Sneak path current is a significant remaining obstacle to the utilization of large crossbar arrays for non-volatile memories and other applications of memristors. A two-terminal selector device with an extremely large current-voltage nonlinearity and low leakage current could solve this problem. We present here a Ag/oxide-based threshold switching (TS) device with attractive features such as high current-voltage nonlinearity (~1010), steep turn-on slope (less than 1 mV/dec), low OFF-state leakage current (~10-14 A), fast turn ON/OFF speeds (<75/250 ns), and good endurance (>108 cycles). The feasibility of using this selector with a typical memristor has been demonstrated by physically integrating them into a multilayered 1S1R cell. Structural analysis of the nanoscale crosspoint device suggests that elongation of a Ag nanoparticle under voltage bias followed by spontaneous reformation of a more spherical shape after power off is responsible for the observed threshold switching of the device. Such mechanism has been quantitatively verified by the Ag nanoparticle dynamics simulation based on thermal diffusion assisted by bipolar electrode effect and interfacial energy minimization.

Moore’s law has until today mostly relied on shrinkage of the size of the devices inintegrated circuits. However, soon the granularity of the atoms will set a limit together with increased error probability of the devices. How can Moore’s law continue in thefuture? To overcome the increased error rate, we need to introduce redundancy. Applyingmethods from biology may be a way forward, using some of the strategies that transformsan egg into a fetus, but with electronic cells. A redundant system is less sensitive to failing components. We define electronic clayas a massive redundancy system of interchangeable and unified subsystems. We show how a mean voter, which is simpler than a majority voter, impact a redundant systemand how optimization can be formalized to minimize the impact of failing subsystems.The performance at given yield can be estimated with a first order model, without the need for Monte-Carlo simulations. The methods are applied and verified on a redundant finite-impulse response filter. The elementary circuit behavior of the memristor, ”the missing circuit element”, is investigated for fundamental understanding and how it can be used in applications. Different available simulation models are presented and the linear drift model is simulated with Joglekar-Wolf and Biolek window functions. Driven by a sinusoidal current, the memristor is a frequency dependent component with a cut-off frequency. The memristor can be densely packed and used in structures that both stores and compute in the same circuit, as neurons do. Surrounding circuit has to affect (write) and react (read) to the memristor with the same two terminals. We looked at artificial neural network for pattern recognition, but also for self organization in electronic cell array. Finally we look at wireless sensor network and how such system can adopt to the environment. This is also a massive redundant clay-like system. Future electronic systems will be massively redundant and adaptive. Moore’s law will continue, not based on shrinking device sizes, but on cheaper, numerous, unified and interchangeable subsystems.

Объектом исследования являются структуры металл/полупроводник/металл на основе анодированных слоев диоксида титана толщиной от 60 до 500 нм с диаметром нанотрубок от 30 до 60 нм, полученных во фторсодержащем растворе. Цель работы – исследование влияния толщины оксидного слоя, материала электрода и его площади на процессы резистивного переключения сэндвич-структур Ti/TiO2/Ме на основе нанотубулярного диоксида титана. Синтезированы сэндвич-структуры Ti/TiO2-НТ/Au и Ti/TiO2-НТ/Ag с диаметрами мемристивных элементов ≈ 100 мкм и ≈ 5,5 мм. Аттестация образцов проведена методами растровой электронной и оптической микроскопии, рентгенофазового анализа и спектроскопии комбинационного рассеяния. Исследованы ВАХ сфабрикованных структур в полных циклах резистивного переключения и в процессах, симулирующих многократное считывание информации. Получено, что микромемристор Ti/TiO2-НТ/Au с толщиной оксидного слоя 160 нм имеет наилучшие характеристики биполярного переключения среди исследованных. Продемонстрирована работоспособность структуры на протяжении 17 тыс. циклов переключения. Сделан вывод о возможности использования микромемристоров Ti/TiO2-НТ/Au в качестве перспективных элементов резистивной памяти. / The object of investigation of metal/semiconductor/metal structures based on the anodized layer of titanium dioxide. Ones are 60 – 500 nm thick with 30 – 60 nm diameter of nanotubes obtained in fluorine-containing solution. The goal of this paper is to investigate the effect of oxide layer thickness, its electrode material and the area on resistive switching processes in sandwich Ti/TiO2/Me nanotubular structures based on titanium dioxide. Sandwich structures of Ti/TiO2-NT/Au and Ti/TiO2-NT/Ag with diameters of memristive elements about 5.5 mm and 100 µm have been synthesized. Characterization of samples was carried out by scanning electron and optical microscopy, X-ray diffraction and Raman spectroscopy. CVC fabricated structures in the full cycle of the resistive switching and processes simulating multiple reading of information were studied. It was found that Ti/TiO2-NT/Au micromemristor with a thickness of the oxide layer about 160 nm has the best bipolar switching characteristics among studied samples. Structure performance within 17 thousands switching cycles was demonstrated. It is concluded that Ti/TiO2-NT/Au micromemristors were proved to be promising resistive memory elements.

