Thin‐Film Transistors for Large Area Opto/Electronics

The present work addresses several issues in the field of organic and transparent electronics. One of them is the prevailing high power consumption in state-of-the-art organic field-effect transistors (OFETs). A possible solution could be the implementation of complementary, rather than unipolar logic, but this development is currently inhibited by a distinct lack of high performance electron transporting (n-channel) OFETs. Here, the issue is addressed by investigating a series of solution processable n-channel fullerene molecules in combination with optimized transistor architectures. Furthermore, the trend towards complementary circuit design could be facilitated by employing ambipolar organic semiconductors, such as squaraine molecules or polymer/fullerene blends. These materials can fill the role of p- or n-channel semiconductors and enable the facile implementation of power saving complementary-like logic, eliminating the cost-intensive patterned deposition of discrete p-and n-channel transistors. Alternatively, a patterning method for organic materials adapted from standard photolithography is discussed. Furthermore, ambipolar FETs are found to be capable of light sensing at wavelength of 400-1000 nm. Hence their use in low-cost, organic based optical sensor arrays can be envisioned. Another strategy to reduce the power consumption and operating voltages of OFETs is the use of ultra-thin, self-assembled molecular gate dielectrics, such as alkyl-phosphonic acid molecules. Based on this approach solution processed n- and p-channel OFETs and a complementary organic inverter circuit are demonstrated, which operate at less than 2 Volts. Finally, transparent oxide semiconductors are investigated for use in thin-film transistors. Titanium dioxide (TiO2) and zinc oxide (ZnO) films are deposited by means of a low-cost large area compatible spray pyrolysis technique. ZnO transistors exhibit high electron mobility of the order of 10 cm2/Vs and stable operation in air at less than 2 Volts. These results are considered significant steps towards the development of organic and transparent large-area optoelectronics

Device engineering of organic field-effect transistors toward complementary circuits

Organic complementary circuits are attracting significant attention due to their high power efficiency and operation robustness, driven by the demands for low-cost, large-area and flexible devices. Previous demonstrations of organic complementary circuits often show high operating voltage, small noise margins, low dc gain, and electrical instability such as hysteresis and threshold voltage shifts. There are two obstacles to developing organic complementary circuits: the lack of high-performance n-channel OFET devices, and the processing difficulty of integrating both n- and p-channel organic field-effect transistors (OFETs) on the same substrate. The operating characteristics of OFETs are often governed by the boundary conditions imposed by the device architecture, such as interfaces and contacts instead of the properties of the semiconductor material. Therefore, the performance of OFETs is often limited if either of the essential interfaces or contacts next to the semiconductor and the channel are not optimized. This dissertation presents research work performed on OFETs and OFET-based complementary inverters in an attempt to address some of these knowledge issues. The objective is to develop high-performance OFETs, with a focus on n-channel OFETs through interface engineering both at the interface between the organic semiconductor and the source/drain electrodes, and at the interface between the organic semiconductor and gate dielectric. Through interface engineering, both p- and n-channel high-performance low-voltage OFETs are realized with high mobilities, low threshold voltages, low subthreshold slopes, and high on/off current ratios. Optimization at the gate dielectric/semiconductor also gives OFET devices excellent reproducibility and good electrical stability under multiple test cycles and continuous electrical stress. Finally, with the interfaces and contacts optimized for both p- and n-channel charge transport, the integration of n- and p-channel OFETs with comparable performance are demonstrated in complementary inverters. The research achieves inverters with a high-gain, a low operation voltage, good electrical stability (absence of hysteresis), and a high switching-speed. A preliminary study of the encapsulation of OFETs and inverters with an additional protective layer is also presented to validate the practicality of organic devices containing air-sensitive n-channel transport.Ph.D.Committee Chair: Kippelen, Bernard; Committee Member: Brand, Oliver; Committee Member: Graham, Samuel; Committee Member: Rohatgi, Ajeet; Committee Member: Shen, Shyh-Chian

Ultra conformable and multimodal tactile sensors based on organic field-effect transistors

