In the last three decades carbon nanomaterials such as fullerenes, carbon nanotubes and graphene have attracted significant attention from the scientific community due to their unique electronic, optical, thermal, mechanical and chemical properties. Among them carbon nanotubes and graphene have been used in numerous applications for future nanoelectronics, biochemical sensors and energy harvesting technologies due to their unique properties including exceptionally high electronic conductivity and mechanical strength. Carbon nanotubes are cylindrical structures and considered to be large mesoscopic molecules with high aspect ratios. Graphene is a single atomic layer of crystalline graphite and prepared by stripping layers off the graphite using Scotch tape. Apart from this scotch tape method, chemical ex-foliation and reduction of graphite oxide produces large amounts of reduced graphene oxide which has similar properties as graphene. This thesis reports on the biosensors made of reduced graphene oxide and single walled carbon nanotubes based on their electronic properties. We also demonstrate the changes in electronic properties of single walled carbon nanotubes due to interactions with dendrimer molecules. Finally, the yielding and flow behaviour of graphene oxide nematic gel are discussed. Chapter 1 gives a general introduction about the preparation and characterization along with the electronic properties of the systems studied in this thesis, namely graphene oxide, reduced graphene oxide and single walled carbon nanotubes. We have also discussed about the experimental techniques such as Raman, UV-visibe and infrared spectroscopy, atomic force and scanning tunneling microscopy and different types of rheometers used in this thesis work. In Chapter 2, we discuss top-gated field effect transistor characteristics of the devices made of reduced graphene oxide monolayer by dielectrophoresis. Raman spectrum of RGO flakes shows a single 2D band at 2687 cm 1, characteristic of a single layer graphene. The two probe current - voltage measurements of RGO flakes, deposited in between the patterned electrodes using a.c. dielectrophoresis show ohmic behavior with a resistance of 37kΩ. The temperature dependence of the resistance (R) of RGO measured between temperatures 305K to 393K yields the temperature coefficient of resistance of -9.5 10 4/K. Ambipolar nature of graphene flakes is observed upto a doping level of 6 1012/cm2 and carrier mobility of 50cm2/V-sec. The source - drain current characteristics shows a tendency of current saturation at high source - drain voltage which is analyzed quantitatively by a diffusive transport model. In Chapter 3, We demonstrate the detection of glucose molecules by using reduced graphene oxide (RGO) and aminophenylboronic acid (APBA) complex with detection limit of 5 nM. APBA functionalized RGO (APBA-RGO) flakes, prepared by stirring the aqueous GO suspension in the presence of APBA molecules at 100◦C, were used as conducting channel in our field effect transistor (FET) devices. The APBA-RGO complex formation was confirmed by atomic force microscopy (AFM), x - ray photoelectron, Raman and UV-visible spectroscopic studies. Detection of glucose molecules was carried out by monitoring the changes in electrical conductance of the APBA-RGO flake in the FET device. FET devices made of non-covelently functionalized APBA-RGO complex (nc-APBA-RGO) exhibited enhanced sensitivity over the devices made of covalently functionalized APBA-RGO complex (c-APBA-RGO). Change in normalized conductance in the FET devices made of nc-APBA-RGO flakes ( 85%) is 4 times more than that of in the devices made of c-APBA-RGO flakes in response to aqueous glucose solution with different concentrations. Specificity of APBA-RGO complex to glucose was proved from the observation of negligible change in electrical conductance of the FET devices made of nc-APBA-RGO complex after exposure to 10 mM lactose solution. Chapter 4 reports unipolar resistive switching in ultrathin films of chemically produced graphene (reduced graphene oxide) and multiwalled carbon nanotubes. The two - terminal devices with yield > 99% are made at room temperature by forming continuous films of graphene of thickness 20 nm on indium tin oxide coated glass electrode, followed by metal (Au or Al) deposition on the lm. These memory devices are non - volatile, rewritable with ON/OFF ratios up to 105 and switching times up to 10 s. The devices made of MWNT films are rewritable with ON/OFF ratios up to 400. The resistive switching mechanism is proposed to be nanogap formation. In the first part of Chapter 5, we study the interactions between SWNT and PETIM dendrimer by measuring the quenching of inherent fluorescence of the dendrimer. Also, the dendrimer - nanotube binding results in the increased electrical resistance of the hole-doped SWNT due to charge transfer interaction between the dendrimer and the nanotube. This charge transfer interaction was further corroborated by observing a shift in frequency of the tangential Raman modes of SWNT. Experimental studies were supplemented by all atom molecular dynamics simulations to provide a microscopic picture of the dendrimer - nanotube complex. The complexation was achieved through charge - transfer and hydrophobic interactions, aided by multitude of oxygen, nitrogen and n-propyl moieties of the dendrimer. We also studied the effect of acidic and neutral pH conditions on the binding affinities. In the second part, we show that SWNT decorated with sugar functionalized PETIM dendrimer is a very sensitive platform to quantitatively detect carbohydrate recognizing proteins, namely, lectins. The changes in electrical conductivity of SWNT in field effect transistor device due to carbohydrate - protein interactions forms the basis of this study. The mannose sugar attached PETIM dendrimers undergo charge - transfer interactions with the SWNT. The changes in the conductance of the dendritic sugar functionalized SWNT after addition of lectins in varying concentrations were found to follow the Langmuir type isotherm, giving the concanavalin A (Con A) - mannose affinity constant to be 8.5 106 M-1. The increase in the device conductance observed after adding 10 nM of Con A is same as after adding 20 µM of a non - specific lectin peanut agglutinin, showing the high specificity of the Con A - mannose interactions. The specificity of sugar-lectin interactions was characterized further by observing significant shifts in Raman modes of the SWNT. Chapter 6 reports the metal to semiconductor transition in metallic single-wall carbon nanotubes (SWNT) due to the wrapping of mannose attached poly (propyl ether imine) dendrimer (DM) molecule. Scanning tunneling spectroscopic (STS) measurements and ionic liquid top gated field effect transistor (FET) characteristics of the