The physical limitations of miniaturization of the traditional silicon-based electronic devices have motivated growing interest in molecular electronics due to its promising potential in transcending Moore's Law. Since the concept of molecular rectifier was first proposed by Ratner and Aviram in 1974, a lot of efforts have been devoted to realizing nondestructive electrical contacts to the individual or ensemble molecules, such as liquid metal contact, break junctions, cross wire junctions, etc. Among them, rolled-up nanotechnology is compatible with the conventional photolithography processes and can provide an efficient strategy to fabricate fully integrated functional molecular devices on a chip via an array of damage-free soft contacts. This nanotechnology takes an important step towards implementing the miniaturization of molecular devices and promotes the development of molecular electronics. In this doctoral thesis, rolled-up nanotechnology is employed to develop functional molecular devices on chips. Enabled by these rolled-up soft contacts, fully integrated molecular rectifiers based on ultrathin molecular heterojunctions are developed for the first time, and they are able to convert alternating current to direct current with frequencies up to 10 MHz. This is also the first time that a nanoscale organic rectifier with an operating frequency exceeding 1 MHz has been fabricated. The remarkable unidirectional current behavior of the molecular devices mainly originates from the intrinsically different surfaces of bottom planar and top microtubular gold electrodes. While the excellent high-frequency response is guaranteed by the charge accumulation in the phthalocyanine molecular heterojunction, which not only improves the charge injection but also increases the carrier density. Then this rolled-up nanotechnology is further employed to explore multi-functional molecular devices. In this thesis, fully integrated process-programmable molecular devices are achieved for the first time, which can switch between photomultiplication photodiodes and bipolar memristors. The transition depends on the release of mobile ions initially stored in the bottom polymeric electrode and can be controlled by modulating the local electric field at the interface between the ultrathin molecular layer and the bottom electrode. Photogenerated-carrier trapping at a low interfacial electric field leads to photomultiplication with an ultrahigh external quantum efficiency (up to 104%). In contrast, mobile-ion polarization triggered by a high interfacial electric field results in ferroelectric-like memristive behaviour with both remarkable resistive on/off ratios and rectification ratios. The combination of the “soft-contact” enabled by rolled-up nanotechnology and the “ion reservoir” provided by the polymeric electrode opens up a novel strategy for integrating multi-functional molecular devices based on the synergistic electronic-ionic reaction to various stimuli.:List of abbreviations 6 Chapter 1 Introduction 8 1.1 Molecular electronics: a brief history 8 1.2 Motivation: why molecular electronics? 9 1.3 Objectives: developing integrated functional molecular devices 14 1.4 Dissertation structure 15 Chapter 2 Fabrication and characterization methods 17 2.1 Core nanotechnology adopted in this thesis: rolled-up nanomembrane contacts 17 2.2 Fabrications 18 2.2.1 Photolithography 18 2.2.2 Spin-coating 23 2.2.3 Electron-beam deposition 24 2.2.4 Sputter deposition 25 2.2.5 Atomic layer deposition 27 2.2.6 Low-temperature evaporation 28 2.3 Characterizations 30 2.3.1 Atomic force microscopy 30 2.3.2 Photoelectron spectroscopy 32 2.3.3 X-ray diffraction 35 Chapter 3 Integrated molecular rectifiers 37 3.1 Introduction 37 3.2 Construction of the organic heterojunction 39 3.3 Microfabrication of the molecular diode 46 3.4 Origination of the rectification 54 3.5 Frequency performance 61 3.6 Discussion 63 Chapter 4 Integrated process-programmable molecular devices 66 4.1 Introduction 66 4.2 Design and microfabrication of the molecular devices 69 4.2.1 Top tubular metallic electrodes 69 4.2.2 Bottom finger polymer electrodes 71 4.3 Function I: Molecular photomultiplication photodiodes 75 4.3.1 Traditional photodiodes and photomultiplication photodiodes 75 4.3.2 Performance of molecular photomultiplication photodiodes 78 4.3.3 Transition voltage spectroscopy 84 4.4 Function II: Molecular bipolar memristors 86 4.4.1 Ion doping-assisted injection 86 4.4.2 Performance of the molecular bipolar memristors 88 4.4.3 Mechanism of the resistance switching 97 4.5 Mechanism of the electric-field-driven transition 106 4.6 Conclusions 108 Chapter 5 Conclusions and outlook 110 5.1 Conclusions 110 5.1.1 Fully integrated molecular rectifiers 110 5.1.2 Fully integrated process-programmable molecular devices 111 5.2 Outlook 111 5.2.1 Improve the yield of the integrated molecular devices 111 5.2.2 Develop integrated molecular functional devices 112 References 113 List of figures and tables 129 Selbständigkeitserklärung 134 Theses 135 Acknowledgments 138 Research achievements 140 Curriculum-vitae 142