Cognitive psychology is the branch of psychology related to all the processes by which sensory input is transformed, processed and used. Academic and industrial research has always invested time and resources to develop devices capable to simulate the behavior of the organs where the perceptions are located. In recent years, in fact, there have been numerous discoveries related to new materials, and new devices, capable of reproducing, in a reliable manner, the sensory behavior of humans. Particular interest in scientific research has been aimed at understanding and reproducing of man's tactile sensations. It is known that, through the receptors of the skin, it is possible to detect sensations such as pain, changes in pressure and/or temperature. The development of tactile sensor technology had a significant increase in the last years of 1970s, thanks to the important surveys of Stojiljkovic, Harmon and Lumelsky who presented the firsts prototype of sensors for artificial skin applications, and summarized the main characteristics and requirements of tactile sensors. Recently, organic electronics has been deeply investigated as technology for the fabrication of tactile sensors using biocompatible materials, which can be deposited and processed on ultra flexible and ultra conformable substrates. In general, the most attractive property of these materials is mainly related to their high mechanical flexibility, which is mandatory for artificial skin applications. The main object of this PhD research activity was the development and optimization of an innovative technology for the realization of physical sensors able to detect pressure and temperature variations, which can be applied in the field of biomedical engineering and biorobotics. By exploiting the particular characteristics of the employed materials, such as mechanical flexibility, the proposed sensors are very suitable to be integrated with flexible structures (for example plastics) as a pressure and temperature sensor, and therefore, ideal for the realization of an artificial skin like. In Chapter 1, the basics of humans somatosensory system will be introduced: after a brief description of tactile thermoreceptors, mechanoreceptors and nociceptors, a definition of electronic skin and its characteristics will be provided. In Chapter 2, a wide analysis of the state of the art will be reported. Several and different examples of tactile sensor (in inorganic and organic technology) will be presented, underlining advantages and disadvantages for each approach. In Chapter 3, the firsts experimental results, obtained in the first part of my PhD program, will be presented. All the steps of the fabrication process of the devices will be described, as well as the measurement setup used for the electrical characterization of the sensors. In Chapter 4, the sensor structure optimization will be presented. It will be demonstrated how the presented devices are able to sense simultaneously thermal and mechanical stimuli. Moreover, it will be demonstrated that, thanks to an alternative and innovative fabrication process, the sensors can be transferred directly on skin, thus proving the suitability of the proposed sensor architecture for tactile applications

Organic Electronic Devices - Fundamentals, Applications, and Novel Concepts

This work addresses two substantial problems of organic electronic devices: the controllability and adjustability of performance, and the integration using scalable, high resolution patterning techniques for planar thin-film transistors and novel vertical transistor devices. Both problems are of particular importance for the success of transparent and flexible organic electronics in the future. To begin with, the static behavior in molecular doped organic pin-diodes is investigated. This allows to deduce important diode parameters such as the depletion capacitance, the number of active dopant states, and the breakdown field. Applying this knowledge, organic pin-diodes are designed for ultra-high-frequency applications and a cut-off-frequency of up to 1GHz can be achieved using optimized parameters for device geometry, layer thickness, and dopant concentration. The second part of this work is devoted to organic thin-film transistors, high resolution patterning techniques, as well as novel vertical transistor concepts. In particular, fluorine based photo-lithography, a high resolution patterning technique compatible to organic semiconductors, is introduced fielding the integration of organic thin-film transistors under ambient conditions. However, as it will be shown, horizontal organic thin-film transistors are substantially limited in their performance by charge carrier injection. Hence, down-scaling is inappropriate to enlarge the transconductance of such transistors. To overcome this drawback, a novel vertical thin-film transistor concept with a vertical channel length of ∼50nm is realized using fluorine based photo-lithography. These vertical devices can surpass the performance of planar transistors and hence are prospective candidates for future integration in complex electronic circuits

Fabrication, characterization, and modeling of organic capacitors, Schottky diodes, and field effect transistors

