This thesis reports the discovery of a wide negative di↵erential resistance (NDR) region in a graphite-silicone composite that was utilized to create a strain-tuned flexible oscillator. Encoding the strain into frequency mimics the behavior of mechanoreceptor neurons in the skin and demonstrates a flexible and electronically active material suitable for state of the art bio-electronic applications. The NDR was investigated over a range of composite filling fractions and temperatures; alongside theoretical modelling to calculate the tunneling current through a graphite-silicone barrier. This led to the understanding that the NDR is the result of a semi-metal to insulator transition of embedded graphene bilayers within the graphite nanoparticles. The transition, brought about by a transverse bias across specifically orientated particles, opens a partial band-gap at the Fermi level of the bilayer. NDR in a flexible material has not been observed before and has potential for creating a flexible active device. The electromechanical properties of the composite were considered through a bend induced bilayer strain. The piezoresistance was found to be dominated by transient resistance spiking from the breaking of conduction lines, which then reform according to the viscoelasticity of the polymer matrix. The resistance spiking was embraced as a novel method for sensitive di↵erential pressure detection, used in the development of two applications. Firstly, it was employed for the detection of ultrasound waves and found to have an acoustic pressure detection threshold as low as 48 Pa. A commensurability was observed between the composite width and ultrasound wavelength which was shown to be consistent with the formation of standing waves, described by Bragg’s law. Secondly, a differential pressure array of 64 composite pixels was fabricated and demonstrated to image pressures under 3.8 kPa at a resolution of 10 dpi. The NDR active region was incorporated into an LC circuit where it was demonstrated to sustain oscillations of up to 12.5 kHz. The composite was then strained and an intrinsic frequency was observed which had a linear dependence on the strain with a frequency shift of 84 Hz / % strain. Lastly the composite was used in a strain-tuned amplifier circuit and shown to provide a gain of up to 4.5. This thesis provided the groundwork for a completely flexible electronically active device for futuristic bio-electronic skins with resolutions and sensitivities rivalling those of human tactile sensing.

Complementing electronic components with molecular analogs is a promising alternative to further miniaturization of conventional silicon electronic devices in the quest to achieve functional molecular nanoscale circuit elements. To this end, molecular units have been widely investigated to evaluate their suitability for future nanoelectronic circuit applications. Previous work has typically either focused on tightly packed layers of dithiol molecule-encapsulated gold nanoparticles or small oligomeric structures comprised of nanoparticles linked by a few dithiol molecules. In this thesis, we study the electrical and electronic properties of metal-molecular networks having an intermediate number of dithiol molecules both theoretically and experimentally. Electronic transport through self-assembled networks with tunable thiol molecule: gold nanoparticle ratios (ranging from 1:1 to 50:1) is studied using two-terminal electrical characterization techniques. The tunability of the electrical properties (e.g., resistance, current etc.) of the molecular networks on modifying the thiol molecule: gold nanoparticle ratios and/or type of molecule used was observed. Specifically, the current in the molecular networks studied typically decreased with increasing molecule: AuNP. For example, in gold-benzenedithiol molecular networks with approximately the same length-to-width ratios, current at low bias, 0.3 V, was found to decrease from the μA range in 1:1 ratio samples to the nA range in 50:1 samples. Additionally, many gold-benzenedithiol molecular networks which had linear I-V characteristics at low biases displayed nonlinearities in their I-Vs at higher biases. In such cases, the nonlinearities in the I-Vs at higher biases became more pronounced with increasing molecule: AuNP ratio. For example, in a control sample, consisting of only gold nanoparticles, linear I-V behaviour was observed, while the 50:1 gold-benzenedithiol molecular network displayed