nanotube-dendrimer complex gives a band gap of 0.42eV, close to the E11 energy gap between the first van Hove singularities of 1.7nm diameter semiconducting nanotubes. The absence of Breit-Wigner-Fano (BWF) component in G band in the Raman spectrum of the nanotube-dendrimer complex corroborates the semiconductor nature of the tubes after wrapping with the dendrimer molecules. Dendrimer molecule breaks the symmetry in metallic SWNT by wrapping around it through the charge transfer interactions. In the first part of Chapter 7, we demonstrate a rigidity percolation transition and the onset of yield stress in a dilute aqueous dispersion of graphene oxide platelets (aspect ratio 5000) above a critical volume fraction of 3.75x10-4 with a percolation exponent of 2.4 ± 0.1.The viscoelastic moduli of the gel at rest measured as a function of time indicates the absence of structural evolution of the 3D percolated network of disks. However, a shear-induced aging giving rise to a compact jammed state and shear rejuvenation indicating a homogenous flow is observed when a steady shear stress (σ ) is imposed in creep experiments. We construct a shear diagram (σ vs volume fraction ϕ) and the critical stress above which shear rejuvenation occurs is identified as the yield stress σ y of the gel. The minimum steady state shear rate ƴm obtained from creep experiments agrees well with the end of the plateau region in a controlled shear rate flow curve, indicating a shear localization below ƴm. A steady state shear banding in the plateau region of the flow curve observed in particle velocimetry measurements in a couette geometry confirms that the dilute suspensions of GO platelets form a thixotropic yield stress fluid (TYSF). In the second part, we report that the creep experiments on a nematic liquid crystalline suspension of Graphene Oxide platelets which was established recently as a TYSF exhibit two characteristic timescales Tc and Tf marking the onset of yielding, and a final steady state of flow respectively. We show that both Tc and Tf exhibit a power law dependence on the applied stress σ which can be linked to the steady state flow behaviour of a TYSF. The smooth transition from Andrade creep to the onset of flow with ƴ~ t 0.7 at a critical strain ƴc for different applied stresses, is well captured by the master curve for the creep compliance, obtained through a simple scaling of the creep times with either Tc or Tf . We propose that the absence of diverging timescales for onset of flow as σ→ yield stress σy from above, is a characteristic feature of TYSF. The thesis concludes with a summary of the main results and a brief account of the scope of future work described in Chapter 8.

[ES] La presente tesis doctoral titulada "Nanodispositivos mesoporosos híbridos funcionalizados con enzimas para detección, liberación controlada y comunicación molecular" se centra en el diseño, preparación, caracterización y evaluación de distintos nanodispositivos híbridos orgánico-inorgánicos utilizando como soporte nanopartículas tipo Janus de oro y sílice mesoporosa, que se equipan con enzimas, especies fluorescentes y puertas moleculares. Como conclusión general, los estudios realizados muestran que la incorporación de enzimas sobre nanopartículas permite introducir funciones de reconocimiento con alta especificidad y diseñar nanodispositivos avanzados para distintas finalidades. La combinación de nanopartículas híbridas con grupos orgánicos como puertas moleculares, efectores enzimáticos y especies cromo- fluorogénicas o fármacos puede resultar muy versátil; y se espera que los resultados obtenidos puedan inspirar el desarrollo de nuevos materiales inteligentes con aplicación en distintas áreas como la nanomedicina y la detección de moléculas de interés. / [CAT] La present tesi doctoral titulada "Nanodispositius mesoporosos híbrids funcionalitzats amb enzims per a detecció, alliberació controlada i comunicació molecular" es centra en el disseny, preparació, caracterització i avaluació de distints nanodispositius híbrids orgànic-inorgànics utilitzant com a suport nanopartícules tipus Janus d'or i sílice mesoporosa, que s'equipen amb enzims, espècies fluorescents i portes moleculars. Com a conclusió general, els estudis realitzats mostren que la incorporació d'enzims sobre nanopartícules permeten introduir funcions de reconeixement amb alta especificitat i dissenyar nanodispositius avançats per a distintes finalitats. La combinació de nanopartícules híbrides amb grups orgànics com portes moleculars, efectors enzimàtics i espècies cromo-fluorogèniques o fàrmacs pot resultar molt versàtil; i s'espera que els resultats obsessos inspiren el desenvolupament de nous materials intel·ligents amb aplicació en distintes àrees com la nanomedicina i la detecció de molècules d'interés. / [EN] This PhD thesis entitled "Enzyme-functionalized hybrid mesoporous nanodevices for sensing, controlled release and molecular communication" is focused on the design, synthesis, characterization and evaluation of several hybrid organic-inorganic nanodevices using Janus gold-mesoporous silica nanoparticles as scaffolds, equipped with enzymes, fluorescent species and molecular gates. In conclusion, these studies show that the incorporation of enzymes on nanoparticles allows to introduce recognition capabilities with high specificity and to design advanced nanodevices for different purposes. The combination of hybrid nanoparticles with organic groups such as molecular gates, enzymatic effectors and chromo-fluorogenic species or drugs can be very versatile; and we hope that the obtained results inspire the development of new smart materials with application in different areas such as nanomedice and sensing. / Llopis Lorente, A. (2019). Enzyme-functionalized hybrid mesoporous nanodevices for sensing, controlled release and molecular communication [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/117612 / TESIS