Memristor, defined as a two-terminal device which exhibits a pinched hysteresis loop in the current-voltage characteristics, is a main component of the resistive random access memory. Both memristor and memristive phenomena, known also as resistive switching (RS), have been thoroughly investigated in the past nearly two decades. This dissertation investigates YMnO3 thin films and explores a new concept concerning utilization of multiferroic properties for activation and/or enhancement of RS. It is hypothesized that the charged domain walls and/or vortex cores in YMnO3 thin films can act as an effective nanoscale features which support formation of the conductive filaments and, in consequence, enable development of an electroforming-free memristive structure. Results of the electrical characterization of YMnO3-based metal-insulator-metal structures indicate that hexagonal YMnO3 films deposited on metal-coated oxide substrate exhibit electroforming-free unipolar resistive switching (URS) while orthorhombic YMnO3 films grown on the doped oxide substrate show bipolar resistive switching (BRS). Observed URS is assigned to the formation and rupture of conductive, metallic-like filaments induced by the thermo-chemical phenomena. Results of polarity-dependent studies reveal that formation of conductive filaments proceeds in the electrostatic discharge event which is followed by their irreversible rupture during the reset process. Main properties of the observed URS include very good retention of programmed states, large memory window (between 10E+2 and 10E+4), high voltage and current required for set and reset, respectively, and low endurance. BRS is attributed to the complementary electronic and ionic processes within the p-n junction formed at the interface between p-YMnO3 and n-type oxide substrate. Results of ferroelectric characterization reveal that resistively switching YMnO3 films do not exhibit ferroelectric properties. Therefore, observed RS in YMnO3-based structures can not be directly related to the presence of charged domain walls and/or multiferroic vortex cores. Prospective functionality extension of YMnO3-based memristive devices is developed and presented on the example of photodetecting properties of metal-YMnO3-insulator-semiconductor stacks. Studies conducted within the framework of this doctoral dissertation investigate the resistive switching behaviour of YMnO3-based junctions. Obtained results contribute to the better understanding of the resistive switching and failure mechanisms in ternary oxides, and provide hints toward device engineering. / Der Memristor ist definiert als eine Zweipol-Vorrichtung, die eine hysteretische Strom-Spannungs-Charakteristik aufweist. Memristoren sind nichtflüchtige Widerstandsspeicher, deren elektrischer Widerstand mittels elektrischer Spannungspulse verändert werden kann. Sowohl Memristoren als auch memristive Widerstandsschalter (RS) werden seit mehr als zwei Jahrzehnten intensiv untersucht. Diese Dissertation untersucht YMnO3-Dünnschichten mit zirkularen Vorderseiten-Elektroden und unstrukturierten Rückseiten-Elektroden und erforscht ein neues Konzept über die Nutzung der multiferroischen Eigenschaften für die Aktivierung und/oder Verbesserung des memristiven Verhaltens. Es wird angenommen, dass die geladenen Domänenwände und/oder Vortices in YMnO3-Dünnschichten die Bildung leitfähiger Filamente wirksam unterstützt und folglich die Entwicklung eines neuartigen, formierungs-freiem Widerstandsspeichersermöglicht. Die Ergebnisse der elektrischen Charakterisierung von YMnO3-basierten Widerstandsschalter zeigen unipolares RS (URS), wenn eine metallische Rückseitenelektrode verwendet wird und bipolares RS (BRS), wenn als Rückseitenelektrode ein metallisch leitendes Oxid-Substrat verwendet werden. Das URS wird als thermochemisches RS klassifiziert und mit der Bildung und Auflösung metallisch leitender Filamente korreliert. Das BRS wird auf das Einfangen/Freigeben von Defekten in der Raumladungszone des YMnO3 im pn-Übergang von p-YMnO3/n-Nb:SrTiO3-Strukturen zurückgeführt. Die wichtigsten Eigenschaften des formierungsfreien URS sind die sehr gute Retention der programmiertenWiderstandszustände, große Speicherfenster (zwischen 10E+2 und 10E+4), die hohe Schreibspannung für den Set-Prozess und der hohe Schreibstrom für den Reset-Prozess. Die Endurance ist aufgrund der Degradation des Vorderseiten-Elektrode gering. Die Ergebnisse des polaritätsabhängigen Widerstandsschaltens zeigen, dass der Set-Prozess mit elektrostatischer Entladung einhergeht. Die ferroelektrische Charakterisierung zeigt, dass die YMnO3–Dünnfilme keine ferroelektrischen Eigenschaften aufweisen. Daher kann das beobachtete URS nicht direkt auf die Anwesenheit von geladenen Domänenwände und Vortices zurückgeführt werden. Darüberhinaus wurden die photodetektierenden Eigenschaften von Metall-YMnO3-Isulator-Halbleiter-Stacks als potenzielle Erweiterung der Funktionalität von YMnO3-basierten memristiven Bauelementen vorgestellt und vorgeschlagen. Im Rahmen der vorliegenden Dissertation wurde das Widerstandsschalten von multiferroischen, YMnO3-basierten Widerstandsschaltern untersucht. Die erhaltenen Ergebnisse tragen zu einem besseren Verständnis des Widerstandsschaltens von multiferroischen Materialien bei.

