In situ real-time investigation of Organic Ultra-Thin-Film transistors: growth, electrical properties and biosensing applications

Organic electronics has grown enormously during the last decades driven by the encouraging results and the potentiality of these materials for allowing innovative applications, such as flexible-large-area displays, low-cost printable circuits, plastic solar cells and lab-on-a-chip devices. Moreover, their possible field of applications reaches from medicine, biotechnology, process control and environmental monitoring to defense and security requirements. However, a large number of questions regarding the mechanism of device operation remain unanswered. Along the most significant is the charge carrier transport in organic semiconductors, which is not yet well understood. Other example is the correlation between the morphology and the electrical response. Even if it is recognized that growth mode plays a crucial role into the performance of devices, it has not been exhaustively investigated. The main goal of this thesis was the finding of a correlation between growth modes, electrical properties and morphology in organic thin-film transistors (OTFTs). In order to study the thickness dependence of electrical performance in organic ultra-thin-film transistors, we have designed and developed a home-built experimental setup for performing real-time electrical monitoring and post-growth in situ electrical characterization techniques. We have grown pentacene TFTs under high vacuum conditions, varying systematically the deposition rate at a fixed room temperature. The drain source current IDS and the gate source current IGS were monitored in real-time; while a complete post-growth in situ electrical characterization was carried out. At the end, an ex situ morphological investigation was performed by using the atomic force microscope (AFM). In this work, we present the correlation for pentacene TFTs between growth conditions, Debye length and morphology (through the correlation length parameter). We have demonstrated that there is a layered charge carriers distribution, which is strongly dependent of the growth mode (i.e. rate deposition for a fixed temperature), leading to a variation of the conduction channel from 2 to 7 monolayers (MLs). We conciliate earlier reported results that were apparently contradictory. Our results made evident the necessity of reconsidering the concept of Debye length in a layered low-dimensional device. Additionally, we introduce by the first time a breakthrough technique. This technique makes evident the percolation of the first MLs on pentacene TFTs by monitoring the IGS in real-time, correlating morphological phenomena with the device electrical response. The present thesis is organized in the following five chapters. Chapter 1 makes an introduction to the organic electronics, illustrating the operation principle of TFTs. Chapter 2 presents the organic growth from theoretical and experimental points of view. The second part of this chapter presents the electrical characterization of OTFTs and the typical performance of pentacene devices is shown. In addition, we introduce a correcting technique for the reconstruction of measurements hampered by leakage current. In chapter 3, we describe in details the design and operation of our innovative home-built experimental setup for performing real-time and in situ electrical measurements. Some preliminary results and the breakthrough technique for correlating morphological and electrical changes are presented. Chapter 4 meets the most important results obtained in real-time and in situ conditions, which correlate growth conditions, electrical properties and morphology of pentacene TFTs. In chapter 5 we describe applicative experiments where the electrical performance of pentacene TFTs has been investigated in ambient conditions, in contact to water or aqueous solutions and, finally, in the detection of DNA concentration as label-free sensor, within the biosensing framework.

In-situ and real time scanning probe microscopy of organic ultra thin films

In recent decades, Organic Thin Film Transistors (OTFTs) have attracted lots of interest due to their low cost, large area and flexible properties which have brought them to be considered the building blocks of the future organic electronics. Experimentally, devices based on the same organic material deposited in different ways, i.e. by varying the deposition rate of the molecules, show different electrical performance. As predicted theoretically, this is due to the speed and rate by which charge carriers can be transported by hopping in organic thin films, transport that depends on the molecular arrangement of the molecules. This strongly suggests a correlation between the morphology of the organic semiconductor and the performance of the OTFT and hence motivated us to carry out an in-situ real time SPM study of organic semiconductor growth as an almost unprecedent experiment with the aim to fully describe the morphological evolution of the ultra-thin film and find the relevant morphological parameters affecting the OTFT electrical response. For the case of 6T on silicon oxide, we have shown that the growth mechanism is 2D+3D, with a roughening transition at the third layer and a rapid roughening. Relevant morphological parameters have been extracted by the AFM images. We also developed an original mathematical model to estimate theoretically and more accurately than before, the capacitance of an EFM tip in front of a metallic substrate. Finally, we obtained Ultra High Vacuum (UHV) AFM images of 6T at lying molecules layer both on silicon oxide and on top of 6T islands. Moreover, we performed ex-situ AFM imaging on a bilayer film composed of pentacene (a p-type semiconductor) and C60 (an n-type semiconductor).