NDR with a measured peak-to-valley ratio of approximately 1.52. A linear resistor circuit model provided accurate approximations of the low bias I-V behaviour of the molecular networks. Experimental studies were complemented with first principles density functional theory-based simulations of the molecular networks. Linear chains and branched networks of interconnected benzenedithiol molecules and Au6 clusters were the systems of interest in this study. Calculated current-voltage characteristics of the metal-molecular networks exhibited nonlinearities and rectification with negative differential resistance (NDR) peaks that became more pronounced with increasing chain length of the linear chains. Peak-to-valley current NDR ratios as large as ~ 500 and rectification ratios of ~ 10 (0.25 V) were shown for linear and branched circuit elements, respectively, illustrating how charge transport through molecular-scale devices could be controlled with precision by modifying the structure and geometry of molecule-nanoparticle networks. Observed nonlinearities (e.g., NDR, hysteresis, and rectification) in the I-Vs of the self-assembled metal-molecular networks studied highlight their potential for application as circuit elements in future nanoelectronic devices and circuits, including memory, logic, switching and sensing. Additionally, the device level physical randomness and imperfections induced during fabrication of the metal-molecular networks, as well as the variability of the resistance of the networks on modifying the molecule: gold nanoparticle ratios can be applied for generating random binary sequences. / Graduate

Replacing electronic components with molecule-sized analogs or hybrids is often seen as a promising alternative to further miniaturization of conventional electronics in the effort to achieve functional nanoscale circuit elements. In this thesis, electronic transport through self-assembled networks with tunable thiolated (alkane(di)thiol and benzenedithiol) molecule-to-colloidal gold (Au) nanoparticle ratios (1:5–50:1) is studied using a combination of broad area and scanning probe microscope-based measurements. The electronic transport paths through the network can be altered by adjusting the (di)thiol molecule–gold nanoparticle ratio and/or type of molecules in the network. Resistance can be controllably tuned by several orders of magnitude (~105 to 1011 ohms for the Au-thiolated structures studied). Two-terminal current–voltage (I-V) measurements of the Au-thiolated networks display linear behavior at low bias. High bias measurements in case of benzenedithiol networks show nonlinear negative differential resistance (NDR) and hysteresis behavior for different benzenedithiol concentrations, which can be attributed to a combination of field-assisted tunneling and charge trapping occurring in the nanoscale networks. Circuit simulations that account for different network morphologies, tunable via molecule-to-nanoparticle ratio, and defects show good agreement with the experiment and provide a guide to engineer network properties using different molecules. In addition, electronic transport properties of nanoscale networks, which are composed of Au metal clusters interconnected with thiolated molecules (benzene/alkanedithiol) and connected in linear chains and branched extended networks, are examined via first-principles density functional theory-based simulations. Calculated I-V characteristics of the metal-molecular networks exhibited nonlinearities and rectification with NDR peaks that became more pronounced with increasing chain length. The transmission spectra of the linear chains and branched networks showed an increase in the number and width of transmission peaks near the Fermi energy, as the structures were extended, indicating enhanced transmission. Peak-to-valley current NDR ratios as large as ~ 500 and rectification ratios of ~ 10 (0.25 V) were shown for linear and branched circuit elements, respectively, illustrating how charge transport through molecular-scale devices could be controlled with precision by modifying the structure and geometry of molecule-nanoparticle networks. These experimental and simulation results are utilized to propose molecular-scale circuits in applications such as memory, switching, and hardware security. The metal nanoparticle molecular electronic networks presented in this thesis provide an avenue for engineering electronics at the molecular level. / Graduate

No description available.