De par ses extraordinaires propriétés physiques, on s'attend à ce que le graphène devienne un matériau de nouvelle génération, susceptible de compléter les semi-conducteurs traditionnels dans les technologies de dispositifs électroniques. Depuis sa découverte expérimentale en 2004, de nombreux travaux ont cherché à en évaluer les potentialités. Toutefois, en vue d'applications en électronique, le graphène souffre d'un inconvénient majeur : l'absence de bande interdite dans sa structure de bandes. Ainsi, il est très difficile de moduler et couper le courant dans un transistor de graphène, ce qui restreint considérablement son champ d'applications. Du point de vue des propriétés thermoélectriques, l'absence de bande interdite empêche la séparation des contributions opposées des électrons et des trous au coefficient Seebeck, qui reste donc faible dans le graphène parfait. Aussi, l'ouverture d'une bande interdite (gap) dans le graphène est une nécessité pour contourner les inconvénients de ce matériau et bénéficier pleinement de ses excellentes propriétés de conduction. Il a été montré que de nombreuses approches de nanostructuration peuvent être utilisées dans ce but : découpage de nanorubans de graphène, bicouche de graphène avec application d'un champ électrique transverse, percement d'un réseau périodique de nano-trous (nanomesh), structures mixtes de graphène et de nitrure de bore, dopage du graphène à l'azote. Cependant, toutes ces approches ont leurs propres difficultés de fabrication et/ou restent encore à confirmer expérimentalement. Dans ce travail, je me suis focalisée sur une autre approche : l'ingénierie de contrainte, qui offre un large éventail de possibilités pour moduler les propriétés électroniques des nanostructures de graphène. Pour ce travail théorique, tous les calculs ont été faits en utilisant essentiellement deux méthodes : un modèle atomistique de Hamiltonien de liaisons fortes pour décrire les propriétés électroniques du matériau et l'approche des fonctions de Green hors-équilibre pour le calcul du transport quantique. Après une introduction du contexte général de ce travail et des techniques de calcul développées dans ce but, j'ai d'abord analysé les effets de contrainte. En fait, une contrainte d'amplitude supérieure à 23% est nécessaire pour ouvrir un gap dans la structure de bande du graphène. Mais je montre qu'avec une contrainte de quelques pourcents, le décalage du point de dirac induit par la contrainte peut suffire à ouvrir un gap de conduction très significatif (500 meV ou plus) dans des hétérostructures de graphène constituées de jonctions graphène contraint/graphène non contraint, alors que chacun des matériaux reste semi-métallique. Après l'analyse détaillée de cette propriété en fonction de l'amplitude de la contrainte, de sa direction et de la direction du transport, j'exploite cet effet dans des jonctions appropriées pour améliore le comportement et les performances de différents types de dispositifs. En particulier, je montre qu'avec une contrainte de seulement 5% il est possible de couper efficacement le courant dans les transistors, de sorte que le rapport ON/OFF peut atteindre 100000, ce qui constitue une très forte amélioration par rapport aux transistors de graphène pristine où ce rapport ne peut pas excéder 10. Puis, nous montrons qu'en combinant ingénieries de contrainte et de dopage dans de telles jonctions, le coefficient Seebeck peut atteindre des valeurs aussi fortes que 1.4 mV/K, ce qui est 17 fois plus élevé que dans le graphène sans gap. Cela peut contribuer à faire du graphène un excellent matériau thermoélectrique. Enfin, j'ai étudié l'effet de conductance différentielle négative (CDE) dans des diodes de graphène, constituées soit d'une simple-barrière contrainte contrôlée par une grille, soit d'une jonction PN. Je montre qu'une ingénierie de contrainte appropriée peut induire de forts effets de CDE, avec un rapport pic/vallée de quelques centaines à température ambiante. / Due to its outstanding physical properties, graphene is expected to become a new generation material, able to replace or complement traditional semiconductors in device technology. Hence, many studies have been led to explore the potential of this material immediately after the successful fabrication of a single layer of graphene in 2004. However, applications of graphene in electronic devices are still questionable due to the gapless character of this material. In particular, regarding electronic applications, the absence of energy bandgap in the band structure makes it difficult to switch off the current in graphene devices like transistors. Regarding thermoelectric properties, the gapless character is also a strong drawback since it prevents the separation of the opposite contributions of electrons and holes to the Seebeck coefficient. Thus, a sizable band gap in graphene is a requirement to overcome the disadvantages of graphene and to fully benefit from its excellent conduction properties. It has been shown that many Nano structuring techniques can be used to open such a bandgap in graphene, e.g., graphene nanoribbons, graphene bilayer with a perpendicular electric field, graphene nanotech lattices, channels based on vertical stack of graphene layers, mixed graphene/hexagonal boron nitride structures, nitrogen doped graphene, and so on. However, each of these methods has its own fabrication issues and/or need to be further confirmed by experiments. In this work, we focus on strain engineering, which offers a wide range of opportunities for modulating the electronic properties of graphene nanostructures. For this theoretical work, all calculations were performed using essentially two main methods, i.e., an atomistic tight binding Hamiltonian model to describe the electronic structure and the non-equilibrium Green's function approach of quantum transport. The main aim is to analyze in details the strain effects in graphene and to provide strategies of strain engineering to improve the performance of both electronic (transistors and diodes) and thermoelectric devices. After introducing the general context if this work and the numerical techniques developed for this purpose, we first analyze the only effect of strain. Actually, if uniformly applied, a strain of large amplitude (> 23%) is required to open a bandgap in the band structure of graphene. However, we show that with a strain of only a few percent, the strain-induced shift of the Dirac point in k-space may be enough to open a sizable conduction gap (500 meV or more) in graphene heterojunctions made of unstrained/strained junctions, though the strained material remains gapless. After analyzing in details this property according the amplitude and direction of strain and the direction of transport, we exploit this effect using appropriate strain junctions to improve the behavior and performance of several types of devices. In particular, we show that with a strain of only 5%, it is possible to switch-off transistors efficiently, so that the ON/OFF current ratio can reach 100000, which is a strong improvement with respect to pristine graphene transistors where this ratio cannot exceed 10. Then we show that by combining strain and doping engineering in such strain junctions the Seebeck coefficient can reach values higher than 1.4 mV/K, which is 17 times higher than in gapless pristine graphene. It can contribute to make graphene an excellent thermoelectric material. Finally, we study the effect of negative differential conductance (NDC) in graphene diodes made of either as single gate-induced strained barrier or a p-n junction. We show that appropriate strain engineering in these devices can lead to very strong NDC effects with peak-to-valley ratios of a few hundred at room temperature.