Study of silicon-on-insulator multiple-gate MOS structures including band-gap engineering and self heating effects

The progresses of electron devices integration have proceeded for more than 40 years following the well–known Moore’s law, which states that the transistors density on chip doubles every 24 months. This trend has been possible due to the downsizing of the MOSFET dimensions (scaling); however, new issues and new challenges are arising, and the conventional ”bulk” architecture is becoming inadequate in order to face them. In order to overcome the limitations related to conventional structures, the researchers community is preparing different solutions, that need to be assessed. Possible solutions currently under scrutiny are represented by: • devices incorporating materials with properties different from those of silicon, for the channel and the source/drain regions; • new architectures as Silicon–On–Insulator (SOI) transistors: the body thickness of Ultra-Thin-Body SOI devices is a new design parameter, and it permits to keep under control Short–Channel–Effects without adopting high doping level in the channel. Among the solutions proposed in order to overcome the difficulties related to scaling, we can highlight heterojunctions at the channel edge, obtained by adopting for the source/drain regions materials with band–gap different from that of the channel material. This solution allows to increase the injection velocity of the particles travelling from the source into the channel, and therefore increase the performance of the transistor in terms of provided drain current. The first part of this thesis work addresses the use of heterojunctions in SOI transistors: chapter 3 outlines the basics of the heterojunctions theory and the adoption of such approach in older technologies as the heterojunction–bipolar–transistors; moreover the modifications introduced in the Monte Carlo code in order to simulate conduction band discontinuities are described, and the simulations performed on unidimensional simplified structures in order to validate them as well. Chapter 4 presents the results obtained from the Monte Carlo simulations performed on double–gate SOI transistors featuring conduction band offsets between the source and drain regions and the channel. In particular, attention has been focused on the drain current and to internal quantities as inversion charge, potential energy and carrier velocities. Both graded and abrupt discontinuities have been considered. The scaling of devices dimensions and the adoption of innovative architectures have consequences on the power dissipation as well. In SOI technologies the channel is thermally insulated from the underlying substrate by a SiO2 buried–oxide layer; this SiO2 layer features a thermal conductivity that is two orders of magnitude lower than the silicon one, and it impedes the dissipation of the heat generated in the active region. Moreover, the thermal conductivity of thin semiconductor films is much lower than that of silicon bulk, due to phonon confinement and boundary scattering. All these aspects cause severe self–heating effects, that detrimentally impact the carrier mobility and therefore the saturation drive current for high–performance transistors; as a consequence, thermal device design is becoming a fundamental part of integrated circuit engineering. The second part of this thesis discusses the problem of self–heating in SOI transistors. Chapter 5 describes the causes of heat generation and dissipation in SOI devices, and it provides a brief overview on the methods that have been proposed in order to model these phenomena. In order to understand how this problem impacts the performance of different SOI architectures, three–dimensional electro–thermal simulations have been applied to the analysis of SHE in planar single and double–gate SOI transistors as well as FinFET, featuring the same isothermal electrical characteristics. In chapter 6 the same simulation approach is extensively employed to study the impact of SHE on the performance of a FinFET representative of the high–performance transistor of the 45 nm technology node. Its effects on the ON–current, the maximum temperatures reached inside the device and the thermal resistance associated to the device itself, as well as the dependence of SHE on the main geometrical parameters have been analyzed. Furthermore, the consequences on self–heating of technological solutions such as raised S/D extensions regions or reduction of fin height are explored as well. Finally, conclusions are drawn in chapter 7.