Es konnte vor kurzem gezeigt werden, daß die Reduktion von Wasserstoffperoxid (H2O2) an Silber in Perchlorsäure (HClO4) über zwei parallele Wege verläuft. Die normale Reduktion wird bei einer Überspannung von -1,5 V beobachtet, während die zweite Reduktionsreaktion bei einer deutlich geringeren Überspannung bei -1,0 V stattfindet. Im zweiten Reaktionsweg wird OHad als instabile Zwischenspezies gebildet und wirkt katalytisch auf die H2O2-Reduktion. Daher wird angenommen, daß die zweite Reaktion eine autokatalytische Reduktion ist. Diese autokatalytische Reaktion wird nach einer ge-wissen Zeit deaktiviert, die von der Rotationsgeschwindigkeit der Elektrode abhängig ist. Sie kann wiedererlangt werden, wenn die Elektrode negativ polarisiert wird. In dieser Arbeit wurden Ex-situ-XPS-Messungen an herausgezogenen Ag(111)-Elektroden durch-geführt. Die Analyse führt zu dem Ergebnis, daß die Deaktivierung durch geringe Chlorid-Verunreinigungen verursacht wird. Elektrochemische Impedanzspektren werden zusammen mit numerischen Simulationen der Faradayschen Impedanz des autokata-lytischen Bereiches gezeigt. Diese basieren auf Annahmen von kinetischen Geschwin-digkeitsgesetzen, die früher postuliert wurden. Die experimentellen Daten stimmen sehr gut mit den Ergebnissen der theoretischen Rechnungen überein. Dies unterstützt den angenommen autokatalytischen Mechanismus. / Recently, it was shown that the hydrogen peroxide (H2O2) reduction on silver in perchloric acid (HClO4) proceeds in two parallel paths. The normal reduction is observed at an overpotential of -1.5 V, whereas a second reduction reaction occurs at a significantly lower overpotential at -1.0 V. The second reaction involves the unstable intermediate OHad, which also acts as a catalyst. Hence, the second reaction has been proposed to be an autocatalytic one. This autocatalytic reaction is deactivated after a certain time that depends on the rotation speed of the electrode. It can be recovered if the electrode is negatively polarized. In this thesis work, ex-situ XPS measurements on emersed Ag(111) electrodes were conducted. The analysis leads to the conclusion that the deactivation is caused by a small amount of chloride contamination. Electrochemical impedance spectra are presented together with numerical simulations for the faradaic impedance in the autocatalytic region based on previously suggested kinetic rate laws. The experimental data fit well with the results of the theoretical calculations, which strongly supports the autocatalytic mechanism.

In this work, homojunction interfacial workfunction internal photoemission (HIWIP) detectors based on GaAs, and heterojunction interfacial workfunction internal photoemission (HEIWIP) detectors based mainly on the Gallium Arsenide/Aluminum Gallium Arsenide material system are presented. Design principles of HIWIP and HEIWIP detectors, such as free carrier absorption, photocarrier generation, photoemission, and responsivity, are discussed in detail. Results of p-type HIWIPs based on GaAs material are presented. Homojunction detectors based on p-type GaAs were found to limit their operating wavelength range. This is mainly due to band depletion arising through carrier transitions from the heavy/light hole bands to the split off band. Designing n-type GaAs HIWIP detectors is difficult as it is strenuous to control their workfunction. Heterojunction detectors based on Gallium Arsenide/Aluminum Gallium Arsenide material system will allow tuning their threshold wavelength by adjusting the alloy composition of the Aluminum Gallium Arsenide/Gallium Arsenide barrier, while keeping a fixed doping density in the emitter. The detectors covered in this work operate from 1 to 128 micron (300 to 2.3 THz). Enhancement of detector response using resonance cavity architecture is demonstrated. Threshold wavelength extension of HEIWIPs by varying the Al composition of the barrier was investigated. The threshold limit of approximately 3.3 THz (92 micron), due to a practical Al fraction limit of approximately 0.005, can be overcome by replacing GaAs emitters in Gallium Arsenide/Aluminum Gallium Arsenide HEIWIPs with Aluminum Gallium Arsenide/Gallium Arsenide emitters. As the initial step, terahertz absorption for 1 micron-thick Be-doped Aluminum Gallium Arsenide epilayers (with different Al fraction and doping density) grown on GaAs substrates was measured. The absorption probability of the epilayers was derived from these absorption measurements. Based on the terahertz absorption results, an Aluminum Gallium Arsenide/Gallium Arsenide HEIWIP detector was designed and the extension of threshold frequency (f0) to 2.3 THz was successfully demonstrated. In a different study, switching in Gallium Arsenide/Aluminum Gallium Arsenide heterostructures from a tunneling dominated low conductance branch to a thermal emission dominated high conductance branch was investigated. This bistability leads to neuron-like voltage pulses observed in some heterostructure devices. The bias field that initiates the switching was determined from an iterative method that uses feedback information, such as carrier drift velocity and electron temperature, from hot carrier transport. The bias voltage needed to switch the device was found to decrease with the increasing device temperature.