The objectives of this project are to fabricate, characterize, and model organic microelectronic devices by traditional lithography techniques and Technology Computer Aided Design (TCAD). Organic microelectronics is becoming a promising field due to its number of advantages in low-cost fabrication for large area substrates. There have been growing studies in organic electronics and optoelectronics. In this project, several organic microelectronic devices are studied with the aid of experimentation and numerical modeling. Organic metal-insulator-metal (MIM) and metal-insulator-semiconductor (MIS) capacitors consisting of insulating polymer poly(4-vinylphenol) (PVP) have been fabricated by spin-coating, photo lithography, and reactive ion etching techniques. Based on the fabricated devices, the dielectric constant of the (PVP) is calculated to be about 5.6–5.94. The MIS capacitor consisting of organic semiconductor pentacene has been investigated. The hole concentration of pentacene is determined to be around 8 × 1016 cm −3. Schottky diodes consisting of aluminum and a layer of p-type semiconducting polymer poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) have been fabricated. Based on the current-voltage (I-V) and capacitance-voltage (C-V) measurements, the temperature dependence of hole mobility in MEH-PPV has been extracted by the space-charge limited conduction (SCLC) model, from 300 to 400 K. Moreover, the value of the effective hole density for MEH-PPV has been determined to be 2.24 × 1017 cm−3. Numerical simulations have been carried out to identify the parameters which affect the performance of devices significantly. Organic n- and p-channel field-effect transistors (FETs) have been designed and fabricated. By using Naphthalene-tetracarboxylic-dianhydride (NTCDA) as an organic semiconductor, n-channel FETs have been fabricated and characterized. At room temperature, the device characteristics have displayed electron mobility of 0.016 cm2/Vs, threshold voltage of −32 V, and on/off ratio of 2.25 × 102. Pentacene, an organic semiconductor offering high device performance, has been employed to fabricate the p-channel FETs. At room temperature, the device characteristics have displayed hole mobility of 0.26 cm2/Vs, threshold voltage of −3.5 V, subthreshold slope of 2.5 V/decade, and on/off ratio of 105. The temperature and field dependence of mobility has been studied based on the experimental results. Based on numerical simulations, the influence of bulk traps has also been identified, and the field-dependent mobility model has been used to obtain more accurate simulation results. Furthermore, electrostatically assembled monolayer (poly(dimethyldiallylammonium chloride) (PDDA)) is introduced at the organic/insulator interface to improve the performance of the FETs. The efforts carried out in this work appear to be the first reported attempt at the investigation of the temperature dependence of mobility for the given organic devices, and the surface modification of organic FETs by electrostatically assembled monolayer