Liquid crystal polymers: macromolecular design for enhanced performances

During this work, done mainly in the laboratories of the department of Industrial Chemistry and Materials of the University of Bologna but also in the laboratories of the Carnegie Mellon University in collaboration with prof. K. Matyjaszewski and at the university of Zaragoza in collaboration with prof. J. Barberá, was focused mainly on the synthesis and characterization of new functional polymeric materials. In the past years our group gained a deep knowledge about the photomodulation of azobenzene containing polymers. The aim of this thesis is to push forward the performances of these materials by the synthesis of well defined materials, in which, by a precise control over the macromolecular structures, better or even new functionality can be delivered to the synthesized material. For this purpose, besides the rich photochemistry of azoaromatic polymers that brings to the application, the control offered from the recent techniques of controlled radical polymerization, ATRP over all, gives an enormous range of opportunity for the developing of a new generation of functional materials whose properties are determinate not only by the chemical nature of the functional center (e.g. azoaromatic chromophore) but are tuned and even amplified by a synergy with the whole macromolecular structure. Old materials in new structures. In this contest the work of this thesis was focused mainly on the synthesis and characterization of well defined azoaromatic polymers in order to establish, for the first time, precise structure-properties correlation. In fact a series of well defined different azopolymers, chiral and achiral, with different molecular weight and highly monodisperse were synthesized and their properties were studied, in terms of photoexpansion and photomodulation of chirality. We were then able to study the influence of the macromolecular structure in terms of molecular weight and ramification on the studied properties. The huge amount of possibility offered by the tailoring of the macromolecular structure were exploited for the synthesis of new cholesteric photochromic polymers that can be used as a smart label for the certification of the thermal history of any thermosensitive product. Finally the ATRP synthesis allowed us to synthesize a total new class of material, named molecular brushes: a flat surface covered with an ultra thin layer of polymeric chain covalently bond onto the surface from one end. This new class of materials is of extreme interest as they offer the possibility to tune and manage the interaction of the surface with the environment. In this contest we synthesized both azoaromatic surfaces, growing directly the polymer from the surface, and mixed brushes: surfaces covered with incompatible macromolecules. Both type of surfaces acts as “smart” surfaces: the first it is able to move the orientation of a LC cell by simply photomodulation and, thanks to the robustness of the covalent bond, can be used as a command surface overcoming all the limitation due to the dewetting of the active layer. The second type of surface, functionalized by a grafting-to method, can self assemble the topmost layer responding to changed environmental conditions, exposing different functionality according to different environment.

Advanced SPM studies on the growth of ultrathin films of organic semiconductors at metal and dielectric interfaces

Many studies on the morphology, molecular orientation, device performance, substrate nature and growth parameter dependence have been carried out since the proposal of Sexithiophene (6T) for organic electronics [ ] However, these studies were mostly performed on films thicker than 20nm and without specifically addressing the relationship between morphology and molecular orientation within the nano and micro structures of ultrathin films of 0-3 monolayers. In 2004, the observation that in OFETs only the first few monolayers at the interface in contact with the gate insulator contribute to the charge transport [ ], underlined the importance to study submonolayer films and their evolution up to a few monolayers of thickness with appropriate experimental techniques. We present here a detailed Non-contact Atomic Force Microscopy and Scanning Tunneling Microscopy study on various substrates aiming at the investigation of growth mechanisms. Most reported similar studies are performed on ideal metals in UHV. However it is important to investigate the details of organic film growth on less ideal and even technological surfaces and device testpatterns. The present work addresses the growth of ultra thin organic films in-situ and quasi real-time by NC-AFM. An organic effusion cell is installed to evaporate the organic material directly onto the SPM sample scanning stage.

Fabrication and characterization of hybrid ferromagnetic-organic heterostructures for spintronics application

Recent research in the field of organic spintronics highlighted the peculiar spin-dependent properties of the interface formed by an organic semiconductor (OSC) chemisorbed over a 3d ferromagnetic metal, also known as spinterface. The hybridization between the molecular and metallic orbitals, typically π orbitals of the molecule and the d orbitals of the ferromagnet, give rise to spin dependent properties that were not expected by considering the single components of interfaces, as for example the appearance of a magnetic moment on non-magnetic molecules or changes in the magnetic behavior of the ferromagnet. From a technological viewpoint these aspects provide novel engineering schemes for spin memory and for spintronics devices, featuring unexpected interfacial magnetoresistance, spin-filtering effects and even modulated magnetic anisotropy. Applications of these concepts to devices require nevertheless to transfer the spinterface effects from an ideal interface to room temperature operating thin films. In this view, my work presents for the first time how spinterface effects can be obtained even at room temperature on polycrystalline ferromagnetic Co thin films interfaced with organic molecules. The considered molecules were commercial and widely used in the field of organic electronics: Fullerene (C60), Gallium Quinoline (Gaq3) and Sexithiophene (T6). An increase of coercivity, up to 100% at room temperature, has been obtained on the Co ultra-thin films by the deposition of an organic molecule. This effect is accompanied by a change of in-plane anisotropy that is molecule-dependent. Moreover the Spinterface effect is not limited to the interfacial layer, but it extends throughout the whole thickness of the ferromagnetic layer, posing new questions on the nature of the 3d metal-molecule interaction.