A busca por dispositivos que possuam uma estrutura micrométrica ou nanomé- trica, tem sido um tópico relevante de pesquisa, pois esse tipo de estrutura permite o estudo de efeitos ainda em análise e com várias questões em aberto, como por exemplo, efeito magnetoelétrico, o qual pode estar atrelado à um efeito de superfície. Estes tipos de efeitos podem surgir em dispositivos elétricos de modo a alterarem suas proprieda- des. Neste trabalho, desenvolveu-se uma heteroestrutura capacitiva composta por dois ele- trodos metálicos (Al na base e Ag no topo) com Al2O3 nanoporoso como separador dielétrico. O NAM foi obtido a partir de uma folha de Al de alta pureza por meio do processo de anodização em duas etapas. Esta técnica permite que, naturalmente, um dos planos da folha original permaneça inalterado, preservando uma fina camada de Al. Antes de revestir o plano oposto com Ag (via pulverização catódica), os na- nofios (Nanofios(Nf)) foram eletrodepositados no arranjo poroso hexagonal (poros de aproximadamente 50nm de diâmetro e 3m de comprimento). A heteroestrutura foi caracterizada por difração de raios X e por Microscopia Eletrônica de Varredura. As medições de capacitância versus tensão para frequências entre 1KHz e 5MHz foram realizadas utilizando uma estação de sonda Cascade Microtech controlada por um ana- lisador B1500A e foram obtidas capacitâncias por unidade de área planar de cerca de 50 nF para esta nanoestrutura. A presença de Nf no capacitor permite estudar o com- portamento da capacitância em função da magnetização deles. Os testes de capacitân- cia foram realizados deixando os Nf em estados magnéticos bem definidos. Primeiro, mediu-se a capacitância com os fios no estado desmagnetizado e, em seguida, com eles em estado remanescente após a saturação magnética no plano. Por fim, mediu-se a capacitância com os fios no estado remanescente após a saturação magnética ao longo do eixo do Nf. Após essas medidas, constatou-se o aumento na capacitância quando a magnetização do Nf aumenta. Este efeito magnetoelétrico é uma evidência experimen- tal do acoplamento de interface entre um dielétrico e um metal polarizado por spin. / The search for devices that have a micrometric or nanometric structure, has been a relevant research topic, since this type of structure allows the study of effects still under analysis and with several open questions, such as, for example, magnetoelectric effect, which can be tied to a surface effect. These types of effects can arise in electrical devices in order to change their properties. In this work, we have developed a capacitive heterostructure consisting of two metal electrodes (Al at the base and Ag at the top) with nanoporous Al2O3 as the dielec- tric separator. The NAM was obtained starting from a high-purity Al sheet, using the two-step anodization process. This technique allows one of the planes of the origi- nal sheet to remain unaltered naturally, preserving a thin layer of Al. Before coating the opposite plane with Ag (via sputtering), nano-wires (NW) were electrodeposited in the hexagonal pore array (pores of approximately 60nm of diameter and 10m of length). The heterostructure was characterized by X-ray diffraction. Measurements of capacitance versus voltage for frequencies between 1KHz e 5MHz were performed using a Cascade Microtech probe station controlled by a B1500A Analyzer and there were obtained capacitances per unit of planar area of around 50 nF for this nanos- tructure. The presence of NW in the capacitor allows the study of the behavior of the capacitance as a function of the magnetization of the NW. The capacitance tests were performed by leaving the NW in well-defined magnetic states. First, the wires were measured in the demagnetized state, than with them in a remanent state after the in-plane magnetic saturation. Finally, measures of capacitance were taken when the wires were in the remanent state after the magnetic saturation along the axis of the NW. There was seen the increase in capacitance when the magnetization of the NW increases. This magnetoelectric effect is an experimental evidence of the interface cou- pling between a dielectric and a spin-polarized metal.

No description available.