Low-voltage organic transistors with high transconductance

This thesis presents the development of low-voltage organic thin-film transistors with high transconductance. This was achieved by employing ultra-thin bi-layer gate dielectric consisting of aluminium oxide (AlOx) and a self-assembled monolayer of octadecyl phosphonic acid (C18PA) and by increasing the channel width of the transistors through the implementation of the multi-finger source/drain contacts. The transistors based on dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) exhibited low turn-on voltage and a.c. transconductance around 30 to 60 µS. Transistor amplifiers based on such transistors exhibited voltage gain approaching 10 V/V and a gain of about 2 V/V when the supply voltage was limited to 5 V. Next, a series of [n]phenacenes ([n] = 5, 6, or 7) was used for the first time in combination with the thin AlOx/C18PA dielectric bi-layer. Regardless of the substrate and the source-drain contact geometry, the field-effect mobility of such transistors was found to increase with increasing length of the conjugated [n]phenacene core, leading to the best performance for [7]phenacene with the largest average field-effect mobility of 0.27 cm2/V⋅s for transistors on glass and 0.092 cm2/V⋅s for transistors on flexible PEN. The highest transconductance of 12.2 µS was achieved for [7]phenacene transistors on glass, which was lower than that achieved for DNTT transistors. In addition, nearly hysteresis-free behaviour, improved charge carrier injection/extraction properties, and reduced threshold voltage were achieved. Finally, a semi-empirical transistor model was developed in Matlab. The model was validated using d.c. and a.c. measurements obtained on DNTT transistors with high transconductance. Four fitting parameters were extracted by optimising a fitting function using genetic algorithm. The model reproduces the d.c. transistor measurements with high accuracy. The error between the measured and simulated peak-to-peak a.c. transconductance values ranged from 1.7% to 11.6%.This thesis presents the development of low-voltage organic thin-film transistors with high transconductance. This was achieved by employing ultra-thin bi-layer gate dielectric consisting of aluminium oxide (AlOx) and a self-assembled monolayer of octadecyl phosphonic acid (C18PA) and by increasing the channel width of the transistors through the implementation of the multi-finger source/drain contacts. The transistors based on dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) exhibited low turn-on voltage and a.c. transconductance around 30 to 60 µS. Transistor amplifiers based on such transistors exhibited voltage gain approaching 10 V/V and a gain of about 2 V/V when the supply voltage was limited to 5 V. Next, a series of [n]phenacenes ([n] = 5, 6, or 7) was used for the first time in combination with the thin AlOx/C18PA dielectric bi-layer. Regardless of the substrate and the source-drain contact geometry, the field-effect mobility of such transistors was found to increase with increasing length of the conjugated [n]phenacene core, leading to the best performance for [7]phenacene with the largest average field-effect mobility of 0.27 cm2/V⋅s for transistors on glass and 0.092 cm2/V⋅s for transistors on flexible PEN. The highest transconductance of 12.2 µS was achieved for [7]phenacene transistors on glass, which was lower than that achieved for DNTT transistors. In addition, nearly hysteresis-free behaviour, improved charge carrier injection/extraction properties, and reduced threshold voltage were achieved. Finally, a semi-empirical transistor model was developed in Matlab. The model was validated using d.c. and a.c. measurements obtained on DNTT transistors with high transconductance. Four fitting parameters were extracted by optimising a fitting function using genetic algorithm. The model reproduces the d.c. transistor measurements with high accuracy. The error between the measured and simulated peak-to-peak a.c. transconductance values ranged from 1.7% to 11.6%

Voltage Modulated Infrared Reflectance Study of Soluble Organic Semiconductors in Thin Film Transistors

Soluble organic semiconductors have attracted interest due to their potential in making flexible and cheap electronics. Though their use is being implemented in electronics today, the conduction mechanism is still under investigation. In order to study the charge transport, this study examines the position, voltage, and frequency dependence of charge induced changes in far infrared absorption in soluble organic semiconductors in thin-film transistor structures. Measurements are compared to a simple model of a one-dimensional conductor which gives insight into the charge distribution and timing in devices. Main results of the study are dynamic measurements of charge taken by varying the frequency of the applied gate voltage while observing signal at one position within the transistor; mobility values obtained from a comparison to the one-dimensional model compare well with standard current-voltage measurements. Two small molecule soluble organic semiconductors were studied: 6,13 bis(triisopropylsilylethynyl)-pentacene and fluorinated 5,11 bis(triethylsilylethynyl) anthradithiophene

Design, Characterization And Analysis Of Electrostatic Discharge (esd) Protection Solutions In Emerging And Modern Technologies