Durant ce travail de thèse, nous avons étudié deux concepts originaux de memristor fondés sur des effets purement électroniques. Un memristor est une nanorésistance variable non-volatile dont la valeur dépend de la quantité de charges qui l'a traversée. Ce composant est particulièrement prometteur pour des applications en tant qu'élément de mémoire binaire multi-niveaux ou en tant que synapse artificielle pour intégration dans des architectures de calculs neuromorphiques. Le premier concept, le memristor spintronique, se base sur une jonction tunnel magnétique dans laquelle une paroi magnétique est introduite. Par l'effet de magnétorésistance tunnel, la résistance de la jonction dépend de la configuration magnétique, et donc de la position de la paroi. La variation de résistance est obtenue en déplaçant la paroi grâce à un courant par effet de transfert de spin. Le deuxième concept, le memristor ferroélectrique, se base sur une jonction tunnel dont la barrière est ferroélectrique. La résistance d'une telle jonction dépend de l'orientation de la polarisation de la barrière ferroélectrique. Nous montrons qu'elle a un fort potentiel en tant qu'élément de mémoire binaire de part la vitesse et l'énergie d'écriture. Le comportement memristif est obtenu par un retournement progressif de la polarisation électrique. Les résultats expérimentaux obtenus apportent la preuve des concepts. Contrairement aux memristors existants basés sur des processus comme l'électromigration ou le changement de phase, ces deux concepts fondés sur des effets purement électroniques sont prometteurs en termes de rapidité et d'endurance.