Electrical and optical characterizations of heterostructures and thin films based on group III-V compound semiconductors are presented. Optical properties of GaMnN thin films grown by Metalorganic Chemical Vapor Deposition (MOCVD) on GaN/Sapphire templates were investigated using IR reflection spectroscopy. Experimental reflection spectra were fitted using a non - linear fitting algorithm, and the high frequency dielectric constant (ε∞), optical phonon frequencies of E1(TO) and E1(LO), and their oscillator strengths (S) and broadening constants (Γ) were obtained for GaMnN thin films with different Mn fraction. The high frequency dielectric constant (ε∞) of InN thin films grown by the high pressure chemical vapor deposition (HPCVD) method was also investigated by IR reflection spectroscopy and the average was found to vary between 7.0 - 8.6. The mobility of free carriers in InN thin films was calculated using the damping constant of the plasma oscillator. The terahertz detection capability of n-type GaAs/AlGaAs Heterojunction Interfacial Workfunction Internal Photoemission (HEIWIP) structures was demonstrated. A threshold frequency of 3.2 THz (93 µm) with a peak responsivity of 6.5 A/W at 7.1 THz was obtained using a 0.7 µm thick 1E18 cm−3 n - type doped GaAs emitter layer and a 1 µm thick undoped Al(0.04)Ga(0.96)As barrier layer. Using n - type doped GaAs emitter layers, the possibility of obtaining small workfunctions (∆) required for terahertz detectors has been successfully demonstrated. In addition, the possibility of using GaN (GaMnN) and InN materials for terahertz detection was investigated and a possible GaN base terahertz detector design is presented. The non - linear behavior of the Inter Pulse Time Intervals (IPTI) of neuron - like electric pulses triggered externally in a GaAs/InGaAs Multi Quantum Well (MQW) structure at low temperature (~10 K) was investigated. It was found that a grouping behavior of IPTIs exists at slow triggering pulse rates. Furthermore, the calculated correlation dimension reveals that the dimensionality of the system is higher than the average dimension found in most of the natural systems. Finally, an investigation of terahertz radiation efect on biological system is reported.

Trotz einer Vielzahl von Forschungsarbeiten auf dem Gebiet der Phthalocyanin-basierten organischen Verbindungen fehlt nach wie vor ein umfassendes Verständnis des Zusammenspiels zwischen strukturellen und elektronischen Eigenschaften, die sich bei der Abscheidung dieser Stoffe auf anorganische kristallinen Substraten ausbilden. Vor diesem Hintergrund wurden für die vorliegende Arbeit vier metallbasierte Phthalocyanine ausgewählt und mittels organischer Molekularstrahl-Abscheidung (OMBD) im Ultrahochvakuum (UHV) auf Ag (111) Einkristalle adsorbiert. Für die anschließende eingehende Untersuchung dieser Proben wurden insbesondere Rastertunnelmikroskopie (STM) und -spektroskopie (STS) angewandt. Ergänzend kamen Ultraviolett- und Röntgen-Photoelektronenspektroskopie (UPS und XPS) zum Einsatz, wodurch komplementäre Informationen gewonnen wurden. Die aus diesen Untersuchungen resultierenden Ergebnisse liefern einen wesentlichen Beitrag zum oben genannten Forschungsgebiet. Die in dieser Arbeit untersuchten Metall-Phthalocyanine (MePc) wurden so ausgewählt, dass eine möglichst große Vielfalt an geometrischen und elektronischen Eigenschaften abgedeckt wurde. Planare cobaltbasierte Phthalocyanin-Moleküle wurden in zwei Konfigurationen untersucht: einerseits das protonierte CoPc, das sich als organischer p-Halbleiter verhält, und andererseits das vollständig fluorinierte F16CoPc, das n-Halbleitereigenschaften besitzt. Bei beiden Systemen zeigte sich an der Position des Cobaltions eine Kopplung zwischen den Molkülorbitalen des Adsorbats und den Elektronenzuständen des Substrates. Das nichtplanare Zinn-Phthalocyanin ist von besonderem Interesse aufgrund seiner beiden möglichen Adsorptionskonformationen up und down, bei denen sich das Sn-Ion oberhalb beziehungsweise unterhalb des Phthalocyaninliganden befindet. Damit stellt dieses System einen möglichen Kandidaten für Anwendungen als molekularer Schalter oder als Speichereinheit dar. In der vorliegenden Studie werden lokalisierte Schaltvorgänge einzelner Moleküle zusammen mit der Möglichkeit einer kontrollierten molekularen Nanostrukturierung gezeigt. Lutetium (III) bisphthalocyanin wurde ausgewählt als Vertreter einer neuen Gruppe von MePc, die eine Sandwichstruktur ausbilden, bei der zwei π-konjugierte Phthalocyaninliganden über ein Seltenerd-Ion miteinander verbunden sind. Die Untersuchung dieses Systems liefert wichtige neue Erkenntnisse, wie zum Beispiel ein umfassendes Verständnis der Vorgänge bei der Selbstassemblierung innerhalb der ersten und zweiten organischen Monolage. Zudem wurde bei der Charakterisierung des Tunneltransports durch einzelne Moleküle mittels STS ein negativer differentieller Widerstand (NDR) gefunden, der von der Anzahl molekularer Lagen abhängt.