When a nanostructure is coupled between two leads, the electron transmission probability as a function of energy, E, is used in the Landauer formula to obtain the electrical conductance of the nanodevice. The electron transmission probability as a function of energy, T (E), is calculated from the appropriate solution of the time independent Schrödinger equation. Recently, a large class of nanostructures called quantum dragons has been discovered. Quantum dragons are nanodevices with correlated disorder but still can have electron transmission probability unity for all energies when connected to appropriate (idealized) leads. Hence for a single channel setup, the electrical conductivity is quantized. Thus quantum dragons have the minimum electrical conductance allowed by quantum mechanics. These quantum dragons have potential applications in nanoelectronics. It is shown that for dimerized leads coupled to a simple two-slice (l = 2, m = 1) device, the matrix method gives the same expression for the electron transmission probability as renormalization group methods and as the well known Green's function method. If a nanodevice has m atoms per slice, with l slices to calculate the electron transmission probability as a function of energy via the matrix method requires the solution of the inverse of a (2 + ml) (2 + ml) matrix. This matrix to invert is of large dimensions for large m and l. Taking the inverse of such a matrix could be done numerically, but getting an exact solution may not be possible. By using the mapping technique, this reduces this large matrix to invert into a simple (l + 2) (l + 2) matrix to invert, which is easier to handle but has the same solution. By using the map-and-tune approach, quantum dragon solutions are shown to exist for single-layer planar rectangular crystals with different boundary conditions. Each chapter provides two different ways on how to find quantum dragons. This work has experimental relevance, since this could pave the way for planar rectangular nanodevices with zero electrical resistance to be found. In the presence of randomness of the single-band tight-binding parameters in the nanodevice, an interesting quantum mechanical phenomenon called Fano resonance of the electron transmission probability is shown to be observed.

Το αντικείμενο της παρούσας Διδακτορικής Διατριβής είναι η ανάπτυξη και ο χαρακτηρισμός προηγμένων υλικών για εφαρμογές σε νανοδιατάξεις. Στα πλαίσια αυτής, επικεντρωθήκαμε στην ανάπτυξη και μελέτη μαγνητικών και ημιαγωγικών λεπτών υμενίων που βασίζονται σε οξείδια παραδοσιακών μετάλλων και ημιαγωγών. Ο μαγνητικός και οπτικός χαρακτηρισμός των υλικών αυτών υπό τη μορφή της νανοδομής του λεπτού υμενίου, αποκαλύπτουν νέες ιδιότητες με εξαιρετικά μεγάλο τεχνολογικό ενδιαφέρον. Πιο συγκεκριμένα, έγινε καταρχήν ανάπτυξη πολυστρωματικών μαγνητικών υμενίων Ni/NiO, μονοστρωματικών ημιαγωγικών υμενίων Cu2O, CuO και NiO, όπως επίσης και μονοστρωματικών άμορφων μονωτικών υμενίων SiOx με ή και χωρίς ενσωματωμένες κβαντικές τελείες Si. Για κάθε σειρά υμενίων από τις κατηγορίες αυτές, έγινε μελέτη των μαγνητικών ή/και των οπτικών τους ιδιοτήτων. Τα υμένια Ni/NiO αναπτύχθηκαν σε διαφορετικά υποστρώματα με τη χρήση μιας μόνο κεφαλής magnetron sputtering και της μεθόδου της φυσικής οξείδωσης. Η διαστρωμάτωση του υλικού και η επαναληψιμότητα της μεθόδου αποδείχθηκαν εξαιρετικής ποιότητας. Για υμένια Ni/NiO με διαφορετικό πάχος στρώματος Ni έγινε εκτεταμένη μελέτη της εξάρτησης της μαγνήτισης και της ανισοτροπίας από τη θερμοκρασία. Βρέθηκε ότι τα υμένια με λεπτά στρώματα Ni εμφανίζουν τάση για κάθετη μαγνητική ανισοτροπία, η οποία προέρχεται από την υπολογίσιμη θετική ανισοτροπία επιφανείας που επιδεικνύουν αυτά. Τα ημιαγωγικά υμένια οξειδίων του Cu και του Νi αναπτύχθηκαν μετά από οξείδωση υμενίων των αντίστοιχων μεταβατικών μετάλλων. Τα άμορφα μονωτικά υμένια SiOx αναπτύχθηκαν με τη τεχνική της “reactive” ιοντοβολής. Στη συνέχεια, μέρος αυτών οξειδώθηκε πλήρως μετά από θέρμανση σε θερμοκρασία 950 οC και σε περιβάλλον αέρα, ενώ κάποια άλλα υποβλήθηκαν σε θερμική αποσύνθεση μετά από θέρμανση