Electrostatic Discharge (ESD) is a significant hazard to electronic components and systems. Based on a specific processing technology, a given circuit application requires a customized ESD consideration that includes the devices’ operating voltage, leakage current, breakdown constraints, and footprint. As new technology nodes mature every 3-5 years, design of effective ESD protection solutions has become more and more challenging due to the narrowed design window, elevated electric field and current density, as well as new failure mechanisms that are not well understood. The endeavor of this research is to develop novel, effective and robust ESD protection solutions for both emerging technologies and modern complementary metal–oxide–semiconductor (CMOS) technologies. The Si nanowire field-effect transistors are projected by the International Technology Roadmap for Semiconductors as promising next-generation CMOS devices due to their superior DC and RF performances, as well as ease of fabrication in existing Silicon processing. Aiming at proposing ESD protection solutions for nanowire based circuits, the dimension parameters, fabrication process, and layout dependency of such devices under Human Body Mode (HBM) ESD stresses are studied experimentally in company with failure analysis revealing the failure mechanism induced by ESD. The findings, including design methodologies, failure mechanism, and technology comparisons should provide practical knowhow of the development of ESD protection schemes for the nanowire based integrated circuits. Organic thin-film transistors (OTFTs) are the basic elements for the emerging flexible, printable, large-area, and low-cost organic electronic circuits. Although there are plentiful studies focusing on the DC stress induced reliability degradation, the operation mechanism of OTFTs iv subject to ESD is not yet available in the literature and are urgently needed before the organic technology can be pushed into consumer market. In this work, the ESD operation mechanism of OTFT depending on gate biasing condition and dimension parameters are investigated by extensive characterization and thorough evaluation. The device degradation evolution and failure mechanism under ESD are also investigated by specially designed experiments. In addition to the exploration of ESD protection solutions in emerging technologies, efforts have also been placed in the design and analysis of a major ESD protection device, diodetriggered-silicon-controlled-rectifier (DTSCR), in modern CMOS technology (90nm bulk). On the one hand, a new type DTSCR having bi-directional conduction capability, optimized design window, high HBM robustness and low parasitic capacitance are developed utilizing the combination of a bi-directional silicon-controlled-rectifier and bi-directional diode strings. On the other hand, the HBM and Charged Device Mode (CDM) ESD robustness of DTSCRs using four typical layout topologies are compared and analyzed in terms of trigger voltage, holding voltage, failure current density, turn-on time, and overshoot voltage. The advantages and drawbacks of each layout are summarized and those offering the best overall performance are suggested at the en

On the Characterization and Manipulation of Interfaces in Organic and Hybrid Electronic Devices

Organic electronics comprises a field of study at the intersection of chemistry, physics, electrical engineering, and materials science focused on the development of electronic devices in which the active charge transporting materials are composed of organic conjugated molecules. This field has grown out of an interest in harnessing many attributes of organic materials not readily available to inorganic semiconductors, including: low synthesis temperatures for organic compounds; a nearly infinite combination of chemical moieties with similar conjugated character; and ease of fabricating thin films of organic compounds through both vacuum and solution processes. These properties make the fabrication of low-cost, highly-customizable electronics commercially viable, despite their inferior carrier transport to crystalline inorganic semiconductors. This key hurdle—understanding charge transport in organic molecules and thin films made from them—has become a primary research objective in the field. Understanding charge transport in organic electronic devices spans analysis across various size scales, each contributing to the observed behavior of an electronic device: * The chemical structure of the constituent conjugated molecules (Ås) * The arrangement of these molecules into ordered and disordered regions within a thin film (10s of Ås) * The configuration of the thin film within the working device (100s of Ås) At each of these scales, the concept of an interface acquires new meaning, scaling from van der Waals forces between molecules, to grain boundaries in polycrystalline materials, and incrementally to device-scale junctions between dissimilar materials. Because each of these interfaces can promote or inhibit carrier transport within an electronic device, a complete understanding of carrier transport in organic semiconductors (OSCs) demands comprehensive characterization of interfaces at each of these scales. The subject of this thesis is a critical examination of the insulator-OSC interface in the context of several electronic device architectures. The properties of this interface are of paramount importance in organic field-effect transistors (OFETs), where the low intrinsic carrier mobilities of OSCs renders them highly susceptible to even the most marginal deviations from an ideal interface. As a result, transistor switching characteristics quickly carry through to circuit-level reliability and power consumption. This dissertation aims to demonstrate the use of existing materials in new ways for exercising nanoscale control over this interface, with an eye towards understanding their individual and collective charge transport behavior. Chapter 1 reviews the state of the art in control over the threshold voltage of OFETs, of which two methods—dipolar self-assembled monolayers (SAMs) and electrostatic poling—are considered in the subsequent chapters. Chapter 2 details the use of SAMs of dipolar alkylsilanes as a surface treatment for tuning VT, reducing leakage currents, and improving switching efficiency. Increases in field-effect transconductance in SAM-treated OFETs are shown to be consistent with the presence of additional surface states. Chapter 3 details an approach to decouple the relative contributions of the insulator/SAM and SAM/OSC interfaces from the capacitive responses of the OFET multilayer, and is compared to recent theoretical predictions of increased energetic disorder in SAM-treated OSC layers. Increased mobility of equilibrium carriers as measured with charge extraction are compared to OFET measurements and are shown to further reinforce the notion that larger molecular dipoles contribute to enhanced carrier transport through changes in the energetic disorder at the insulator/OSC interface. In Chapter 4 electrostatic poling, or gate stressing, of lateral OFETs is explored. A Poisson’s equation model is applied to surface potential images of stressed lateral OFETs and shown to accurately predict the observed threshold voltage shift. Lastly, Chapter 5 presents future directions for the study of SAM-treated interfaces using charge extraction, with a focus on the use of SAMs as remedial layers for marginal quality OSCs. In addition, the potential of surface potential-derived charge densities for sensing applications is discussed