Habilitacinei procedūrai teikiamų darbų apžvalgoje yra pateikiama autoriaus atlikta ir kitų autorių įvairių kristalinių (ZnS, ZnSe) ir organinių junginių diodų, nanovamzdelių, plonų plėvelių, nanofibrų, ir kitų nanodarinių mokslinėje literatūroje skelbtų eksperimentinių elektrinio laidumo tyrimų rezultatų analizė bei šių rezultatų sugretinimas su fononais stimuliuoto tuneliavimo (FST) teorijų pagrindu paskaičiuotomis tuneliavimo tikimybių priklausomybėmis. Tyrimo rezultatai leido išsiaiškinti tai, kad krūvininkų generacijos procesas yra jų tuneliavimas iš gaudiklių dalyvaujant fononams. Įrodyta, kad organiniuose dariniuose (jų tarpe ir nanodariniuose) stebimą virsmą iš puslaidininkinio laidumo į metalinį laidumą (kai virsmo temperatūra TC) galima paaiškinti krūvininkų tunelinio proceso metu susidariusiu balansu tarp fononų absorbcijos ir jų generacijos, kai proceso metu elektrinis laukas krūvininkus išlaisvina iš lokalizuotos būsenos į laidumo būseną. Toje temperatūrų srityje, kur T < TC, tuneliavime dominuoja fononų absorbcija, ir todėl ten tunelinio perėjimo tikimybė, temperatūrai augant, padidėja. Priešingai, tose srityse, kur T > TC, procese dominuoja fononų emisija ir todėl ji sumažina krūvininkų tuneliavimo tikimybę, tuo pačiu iššaukdama elektrinio laidumo sumažėjimą kylant temperatūrai. Tokio FST modelio pagrįstumą įrodo ir tai, kad tiek plačiame elektrinių laukų, tiek ir temperatūrų intervale, tuneliavimo procesas yra vieningai aprašomas tų pačių parametrų... [toliau žr. visą tekstą] / Habilitation procedure review is for to clarify the conductance mechanism in polymers and other conducting nanodevices. The model based on the phonon-assisted tunnelling (PhAT) process, initiated by an electric field. An advantage of this PhAT model over the other models is the possibility to describe the behaviour of conductivity data measured at both low and high temperatures with the same set of parameters: εT - the energetic depth of the center, m* - the effective mass, T- temperature, E- the electric field, ħω - the phonon energy and a- the electron-phonon interaction constant. From these ones only the electron-phonon coupling constant a, and the phonon energy ħω are the fitting parameters estimated from the best fitting of the experimental data and the theory. Other parameters are from experiments or from literary sources known. Therefore, the PhAT mechanism could be dominant in the conductance of the MWNT, so as was shown, also in the case of the single-wall nanotubes. On the basis of this proposed model, the phenomenon of the crossover from non-metallic to metallic behavior of the conductivity is also explained. The decrease of conductivity in the framework of this model occurs at the temperatures T > TC when the phonon emission in the process of tunnelling dominates over the phonon absorption. The obtained agreement between the theoretical and experimental results, is not accidental but is due to the fact that the proposed model includes ultimate pictures of charge... [to full text]

Nanotechnology and nanoscience are experiencing rapid development in the last decade. Intensive research has been carried out on nanostructures synthesis and nanodevices fabrication. Due to its small size, a nanodevice usually requires an extremely small power to operate. However, to make the novel nanodevice work, an external power source is normally needed, which can either be a battery or a power source, thus, the size of the battery is usually much larger than that of the device and its life time is limited. It is highly desired to have a nanoscale size power source that harvests its energy from the environment so that it works independently and wirelessly to provide power to the nanodevices. This dissertation provides a solid solution to this dilemma based on nanotechnology. Starting from the synthesis of well aligned ZnO nanowire arrays on different substrates, an innovative method is presented first to measure the mechanical property of the as-synthesized ZnO nanowire arrays by using AFM without destroying and manipulating the sample. This technique is then extended to converte mechanical energy into electricity by scanning the nanowire arrays using a AFM tip in contact mode. Due to the unique semiconducting and piezoelectric dual properties of ZnO, mechanical energy is converted into electricity and is effectively output. This is the invention of the piezoelectric nanogenerator. Then, by replacing AFM tips using a zigzag top electrode, the first prototype direct-cirrent nanogenerator driven by ultrasonic wave has been fabricated. Further investigations have also been carried out about the effect of ZnO carrier density on the output power, and the power generating property of oligomer functionalized ZnO nanowires. This desertation established the fundamental mechanism for the nanogenerator, and it provides a new path towards self-powered nanosystems, which has key applications in in-vivo biosensing, MEMS, environmental mornitoring, defence technology and even personal electronics.