σε συνθήκες κενού στους 1000 οC. Με τη διαδικασία της θερμικής αποσύνθεσης, όπως αποδεικνύουν και οι εικόνες ηλεκτρονικής μικροσκοπίας, σχηματίζονται νανοκρύσταλλοι Si ενσωματωμένοι σε άμορφη μήτρα οξειδίου του Si. Για τα υμένια των οξειδίων του Cu και του Ni μελετήθηκαν με τη χρήση της φασματοσκοπίας UV-VIS τα φαινόμενα κβαντικού περιορισμού που παρουσιάζουν αυτά. Βρέθηκε ότι σε κάθε περίπτωση εμφανίζεται μετατόπιση της ακμής απορρόφησης προς μεγαλύτερες ενέργειες, καθώς το πάχος του υμενίου μειώνεται και γίνεται συγκρίσιμο με την εξιτονική ακτίνα Bohr του αντίστοιχου υλικού. Τα υμένια SiOx βρέθηκε ότι μετά από τη διαδικασία της θερμικής τους αποσύνθεσης παρουσιάζουν φωτοφωταύγεια, η οποία προέρχεται από τις εξιτονικές επανασυνδέσεις στις κβαντικές τελείες Si που εμπεριέχονται σ’ αυτά. Από την εργασία στα πλαίσια αυτής της Διατριβής, διαπιστώνουμε ότι μπορούμε να μεταβάλλουμε τις ιδιότητες παραδοσιακών υλικών, όπως είναι για παράδειγμα τα μέταλλα, οι κλασσικοί ημιαγωγοί και τα οξείδια αυτών, όταν αυτά αναπτύσσονται υπό τη μορφή νανοδομών. Οι νανοδομές αυτές μπορεί να εμφανίζουν εξαιρετικό ενδιαφέρον για εφαρμογές σε νανοδιατάξεις με καινούργιες αλλά κι εντελώς ελεγχόμενες ιδιότητες. / The objective of this Thesis is the growth and the characterization of high tech materials which can be possible candidates for future applications in nanodevices. In the framework of the Thesis, we were mainly focused on the production and the study of magnetic and semiconducting thin films, which are based on oxides of metals and of conventional semiconductors. The magnetic and optical characterizations reveal that these materials, in the form of thin films exhibit new properties with exceptionally large technological interest. In more detail, magnetic Ni/NiO multilayers, semiconducting Cu2O, CuO and NiO thin films, as well as insulating amorphous SiOx thin films with or without embedded Si quantum dots, were produced. The magnetic and/or optical properties of each of the aforementioned thin film categories were studied and their impact on possible future applications was examined. The Ni/NiO multilayers were produced on various substrates with the aid of a single magnetron sputtering head and the natural oxidation process. The produced multilayers were of excellent layering and interface quality. An extended study of both the magnetization and the anisotropy as a function of the temperature and the varying Ni layer thickness was performed. It is found from the magnetic investigations, that the multilayers with thin Ni layers exhibit a trend for perpendicular magnetic anisotropy, which is attributed to the considerable positive surface anisotropy of the Ni/NiO interfaces. The semiconducting copper and nickel oxide thin films were produced via the oxidation of the corresponding metallic films. The amorphous SiOx films were fabricated via the reactive sputtering method. Part of the as deposited films was fully oxidized at 950 oC under the ambient air environment, whereas another part was thermally decomposed under vacuum conditions at 1000 oC. Electron microscopy investigations reveal that upon the thermal decomposition process of the films, embedded Si nanocrystals are formed in the amorphous matrix of the Si oxide. The Cu and Ni oxide films exhibited quantum confinement effects, which were studied via the UV-VIS spectroscopy. The recorded spectra reveal that the absorption edge shifts towards higher energies, as the layer thickness is reduced and becomes comparable with the excitonic Bohr radius of the material. The Si oxide thin films, after the thermal decomposition treatment are found to exhibit photoluminescence at the region between 1.3 and 1.5 eV which is originated to the excitonic recombination in the embedded Si quantum dots. Finally, it is deduced that conventional materials like metals, semiconductors and the oxides of them, can exhibit new properties when they are prepared in the form of nanostructure. These nanostructures can attract a lot of interest for possible applications in nanodevices with new but completely controllable properties.