Although scalingof CMOS technology has been predicted to continue for another decade, novel technological solutions are required to overcome the fundamental limitations of the decananometer MOS transistors. Single Electron Transistor (SET) has attracted attention mainly because of its unique Coulomb blockade oscillations characteristics, ultra low power dissipation and nanoscale feature size. Despite the high potential, due to some intrinsic limitations (e.g., very low current drive) it will be very difficult for SET to compete head-to-head with CMOS’s large-scale infrastructure, proven design methodologies, and economic predictability. Nevertheless, the characteristics of SET and MOS transistors are quite complementary. SET advocates low-power consumption and new functionality (related to the Coulomb blockade oscillations), while CMOS has advantages like high-speed driving and voltage gain that can compensate the intrinsic drawbacks of SET. Therefore, although a complete replacement of CMOS by single-electronics is unlikely in the near future, it is also true that combining SET and CMOS one can bring out new functionalities, which are unmirrored in pure CMOS technology. As the hybridization of CMOSand SET is gaining popularity, silicon SETs are appearing to be more promising than metallic SETs for their possible integration with CMOS. SETs are normally studied on the basis of the classical Orthodox Theory, where quantization of energy states in the island is completely ignored. Though this assumption greatly simplifies the physics involved, it is valid only when the SET is made of metallic island. As one cannot neglect the quantization of energy states in a semi conductive island, it is extremely important to study the effects of energy quantization on hybrid CMOSSET integrated circuits. The main objectives of this thesis are: (1) understand energy quantization effects on SET by numerical simulations; (2) develop simple analytical models that can capture the energy quantization effects; (3)analyze the effects of energy quantization on SET logic inverter, and finally; (4)developa CAD framework for CMOS-SETco-simulation and to study the effects of energy quantization on hybrid circuits using that framework. In this work the widely accepted SIMON Monte Carlo (MC) simulator for single electron devices and circuits is used to study the effects of energy quantization. So far SIMON has been used to study SETs having metallic island. In this work, for the first time, we have shown how one can use SIMON to analyze SET island properties having discrete energy states.It is shown that energy quantization mainly changes the Coulomb Blockade region and drain current of SET devices and thus affects the noise margin, power dissipation, and the propagation delay of SET logic inverter. Anew model for the noise margin of SET inverter is proposed, which includes the energy quantization term. Using the noise margin as a metric, the robustness of SET inverter is studied against the effects of energy quantization. An analytical expression is developed, which explicitly defines the maximum energy quantization (termedas “Quantization Threshold”)that an SET inverter logic circuit can withstand before its noise margin upper bound crosses the acceptable tolerance limit. It is found that SET inverter designed with CT : CG =0.366 (where CT and CG are tunnel junction and gate capacitances respectively) offers maximum robustness against energy quantization. Then the effects of energy quantization are studied for Current biased SET (CBS), which is an integral part of almost all hybrid CMOS-SET circuits. It is demonstrated that energy quantization has no impact on the gain of the CBS characteristics though it changes the output voltage levels and oscillation periodicity. The effects of energy quantization are further studied for two circuits: Negative Differential Resistance (NDR) and Neurone Cell, which use CBS. A new model for the conductance of NDR characteristics is also formulated that includes the energy quantization term. A novel CAD framework is then developed for CMOS-SET co-simulation, whichuses MCsimulator for SET devices alongwithconventional SPICE. Using this framework, the effects of energy quantization are studied for some hybrid circuits, namely, SETMOS, multiband voltage filter, and multiple valued logic circuits. It is found that energy quantization degrades the performance of hybrid circuit, which could be compensated by properly tuning the bias current of SET devices. Though this study is primarily done by exhaustive MC simulation, effort has also been put to develop first order compact model for SET that includes energy quantization effects. Finally it has been demonstrated that the SET behavior under energy quantization can be predicted byslightlymodifyingthe existing SETcompact models that are valid for metallic devices having continuous energy states.