Molybdenum disulfide (MoS2) has been demonstrated to be a potential catalyst in the hydrogen evolution reaction (HER). Due to its highly active edge site, abundance, and low cost, it rivals Pt. However, the potential activity of the MoS2 basal plane has largely been ignored. The physical characteristics of MoS2 and its corresponding band structure change significantly with decreasing thickness, especially at the monolayer limit. Thus, an investigation on the thickness dependence may provide important insights into the MoS2 basal plane activity. In this thesis, the layer dependent electrocatalytic performance is investigated with mono-, bi- and multilayer MoS2 based individual nanodevices. Three conclusions were reached. (1) Monolayers showed exchange current densities more than one order of magnitude higher than that of the multilayers, 0.12 mA/cm2 and 8.7 mA/cm2, respectively. Furthermore, the onset potential of the monolayer was several hundred millivolts lower than that of the multilayer, about 0.2 V vs RHE for the monolayer versus 0.5 V vs RHE for the multilayer. The Tafel slope of 100-200 mV/dec revealed that the rate limiting step was the adsorption of hydrogen. (2) Interestingly, the bilayer sample exhibited an increase in its exchange current density from 0.3 mA/cm2 to 8 mA/cm2 when cycled extensively. This is suspected to be caused by intercalation of hydrogen between the atomic layers. (3) Additionally, the back-gate voltage is applied to tune the Fermi level of the material and the catalytic performance. It was found that the back-gate voltage induces an irreversible change in all samples, increasing the exchange current density by an order of magnitude. The superior basal plane performance of the monolayers to that of the multilayers reveals a new way to optimize the performance of MoS2 as a HER catalyst. In addition, the results above illuminate the yellow brick road to potential improvements in other layered materials as well.

Dans la prochaine ère de l'informatique distribuée, les ordinateurs inspirés par le cerveau qui effectuent des opérations localement plutôt que dans des serveurs distants seraient un avantage majeur en réduisant les coûts énergétiques et réduisant l'impact environnemental. Une nouvelle génération de nanodispositifs de mémoire non-volatile est un candidat de premier plan pour réaliser cette vision neuromorphique. À l'aide de travaux théoriques et expérimentaux, nous avons exploré les problèmes critiques qui se posent lors de la réalisation physique des architectures de réseaux de neurones artificiels modernes (ANN) en utilisant des dispositifs de mémoire émergents (nanodispositifs « memristifs »). Dans notre travail expérimental, nos dispositifs organiques (polymeriques) se sont adaptés avec succès et automatiquement en tant que portes logiques reconfigurables en coopérant avec un neurone digital et programmable (FGPA). Dans nos travaux théoriques, nous aussi avons considéré les multicouches memristives ANNs. Nous avons développé et simulé des variantes de projection aléatoire (un système NoProp) et de rétropropagation (un système perceptron multicouche) qui utilisent deux crossbars. Ces systèmes d'apprentissage locaux ont montré des dépendances critiques sur les contraintes physiques des nanodispositifs. Enfin, nous avons examiné comment les conceptions ANNs “feed-forward” peuvent être modi-fiées pour exploiter les effets temporels. Nous avons amélioré la bio-inspiration et la performance du système NoProp, par exemple, avec des effets de plasticité dans la première couche. Ces effets ont été obtenus en utilisant un nanodispositif à ionisation d'argent avec un comportement de transition de plasticité intrinsèque. / In the next era of distributed computing, brain-based computers that perform operations locally rather than in remote servers would be a major benefit in reducing global energy costs. A new generation of emerging nonvolatile memory devices is a leading candidate for achieving this neuromorphic vision. Using theoretical and experimental work, we have explored critical issues that arise when physically realizing modern artificial neural network (ANN) architectures using emerging memory devices (“memristors”). In our experimental work, we showed organic nanosynapses adapting automatically as logic gates via a companion digital neuron and programmable logic cell (FGPA). In our theoretical work, we also considered multilayer memristive ANNs. We have developed and simulated random projection (NoProp) and backpropagation (Multilayer Perceptron) variants that use two crossbars. These local learning systems showed critical dependencies on the physical constraints of nanodevices. Finally, we examined how feed-forward ANN designs can be modified to exploit temporal effects. We focused in particular on improving bio-inspiration and performance of the NoProp system, for example, we improved the performance with plasticity effects in the first layer. These effects were obtained using a silver ionic nanodevice with intrinsic plasticity transition behavior.