Zinc oxide (ZnO) is perhaps one of the most widely studied material in the last two decades. It has received so much of attention because of its incredible potential for wide ranging applications. ZnO is a wide band gap semiconductor (Eg = 3.37 eV at 300 K) with a rather large excitonic binding energy (~60 meV). This combination of properties makes it an ideal choice for several optoelectronic devices that can easily work at room temperature. ZnO is a truly multifunctional material possessing several desirable electrical, optical, optoelectronic, and piezoelectric properties. In addition, it is highly amenable to production of various kinds of nanostructures such as nanorods, nanotubes, nanoribbons, nanoneedles, etc., which makes it even more desirable for nanoscale devices. Examples of ZnO based nanodevices could include photodiodes, photodetectors, nano-lasers, field-emission devices and memristors. In order to make such devices, one could need device quality nanostructures that must be reproducible and cost effective. Naturally, one has to look for a synthesis process that has great controls and is relatively inexpensive. The study provided here shows that among the various methods available for ZnO synthesis, the microwave-assisted chemical synthesis offers outstanding advantages in terms of rapid growth of nanostructures, economical use of energy and excellent controls of process parameters. In order to produce device quality ZnO nanostructures using microwave-assisted synthesis, one has to study the effect of various process parameters and optimise them for the desired growth. Therefore, in the current study, first, a systematic study was undertaken to synthesize ZnO nanostructures both in a aqueous and non-aqueous medium and their characterization was carried out in order to understand the effect of microwave power, time of irradiation, pressure, solvent and salt concentration, etc. The goal was to develop synthesis protocols for various kinds of nanostructures that could guarantee reproducibility, good yield, and device quality structures. This study has led to successful growth of ZnO nanostructures on various substrates, vertically aligned ZnO nanorods and templated arrays of desired structures, all with outstanding properties of the structures as confirmed by XRD, MicroRaman, photoluminescence, cathodoluminescence, FESEM, TEM, PFM studies and pole figure analysis. Piezoelectric force microscopy (PFM) and physical property measurement system (PPMS, Quantum Design), have been used to study the multifunctional properties of ZnO nanostructures. The PFM is a powerful technique to measure the local piezoelectric coefficient of nanostructures and nanoscale thin films. PFM works on the converse piezoelectric effect in which electric potential is applied and mechanical strain is measured using a cantilever deflection. The PFM (Brucker’s AFM dimension Scan Assist) was used to characterize individual ZnO nanorods. Extensive studies were carried out with PFM measurements and it was observed that the nanorods consistently showed high piezoelectric coupling coefficients (d33~50-154 pm/V). It was also found that the variation in d33 depended on morphology and size of nanostructure. The multifunctional properties were observed in small ZnO nanocrystals (NCs). Such high values of piezoelectric coupling coefficients open the door for novel ZnO based nanoscale sensors and actuators. The synthesized ZnO nanostructures were further optimized and characterized keeping in view three device applications namely Field emission, Memristors and Gas Sensors. The fabrication and characterization of these three devices with ZnO nanostructure was carried out using electron beam lithography and direct laser writing micromachining. Device fabrication using lithography involved several steps such as substrate cleaning, photoresist spin coating, pre-baking, post-baking, pattern writing, developing, sputtering/deposition of material for lift-off, ZnO growth, and overlay lithography. For field emission devices, high quality, well aligned, c-axis oriented ZnO nano-needles were grown on sputter coated Ti/Pt (20nm/100nm) on SiO2/Si substrate by rapid microwave-assisted method in aqueous medium. The diameter of the tip was found to be 1~2 nm and the length of the rod was approximately 3~5μm. For a particular batch the tip size, morphology, and lengths were found to be the same and highly repeatable. Pole figure analysis revealed that nanorods were highly oriented towards <002> direction. Field-emission measurements using the ZnO nanoneedles arrays as cathode showed very low turn-on electric field of 0.9 V/μm and a very high field enhancement factor ~ 20200. Such a high emission current density, low turn-on electric field, and high field enhancement factor are attributed to the high aspect ratio, narrow tip size, high quality and single crystallinity of the nanoneedles. The high emission current density, high stability, low threshold electric field (0.95 V/μm) and low turn-on field make the ZnO nanoneedle arrays one of the ideal candidates for field-emission displays and field emission sensors. In the suitability of ZnO nanostructures for memristor application it was found that the single crystalline ZnO nanorods were not suitable as they did not show memristive behaviour but the ZnO nanorods with native defects exhibited considerable memristive behaviour. Therefore the microwave-assisted grown ZnO nanorods with defects were used to fabricate memristive devices. Single and multiple ZnO nanorods based memristors were fabricated using electron beam lithography. These devices were characterized electrically by measuring the hysteresis in the I/V characteristics. A high degree of repeatability has been established in terms of growth, device fabrication, and measurements. The switching in single nanorod based devices was found to have “ON-to- OFF” resistance ratio of approximately 104 and current switching ratio (ION/IOFF) of 106. Gas sensing based on electrical resistance change depends on absorption and desorption rate of gases on the analyte which is governed by surface properties, morphologies and activation energy. Therefore, various morphologies of nanostructure were grown for gas sensing application. Through experimentation, the emphasis shifted to c-axis oriented ZnO nanostructures on SiO2 substrate for gas sensing. The c-axis orientation of ZnO nanostructures was preferred mainly due to its huge surface area. The measurements showed that the c-axis oriented ZnO nanorods were excellent hydrogen sensors, able to detect H2 as low concentration as 2 ppm, even when the sensing temperature is as low as 200 ˚C. However, oxygen sensing was achieved at a higher temperature (300 ˚C). Thus, the study undertaken in this thesis presents a microwave based rapid and economical method for synthesizing high quality, device grade ZnO nanostructures, their extensive characterization that shows the multifunctional properties of these structures, and there examples of varied device applications of the synthesized nanostructures as field emitters, memristors, and gas sensors.