Abstract In this thesis several novel inks based on dry inorganic powders enabling magnetic, piezoelectric and memory resistive (memristive) function were researched for printed electronics applications. Low curing temperature screen–printable magnetic inks for high frequency applications based on dry cobalt nanoparticles were developed in the first part of the work. Three publications were achieved. The first one concentrated on ink formulation and its process development, the second on the utilization of multifunctional surfactant, and the third on the development of the inks for plastic substrates. The magnetic inks developed were cured at 120 &#176;C. The electrical performance, microstructure, surface quality and mechanical durability of printed and cured layers were investigated. Relative permeability values up to 3 and related loss tangents up to 0.01 were achieved at 2 GHz frequency, as well as a pull–off strength of up to 5.2 MPa. The maximum loading level of cobalt nanoparticles was 60 vol–%, after which the stability of the ink started to degrade. The developed ink enabled the miniaturization of a patch antenna. In the second part of the thesis, the formulation of inks based on piezoelectric ceramic particles in powder form with ferroelectric polymers as a matrix material is introduced. The performance and quality of the printed inks and cured layers were investigated. The measured pull off –strength was up to 3.25 MPa, relative permittivity was up to 48 at 1 kHz and piezoelectric constant d31 up to 17 pm/V. The printed piezoelectric layer can be utilized in a pressure sensor. In the third part of the thesis, the development of inks for a novel printed memory component, a memristor, is researched. A synthesis route was developed for an organometallic precursor solution, which was formulated into inkjet–printable form. The printing tests were carried out in order to find the most feasible layer thickness with memristive behaviour. The influence of substrate materials and different thermal treatments on the components’ electrical properties, durability of read/erase –cycles and overall lifetime were also investigated. The prepared memristive patterns remained functional for up to 35 days, while the precursor solution remained usable for over a year. The memristive areas withstood up to 30 read/erase cycles and by utilizing heat treatments the shift in resistance value increased by up to three orders of magnitude. / Tiivistelmä Väitöstyössä kehitettiin epäorgaanisten kuivien jauhemaisten materiaalien pohjalta magneettisia, pietsosähköisiä ja memristiivisiä musteita käytettäviksi painettavan elektroniikan sovelluksissa. Työn ensimmäisessä osassa tutkittiin korkean taajuuden sovelluksissa käytettävien magneettisten, matalassa lämpötilassa kovetettavien, jauhemaisiin kobolttinanopartikkeleihin perustuvien silkkipainomusteiden valmistamista. Tulokset on esitetty kolmessa julkaisussa, joista ensimmäinen keskittyi musteen formulointiin, toinen monifunktionaalisen surfaktantin hyödyntämiseen ja kolmas musteen kehittämiseen muovialustalle sopivaksi. Työssä kehitettiin 120 &#176;C:ssa kovettuvia musteita, joista valmistettujen kalvojen suhteellisen permeabiliteetin maksimiarvoksi saatiin 3 ja häviöiden minimiarvoksi 0,01 kahden gigahertsin taajuudella. Pull–off –vetotestin tulokseksi saatiin jopa 5,2 MPa. Musteet säilyivät vakaina enimmillään 60 tilavuusprosentin metallipitoisuudella. Kehitettyä mustetta käytettiin tasoantennin miniatyrisoinnissa. Toisessa osassa kehitettiin pietsosähköisiä musteita, jotka pohjautuivat keraamijauheeseen ja matriisimateriaalina toimivaan ferrosähköiseen muoviin. Niistä valmistettujen kalvojen parhaaksi pull off –vetotestin tulokseksi saatiin 3,25 MPa, permittiivisyyden maksimiarvoksi 48 yhden kilohertsin taajuudella ja d31–pietsovakion maksimiarvoksi jopa 17 pm/V. Kehitettyjä painettuja rakenteita voidaan käyttää painettavissa paineantureissa. Kolmannessa osassa kehitettiin uudentyyppinen painettava muistikomponentti, memristori ja komponenttien valmistamiseksi uusi prekursoriliuoksen synteesi. Syntetisoitu liuos muokattiin mustesuihkutulostettavaksi. Painokokeiden avulla selvitettiin materiaalin paksuus, jolla saatiin aikaan muistivastukselle ominainen memristiivinen käyttäytyminen. Työssä tutkittiin substraattimateriaalien ja mahdollisten lämpökäsittelyjen vaikutusta komponenttien sähköisiin ominaisuuksiin, luku/kirjoitussyklien kestoon sekä käyttöikään. Valmistetut memristiiviset kalvot säilyivät toimivina 35 vuorokautta ja prekursoriliuos yli vuoden. Memristiiviset pinnat kestivät jopa 30 luku/kirjoitussykliä ja vastusarvon muutos saatiin lämpökäsittelyllä kolmea kertaluokkaa suuremmaksi.

Memristor is a novel passive electronic device and a promising candidate for new generation non-volatile memory and analog computing. Analog computing based on memristors has been explored in this study. Due to the lack of commercial electrical testing instruments for those emerging devices and crossbar arrays, we have designed and built testing circuits to implement analog and parallel computing operations. With the setup developed in this study, we have successfully demonstrated image processing functions utilizing large memristor crossbar arrays. We further designed and experimentally demonstrated the first memristor based field programmable analog array (FPAA), which was successfully configured for audio equalizer and frequency classifier demonstration as exemplary applications of such memristive FPAA (memFPAA).

No description available.

A 2T2C ferroelectric memory cell consisting of a select transistor, a read transistor and two ferroelectric capacitors that can be operated either in FeRAM mode or in memristive ferroelectric tunnel junction mode is proposed. The two memory devices can be programmed individually. By performing a combined readout operation, the two stored bits of the memory cells can be combined to perform in-memory logic operation. Moreover, additional input logic signals that are applied as external readout voltage pulses can be used to perform logic operation together with the stored logic states of the ferroelectric capacitors. Electrical characterization results of the logic-in-memory (LiM) functionality is presented.