Hybridization of two or more DNA or RNA strands is well documented for the process taking place with all strands free in solution or when one strand is immobilized on a substrate. This study contributes to the investigation of the hybridization process when two single DNA strands (ssDNA) are in close proximity. We took advantage of an X sensor in which hybridization of four DNA strands enables the formation of a DNA four-way junction (crossover or X) structure. We immobilized multiple layers of crossover structures to study its hybridization being triggered by short ssDNA coming from solution and further investigate how many layers of these structures can hybridize by the addition of only one ssDNA (called input). Using a molecular beacon as reporter, we combined crossover DNA strands that recognize the reporter sequence at one side and at the other, the sequence of its input or downward crossover layer. Fluorescent signal was detected by separation of the molecular beacon’s fluorophore and quencher, as it hybridizes with the system of layers. Immobilization of the X structures into the scaffold proved to increase their communication, in comparison to being free in solution. This evidence gives us significant information for the communication of hybridized layers in a localized system, showing a promising standard for development of multilayered logic gates. The potential of these crossover DNA strands using X structure include applications in the future of biological systems, nanotechnology, and target DNA recognition for its ability to quickly recognize a signal and propagate it through extended DNA nanostructure in a controlled manner.

Uma das metas para a expansão do conhecimento em eletrônica molecular pode ser encontrada no projeto relacionado com a criação de circuitos em nanoescala com base em características de corrente-tensão não lineares, composto por moléculas ligadas a eletrodos metálicos sob a ação de um campo elétrico externo. O desenvolvimento de dispositivos eletrônicos moleculares que utilizam sistemas exibindo recursos semelhantes como materiais semicondutores intrínsecos é uma das metas a serem atingidas por uma extensa pesquisa em nanotecnologia. Assim, este trabalho tem como objetivo a expansão do conhecimento não só do transporte eletrônico, mas também as características físicas que justificam o regime de ressonância para o transporte eletrônico, como a condutância e Espectroscopia de Voltagem de Transição. Foi investigado teoricamente o transporte de carga eletrônica em um sistema molecular composto por estruturas de carbyne levando em conta as variações nos tipos de ligações −≡− (ligações simples e triplas para cada carbono). Os cálculos e aproximações ab initio são realizados para investigar a distribuição de estados de elétrons através da molécula na presença de um campo elétrico externo. Este novo dispositivo nanoeletrônico suscitará vantagem para o projeto de grandes circuitos orgânicos/metálicos híbridos 1D com um aumento do fluxo eletrônico que é importante para as necessidades da nanotecnologia. / One of the goals for the expansion of knowledge in molecular electronics may be found in the Project related to the creation of nanoscale circuits based on nonlinear current–voltage characteristics composed by molecules connected to metallic electrodes under the action of an external electric field. The development of molecular electronic devices using systems exhibiting similar feature as intrinsic semiconductor materials is one of the goals to be achieved by an extensive research in nanotechnology. Thus, this work aims at expanding of knowledge not only of the electronic transport, but also the physical features that justify the resonant regime for electronic transport, such as conductance and Transition Voltage Spectroscopy. We theoretically investigate the electronic charge transport in a molecular system composed by carbyne structures taking into account the variations in the bonds −≡− type (simple and triple bonds for each carbon). Ab initio calculations approximations are performed to investigate the distribution of electron states over the molecule in the presence of an external electric field. This new nanoelectronic device raise up advantage for the design of large 1D hybrid organic/metallic circuits with an increased electronic flow that is importante for the needs of nanotechnology.