Tesis por compendio / [ES] La presente tesis doctoral se centra en el diseño, síntesis y caracterización de varios nanodispositivos híbridos orgánico-inorgánicos, utilizando como soporte nanopartículas de sílice mesoporosa equipadas con enzimas y puertas moleculares, los cuales muestran capacidades comunicativas además de la evaluación de diferentes estrategias de comunicación. El primer capítulo incluye un resumen de diferentes conceptos sobre los que se fundamentan los estudios realizados tales como nanotecnología, materiales de sílice mesoporosa, materiales con puertas moleculares que reaccionan a estímulos específicos, partículas Janus y biocomputación. Finalmente, se incluyen conceptos básicos acerca de la comunicación química, materiales y estrategias empleados hasta ahora y ejemplos representativos. A continuación, en el segundo capítulo, se presentan los objetivos generales de esta tesis doctoral que son abordados en los siguientes capítulos experimentales. El tercer capítulo muestra un sistema de biocomputación para liberación basado en nanopartículas Janus de oro-sílice mesoporosa capaces de comunicarse con el entorno procesando la información e imitando la función lógica booleana propia de un demultiplexer y que resulta en la liberación controlada de la carga. Se muestra que dicho nanodispositivo puede llevar a cabo sus funciones en medios complejos como en células cancerígenas. En el cuarto capítulo, se presenta un modelo circular de comunicación dentro de una red de tres nanopartículas diferentes basado en el intercambio jerárquicamente programado de mensajes químicos. La parte mesoporosa del nanodispositivo 1 (S1βgal) es cargada con la especie fluorescente [Ru(bpy)3]Cl2 y tapada con cadenas de oligo(etilenglicol) que contienen puentes disulfuro y que funcionan como puertas moleculares, mientras que la enzima β-galactosidasa es unida a la parte del oro. En la nanopartícula 2 (S2galox), la enzima galactosa oxidasa es inmovilizada en la cara del oro mientras que la sílice mesoporosa es cargada con 4-(bromometil)benzoato de metilo y los poros tapados con un derivado de arilboronato autoinmolante sensible a H2O2 que forma un complejo huéspedanfitrión con β-ciclodextrina. Finalmente, el nanodispositivo 3 (S3est) es funcionalizado con la enzima esterasa en la parte del oro, cargada con la especie reductora hidroclururo de tris(2-carboxietil)fosfina (TCEP) en la parte mesoporosa y tapada con una nanoválvula supramolecular que responde a pH (βciclodextrina:benzimidazol). En el quinto capítulo, se muestra un modelo interactivo de comunicación química entre una nanopartícula Janus abiótica y un organismo vivo (Saccharomyces cerevisiae). En particular, el nanodispositivo está basado en nanopartículas funcionalizadas con glucosa oxidasa en la parte del oro, cargadas con el genotóxico fleomicina y tapadas con la puerta molecular sensible a pH (βciclodextrina:benzimidazol). El microorganismo usado en el estudio es una levadura modificada que expresa GFP bajo el control del promotor del gen RNR3; la transcripción de dicho gen es inducida con la exposición a agentes que dañan el ADN. La ruta de comunicación interactiva empieza con la adición de sacarosa (estímulo de entrada) la cual es hidrolizada en glucosa por la invertasa localizada en el espacio periplásmico de las levaduras y que difunde al nanodispositivo donde es trasformada en el correspondiente ácido por la glucosa oxidasa de la parte del oro. La bajada local de pH da lugar a la apertura de la nanoválvula sensible a pH del nanovehículo y con ello a la liberación de fleomicina (mensaje de vuelta) que induce la expresión de GFP (señal de salida) en las levaduras. En el sexto capítulo, proponemos una estrategia para establecer una comunicación lineal entre dos microorganismos diferentes que no interactúan entre ellos mediada por un nanodispositivo que actúa como traductor químico. Finalmente, las conclusiones generales de la presente tesis doctoral son expuestas en el capítulo siete. El estudio de las capacidades comunicativas de los nanodispositivos mesoporosos funcionalizados con enzimas permite la construcción de estrategias de cooperación entre diferentes entidades que permiten funcionalidades que van más allá que aquellas llevadas a cabo por agentes individuales. / [CA] La present tesi doctoral es centra en el disseny, síntesi i caracterització de diversos nanodispositius híbrids orgànic-inorgànics, utilitzant com a suport nanopartícules de sílice mesoporosa equipades amb enzims i portes moleculars, i que mostren capacitats comunicatives a més de l’avaluació de diferents estratègies de comunicació. El primer capítol inclou un resum de diferents conceptes sobre els quals es fonamenten els estudis realitzats com ara nanotecnologia, materials de sílice mesoporosa, materials amb portes moleculars que reaccionen a estímuls específics, partícules Janus i biocomputació. Finalment, s’inclouen conceptes bàsics sobre la comunicació química, materials i estratègies utilitzades fins ara i exemples representatius. A continuació, en el segon capítol, es presenten els objectius generals d’aquesta tesi doctoral que són abordats en els següents capítols experimentals. El tercer capítol mostra un sistema de biocomputació per alliberament basat en nanopartícules Janus d’or-sílice mesoporosa capaços de comunicar-se amb l’entorn processant la informació i imitant la funció lògica booleana pròpia d’un demultiplexer i que resulta en l’alliberament controlat de la càrrega. Es mostra que aquest nanodispositiu pot dur a terme les seves funcions en mitjans complexos com en cèl·lules canceroses. En el quart capítol, es presenta un model circular de comunicació dins d’una xarxa de tres nanopartícules diferents basat en l’intercanvi jeràrquicament programat de missatges químics. La part mesoporosa del nanodispositiu 1 (S1βgal) es carrega amb l’espècie fluorescent [Ru(bpy)3]Cl2 i es tapa amb cadenes d’oligo(etilenglicol) que contenen ponts disulfur i que funcionen com portes moleculars, mentre que l’enzim β-galactosidasa s’immobilitza a la part de l’or. A la nanopartícula 2 (S2galox), l’enzim galactosa oxidasa s’immobilitza a la cara de l’or mentre que la sílice mesoporosa es carrega amb 4-(bromometil)benzoat de metil i els porus són tapats amb un derivat d’arilboronat autoimmolant sensible a H2O2 que forma un complex hoste-amfitrió amb β-ciclodextrina. Finalment, el nanodispositu 3 (S3est) es funcionalitza amb l’enzim esterasa en la part de l’or, es carrega amb l’espècie reductora hidroclurur de tris (2-carboxietil) fosfina (TCEP) a la