High-throughput large-area plastic nanoelectronics

Large-area electronics (LAE) manufacturing has been a key focus of both academic and industrial research, especially within the last decade. The growing interest is born out of the possibility of adding attractive properties (flexibility, light weight or minimal thickness) at low cost to well-established technologies, such as photovoltaics, displays, sensors or enabling the realisation of emerging technologies such as wearable devices and the Internet of Things. As such there has been great progress in the development of materials specifically designed to be employed in solution processed (plastic) electronics, including organic, transparent metal oxide and nanoscale semiconductors, as well as progress in the deposition methods of these materials using low-cost high-throughput printing techniques, such as gravure printing, inkjet printing, and roll-to-roll vacuum deposition. Meanwhile, industry innovation driven by Moore’s law has pushed conventional silicon-based electronic components to the nanoscale. The processes developed for LAE must strive to reach these dimensions. Given that the complex and expensive patterning techniques employed by the semiconductor industry so far are not compatible with LAE, there is clearly a need to develop large-area high throughput nanofabrication techniques. This thesis presents progress in adhesion lithography (a-Lith), a nanogap electrode fabrication process that can be applied over large areas on arbitrary substrates. A-Lith is a self-alignment process based on the alteration of surface energies of a starting metal electrode which allows the removal of any overlap of a secondary metal electrode. Importantly, it is an inexpensive, scalable and high throughput technique, and, especially if combined with low temperature deposition of the active material, it is fundamentally compatible with large-area fabrication of nanoscale electronic devices on flexible (plastic) substrates. Herein, I present routes towards process optimisation with a focus on gap size reduction and yield maximisation. Asymmetric gaps with sizes below 10 nm and yields of > 90 % for hundreds of electrode pairs generated on a single substrate are demonstrated. These large width electrode nanogaps represent the highest aspect ratio nanogaps (up to 108) fabricated to date. As a next step, arrays of Schottky nanodiodes are fabricated by deposition of a suitable semiconductor from solution into the nanogap structures. Of principal interest is the wide bandgap transparent semiconductor, zinc oxide (ZnO). Lateral ZnO Schottky diodes show outstanding characteristics, with on-off ratios of up to 106 and forward current values up to 10 mA for obtained upon combining a-Lith with low-temperature solution processing. These unique devices are further investigated for application in rectifier circuits, and in particular for potential use in radio frequency identification (RFID) tag technology. The ZnO diodes are found to surpass the 13.56 MHz frequency bernchmark used in commercial applications and approach the ultra-high frequency (UHF) band (hundreds of megahertz), outperforming current state of the art printed diodes. Solution processed fullerene (C60) is also shown to approach the UHF band in this co-planar device configuration, highlighting the viability of a-Lith for enabling large-area flexible radio frequency nanoelectronics. Finally, resistive switching memory device arrays based on a-Lith patterned nanogap aluminium symmetric electrodes are demonstrated for the first time. These devices are based either on empty aluminium nanogap electrodes, or with the gap filled with a solution-processed semiconductor, the latter being ZnO, the semiconducting polymer poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) or carbon nanotube/polyfluorene blends. The switching mechanism, retention time and switching speed are investigated and compared with published data. The fabrication of arrays of these devices illustrates the potential of a-Lith as a simple technique for the realisation of large-area high-density memory applications.Open Acces