In this thesis, a systematic study has been carried out on the synthesis, characterization and device fabrication of piezoelectric ZnO nanstructures. The achieved results are composed of the following four parts. Firstly, through a systematic investigation on the Sn-catalyzed ZnO nanostructure, an improved understanding of the chemical and physical process occurring during the growth of hierarchical nanostructures has been achieved. Decomposed Sn from SnO2 has been successfully demonstrated and proved to be an effective catalyst guiding the growth of not only aligned ZnO nanowires, but also the hierarchical nanowire-nanoribbon junction arrays and nanopropeller arrays. During the vapor-liquid-solid (VLS) catalyzing growth process at high temperature, Sn in the liquid state has been proved to be able to guide the growth of nanowires and nanoribbons in terms of growth directions, side facets, and crystallographic interfaces between Sn and ZnO nanostructures. Secondly, using pure ZnO as the only source material, by precisely tuning and controlling the growth kinetics, a variety of hierarchical polar surface dominated nanostructures have been achieved, such as single crystal nanorings, nanobows, nanosprings and superlattice nanohelices. High yield synthesis of ZnO nanosprings over 50% has been successfully obtained by mainly controlling the pre-pumping level associated with the partial pressure of residual oxygen during the vapor-solid growth process. The rigid superlattice nanohelices of ZnO have been discovered, which is a result of minimization of the electrostatic energy induced by polar surfaces. The formation process of the nanohelix has been systematically characterized. Thirdly, two new strategies have been successfully developed for fabricating ZnO quantum dots and synthesis of ZnO nanodiskettes and nanotubes. The formation process is based on a common concept of self-assembly. Finally, a series of devices and applications studies based on several piezoelectric ZnO nanostructures, such as nanobelts, nanopropellers and nanohelices, have been carried out utilizing the electro-mechanical resonance, bio-surface functionalization, devices fabrication and electrical characterization. Individual nanobelt and nanohelix based nanodevices have been successfully fabricated for applications in chemical and biological sensing. The study opens a few new areas in oxide nanostructures and applications.