Trotz einer Vielzahl von Forschungsarbeiten auf dem Gebiet der Phthalocyanin-basierten organischen Verbindungen fehlt nach wie vor ein umfassendes Verständnis des Zusammenspiels zwischen strukturellen und elektronischen Eigenschaften, die sich bei der Abscheidung dieser Stoffe auf anorganische kristallinen Substraten ausbilden. Vor diesem Hintergrund wurden für die vorliegende Arbeit vier metallbasierte Phthalocyanine ausgewählt und mittels organischer Molekularstrahl-Abscheidung (OMBD) im Ultrahochvakuum (UHV) auf Ag (111) Einkristalle adsorbiert. Für die anschließende eingehende Untersuchung dieser Proben wurden insbesondere Rastertunnelmikroskopie (STM) und -spektroskopie (STS) angewandt. Ergänzend kamen Ultraviolett- und Röntgen-Photoelektronenspektroskopie (UPS und XPS) zum Einsatz, wodurch komplementäre Informationen gewonnen wurden. Die aus diesen Untersuchungen resultierenden Ergebnisse liefern einen wesentlichen Beitrag zum oben genannten Forschungsgebiet. Die in dieser Arbeit untersuchten Metall-Phthalocyanine (MePc) wurden so ausgewählt, dass eine möglichst große Vielfalt an geometrischen und elektronischen Eigenschaften abgedeckt wurde. Planare cobaltbasierte Phthalocyanin-Moleküle wurden in zwei Konfigurationen untersucht: einerseits das protonierte CoPc, das sich als organischer p-Halbleiter verhält, und andererseits das vollständig fluorinierte F16CoPc, das n-Halbleitereigenschaften besitzt. Bei beiden Systemen zeigte sich an der Position des Cobaltions eine Kopplung zwischen den Molkülorbitalen des Adsorbats und den Elektronenzuständen des Substrates. Das nichtplanare Zinn-Phthalocyanin ist von besonderem Interesse aufgrund seiner beiden möglichen Adsorptionskonformationen up und down, bei denen sich das Sn-Ion oberhalb beziehungsweise unterhalb des Phthalocyaninliganden befindet. Damit stellt dieses System einen möglichen Kandidaten für Anwendungen als molekularer Schalter oder als Speichereinheit dar. In der vorliegenden Studie werden lokalisierte Schaltvorgänge einzelner Moleküle zusammen mit der Möglichkeit einer kontrollierten molekularen Nanostrukturierung gezeigt. Lutetium (III) bisphthalocyanin wurde ausgewählt als Vertreter einer neuen Gruppe von MePc, die eine Sandwichstruktur ausbilden, bei der zwei π-konjugierte Phthalocyaninliganden über ein Seltenerd-Ion miteinander verbunden sind. Die Untersuchung dieses Systems liefert wichtige neue Erkenntnisse, wie zum Beispiel ein umfassendes Verständnis der Vorgänge bei der Selbstassemblierung innerhalb der ersten und zweiten organischen Monolage. Zudem wurde bei der Charakterisierung des Tunneltransports durch einzelne Moleküle mittels STS ein negativer differentieller Widerstand (NDR) gefunden, der von der Anzahl molekularer Lagen abhängt.