part mesoporosa i es tapa amb una nanoválvula supramolecular que respon a pH (β-ciclodextrina:benzimidazol). En el cinqué capítol, es mostra un model interactiu de comunicació química entre una nanopartícula Janus abiòtica i un organisme viu (Saccharomyces cerevisiae). En particular, el nanodispositiu està basat en nanopartícules funcionalitzades amb glucosa oxidasa en la part de l’or, carregades amb el genotòxic fleomicina i tapades amb la porta molecular sensible a pH (βciclodextrina:benzimidazol). El microorganisme utilitzat en l’estudi és un rent modificat que expressa GFP sota el control del promotor del gen RNR3; la transcripció d’aquest gen és induïda amb l’exposició a agents que danyen l’ADN. La ruta de comunicació interactiva comença amb l’addició de sacarosa (estímul d’entrada) la qual és hidrolitzada en glucosa per la invertasa localitzada en l’espai periplasmàtic dels rents i que difon al nanodispositiu on és transformada en el corresponent àcid per la glucosa oxidasa de la part de l’or. La baixada local de pH dona lloc a l’obertura de la nanoválvula sensible a pH del nanovehicle i amb això l’alliberament de fleomicina (missatge de tornada) que indueix l’expressió de GFP (senyal de sortida) en el rent. En el sisé capítol, proposem una estratègia per establir una comunicació lineal entre dos microorganismes diferents que no interactuen entre ells facilitada per un nanodispositiu que actua com a traductor químic. Finalment, les conclusions generals de la present tesi doctoral són exposades en el capítol set. L’estudi de les capacitats comunicatives dels nanodispositius mesoporosos funcionalitzats amb enzims permet la construcció d’estratègies de cooperació entre diferents entitats que permeten funcionalitats que van més enllà que aquelles dutes a terme per agents individuals. Esperem que els resultats obtinguts inspiren aplicacions futures en diferents àrees com ara biomedicina, nanorobots, materials que imiten la naturalesa i tecnologies de la informació. / [EN] This PhD Thesis is focused on the design, synthesis and characterization of several hybrid organic-inorganic nanodevices using mesoporous silica nanoparticles equipped with enzymes and molecular gates which display communication capabilities as well as the design and evaluation of different communication strategies. The first chapter includes an overview of the different concepts which lay the foundations of the presented studies such as nanotechnology, mesoporous silica materials, stimuli-responsive gated materials, Janus particles and biocomputing. Basic concepts of chemical communication, materials and enabling technologies employed so far and representative examples in this field are also included. Next, in the second chapter, the general objectives of this PhD Thesis that are addressed in the following experimental chapters are presented. The third chapter shows a biocomputing delivery system based on Janus gold-mesoporous silica nanoparticles capable of chemically communicating with the environment and processing the information mimicking a demultiplexer Boolean logic function which results in a programmed cargo release. Finally, it is shown that such nanodevice is operative in complex media such as cancer cells. In the fourth chapter, it is presented a circular model of communication within a network of three different nanoparticles based on the hierarchically programmed exchange of chemical messages. The mesoporous face of nanodevice 1 (S1βgal) is loaded with the fluorescent dye [Ru(bpy)3]Cl2 and capped with disulfidecontaining oligo(ethylene glycol) chains acting as gatekeepers, whereas the enzyme β-galactosidase is attached to the gold face. In nanoparticle 2 (S2galox), the enzyme galactose oxidase is immobilized on the Au face, while the mesoporous silica is loaded with methyl 4-(bromomethyl)benzoate and the mesopores capped with a H2O2-sensitive self-immolative arylboronate derivative which forms a host-guest complex with β-cyclodextrin. Finally, the nanodevice 3 (S3est) is functionalized with the enzyme esterase on the Au face, loaded with the reductive species tris(2- carboxyethyl)phosphine hydrochloride (TCEP) in the mesoporous face and capped with a pH-responsive supramolecular nanovalve (β-cyclodextrin:benzimidazole). In the fifth chapter, it is showed an interactive model of chemical communication between an abiotic Janus nanoparticle and a living organism (Saccharomyces cerevisiae). In particular, the nanodevice is based on Janus goldmesoporous silica nanoparticles functionalized with glucose oxidase on the Au face, loaded with the genotoxin phleomycin and capped with a pH-responsive (βcyclodextrin:benzimidazole) gatekeeper. The microorganism used in the studies is an engineered budding yeast that expresses GFP under the control of the RNR3 promoter; RNR3 gene transcription is induced upon exposure to DNA-damaging agents. The interactive communication pathway starts with the addition of sucrose (input) which is hydrolyzed into glucose by invertase located in periplasmic space of yeasts and diffuses to the nanodevice where it is transformed into the corresponding acid by glucose oxidase on the Au face. The local drop in pH leads to uncapping of the pH-sensitive nanovalve in the nanocarrier and the release of phleomycin (feedback messenger) that induces GFP expression (output) in yeasts. In the sixth chapter, we propose a strategy to establish linear communication between two different non-interacting microorganisms mediated by a nanodevice which acts as a chemical “nanotranslator”. Finally, the general conclusions from this PhD Thesis are presented in chapter seven. The study of communication capabilities of enzyme-functionalized mesoporous nanodevices enables the construction of strategies of cooperation between different entities allowing sophisticated functionalities that go beyond those carried out by individual agents. We hope that the obtained results inspire future applications in different areas such as biomedicine, nanorobots, life-like materials and information technologies. / The authors wish to thank the Spanish Government (projects RTI2018-100910-B-C41 and RTI2018-101599-B-C22 (MCUI/AEI/FEDER, UE), CTQ2017-87954-P), the Generalitat Valenciana (PROMETEO 2018/024), the Comunidad de Madrid (IND2017/BMD7642) and CIBER-BBN (NANOCOMMUNITY project) for support. / De Luis Fernández, B. (2021). Development of enzyme-functionalized hybrid mesoporous nanodevices for advanced chemical communication [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/171506 / TESIS / Compendio