Abstract This thesis focuses on THz band channel modeling and characterization. This vast frequency band spans from 100 GHz to 10 THz. The approximately 10,000 GHz bandwidth together with advances in THz capable electronics have made this band highly potential for many future applications, e.g., imaging and nanodevice-to-nanodevice communications. The latter is the reference application of this thesis and it focuses on the communication among very small and simple devices. The main focus of the thesis is on the THz channel characterization. Therefore, the channel models presented herein are also suitable for communications at macroscopic scale. The THz band offers opportunities, but has many problems as well. One of these is molecular absorption, which causes frequency selective fading to signals. The fading is caused by the signals’ energy absorption in the resonance frequencies of the molecules in the communication medium. Based on the conservation of energy, the absorption is understood to cause a new type of noise in the THz links: transmission induced noise. This noise component is analyzed from multiple physical viewpoints. The THz signals have short enough wavelengths to theoretically allow scattering on aerosols in the atmosphere. Scattering causes frequency dependent loss of the signals, but also a signal spread in time over multiple scattering events. It is shown here that in some specific atmospheric conditions the scattering causes signal loss and time spread. In addition to the theoretical channel models, measurements on a variety of propagation phenomena are con- ducted and analyzed. These include penetration losses, rough surface reflections and scattering, and diffraction. Through the measurements, it can be shown that the THz band communications is feasible in non-line-of-sight (NLOS) conditions in spite of the above phenomena. In the last part of this thesis, stochastic geometry is applied to the THz band in order to estimate the mean interference power and outage probabilities in dense networks formed from nanodevices. Because of the large losses in the channel, large interference levels require large numbers of devices. Stochastic geometry offers perfect tools to estimate the mean interference, and also in the case of directional antennas, which are most likely implemented in all the THz band devices due to large power losses in the channel. / Tiivistelmä Tämä väitöskirja paneutuu THz-taajuisien kanavien mallintamiseen. Tämä valtavan laaja kaista ulottuu sadasta gigahertsistä aina kymmeneen terahertsiin asti. Noin 10000 GHz:n kaistanleveys, yhdistettynä THz-taajuudet mahdollistavien elektroniikan komponenttien kehitykseen, tekee tästä kaistasta erittäin houkuttelevan vaihtoehdon moniin tulevaisuuden sovelluksiin. Näitä ovat mm. kuvantaminen ja nanolaitteiden välinen tietoliikenne. Viimeisin on tämän väitöskirjan viitekehys ja keskittyy hyvin pienien ja yksinkertaisien laitteiden väliseen viestintään. Työn keskittyy pääosin THz-kanavamallinnukseen, joten esitettyjä tuloksia voidaan hyödyntää myös nanoskaalaa suuremmissa verkoissa. THz-taajuudet avaavat mahdollisuuksia, mutta tuovat myös ongelmia. Yksi näistä on molekulaariabsorptio, joka aiheuttaa taajuusselektiivistä häipymää signaaleihin. Tämä ilmiö johtuu sähkömagneetisen energian absorbotumisesta ilman molekyylien resonanssitaajuuksilla. Sen on myös arveltu johtavan uudenlaisen kohinan syntyyn, lähetysten indusoimaan kohinaan, perustuen energian säilymislakiin. Lähetysten indusoimaa kohinaa tutkitaan tässä työssä erilaisista fysikaalisista näkökulmista. THz-taajuisen säteilyn aallonpituus on riittävän lyhyt mahdollistamaan sironta ilmassa olevista aerosoleista. Sironta aerosoleista johtaa taajusriippuvaan signaalitehon häviöön, mutta myös signaalitehon leviämiseen ajassa monisironnan kautta. Työssä todennetaan, että sopivissa olosuhteissa sironta lisää häviöitä ja viivehajetta kanavassa. Teoreettisten kanavamallien lisäksi analysoidaan mittauksin alemmilta taajuusalueilta tuttuja etenemisilmiöitä, kuten signaalin läpäisyä, heijastuksia ja sirontaa pinnoilta, sekä diffraktioita. Mittausten kautta voidaan näyttää, että THz-taajuinen tiedonsiirtolinkki voidaan luoda myös ilman näköyhteyttä yllä mainittujen ilmiöiden kautta. Työn viimeisessä osassa sovelletaan stokastista geometriaa THz-taajuuksille keskimääräisen häiriötehon ja toimintakyvyttömyystodennäköisyyden selvittämiseksi tiheissä nanolaitteiden muodostamissa verkoissa. Isojen kanavahäviöiden takia suuri häiriötaso vaatii suuren määrän laitteita. Stokastinen geometria antaa täydelliset työkalut häiriötason estimointiin. Tätä voidaan myös hyödyntää suuntaavien antennien tapauksessa, joita tullaan suurella todennäköisyydellä käyttämään kaikissa THz-laitteissa johtuen suurista signaalihäviöistä kanavassa.