a pixel. The implemented characterization experiment highlighted the complexity of carrying out a systematic, calibrated piezoelectric measurement, decorrelated from the environment of the pixel. Adequate technological solutions could then be implemented through the fabrication of elementary pixels suitable for characterization and whose piezoelectric response could be predictively modeled.This technological part of the work encompassed several development stages, including the chemical growth of ZnO nanowires and the design of the electrode matrix contacting the nanowires individually. The former splits into two steps: first choosing a clean-room compatible seed layer which will favor growth on a Silicon chip; secondly developing a selective growth process enabling the localization of nanowires within a predefined matrix of electrodes. The second part of the fabrication work focused on defining and optimizing the technological stack with respect to all the above mentioned considerations, and implementing the technological processes yielding the final targeted matrix.

L’objectif de ce travail est d’élaborer des méthodes peu chères pour produire desmatériaux semi-conducteurs pouvant entrer dans la fabrication de cellules solaires de type"eta" (extremely thin absorber). Ces cellules sont constituées d’une couche extrêmement fined’un adsorbeur inorganique dont la bande interdite est situé entre 1.1 et 1.8 eV placée entredeux nanostructures transparentes l’une de type n et l’autre de type p et dont les bandesinterdites doivent être supérieurs à 3.3 eV. Une couche compacte et des nanofils de ZnO ontété préparés en mode galvanostatique. Les dimensions des nanofils ont été contrôlées à l’aidede la couche compacte et de la densité du courant appliqué. La photosensibilisation desnanofils par des couches uniformes de CdS, CdSe et CdTe préparée par la méthode SILAR(Successive Ionic Layer Adsorption and Reaction) a été étudiée. Les propriétés de cescouches ont été améliorées par recuit et traitement chimique. En ce qui concerne les finescoquilles de CdTe deux autres méthodes de sensibilisation ont été également étudiées : la CSS(Close Spaced Sublimation) et les QDs (Quantum Dots). La première méthode conduit à unfaible recouvrement alors que la seconde produit un matériau mal défini optiquement. Leshétérostructures formées sur les nanofils ont été complétées par une couche de CuSCN, unsemi-conducteur de type p, préparée par trois méthodes différentes. L’influence de lamorphologie de ces couches sur les propriétés des cellules eta a été étudiée. Les filmspréparés par électrodéposition et SILAR sont plus rugueux que ceux obtenus parimprégnation et leur conductivité est moins bonne. Les hétérostructures (avec CdS et CdSecomme absorbeurs) ont été testées dans une cellule photoélectrochimique et les rendementsobtenus (jusque 2%) montrent une amélioration certaine des propriétés de ces matériauxpréparée par SILAR-modifiée ainsi que des interfaces ZnO/absorbeur. La qualité desmatériaux obtenus par SILAR montre qu’aujourd’hui on peut s’attendre à une Renaissance decette technique. / The development of semiconducting materials for the extremely thin absorber (eta)solar cell using cheap and scalable methods was the main objective of this work. The eta-solarcell is composed of all inorganic materials consisting of an extremely thin layer of absorbingmaterial (1.1 <Eg< 1.8 eV) sandwiched between nanostructured transparent electron and holeconductors (Eg ≥ 3.3 eV). Compact and defect free ZnO thin film and nanowires (NWs) wereprepared galvanostatically. The ZnO nanowire dimensions were controlled with the ZnO seedlayer or the applied current density. The photosensitization of the ZnO nanowires withconformal layers of CdS, CdSe and CdTe prepared by Successive Ionic Layer Adsorption andReaction (SILAR) was studied. The improvement of the absorber structural and opticalproperties by annealing and chemical treatment was achieved. The Close Spaced Sublimation(CSS) and Quantum Dot (QD) sensitization were also used for CdTe thin shell deposition,while the first method produced low coverage, the second resulted in better coverage but withnot optimal optical features. The ZnO NW/absorber heterostructure was completed with ahole conducting CuSCN layer. The influence of the CuSCN layer (prepared by three methods)morphology on the eta-solar cell performance is discussed. Electrodeposited and SILARprepared films exhibited rougher surfaces than that by the Impregnation technique (whichaffects the electrical conductivity). The ZnO/absorber core/shell heterostructures were alsotested in a photoelectrochemical cell. The recorded efficiencies (up to 2 %) for the case ofCdS and CdSe photosensitizers demonstrated an improvement of the ZnO/absorber interfacesand the material quality achieved by the modified-SILAR technique. These results let us toconsider that today a Renascence of the SILAR method is happening.