Crystallization and Organic Field-Effect Transistor Performance of a Hydrogen-Bonded Quaterthiophene

Crystalline thin films of pi-conjugated molecules are relevant as the active layers in organic electronic devices. Therefore, materials with enhanced control over the supramolecular arrangement, crystallinity, and thin-film morphology are desirable. Herein, it is reported that hydrogen-bonded substituents serve as additional structure-directing elements that positively affect crystallization, thin-film morphology, and device performance of p-type organic semiconductors. It is observed that a quaterthiophene diacetamide exhibits a denser packing than that of other quaterthiophenes in the single-crystal structure and, as a result, displays enhanced intermolecular electronic interactions. This feature was preserved in crystalline thin films that exhibited a layer-by-layer morphology, with large domain sizes and high internal order. As a result, organic field-effect transistors of these polycrystalline thin films showed mobilities in the range of the best mobility values reported for single-crystalline quaterthiophenes. The use of hydrogen-bonded groups may, thus, provide an avenue for organic semiconducting materials with improved morphology and performance.

Approches numériques du transport de charges dans les semiconducteurs organiques

Hocine Houili

Using plastics or dyes like molecular semiconductors to make optoelectronic devices at low cost is a project in industry that is of great interest to the "Information Community" of this beginning of the 21st century. Some applications of this technology have already been realized including flexible flat-panel displays made with organic light-emitting diodes, organic transistors for active matrices, organic solar cells and sensors. In all these applications it is essential to deduce and understand the laws that determine the charge transport and the light emission in these materials. The goal of this thesis is to contribute to the theoretical models that describe these transport processes. In order to predict the behaviour of charge carriers in a given device, one can choose two methods. One can either numerically solve the master equations that describe the general behaviour of charges and currents in each part of the device, or one can simulate the detailed behaviour of each charge in the device by fixing the conditions of its movement using a procedure known as "Monte Carlo". In this thesis I addressed the two approaches. I have been interested successively in the prediction of the electric properties of multilayer light-emitting devices, considered as a whole. Then I was able to understand in detail the processes accruing at the organic-organic interfaces by using the Monte Carlo method. My last project involved the study of the channel of an organic transistor. In each one of these cases I took account of the characteristic features of small molecule organic materials in order to develop models for charge transport for the study and optimization of two important types of organic devices : organic light-emitting diodes and field-effect transistors. Amorphous organic semiconductors are mainly used for the fabrication of organic diodes. They are characterized by an energetically disordered density of states that is assumed to be Gaussian. The transport of charges in these materials occurs via hopping from one molecule to another in this density of states. The correlations between the energies of the molecular sites have important effects on transport ; the dependence of mobility on the applied electric field in particular. If the energetic disorder is due to the random orientations of the permanent dipoles of the molecules, then the correlations between the orientations of these dipoles can profoundly change the spatial configuration of the energetic disorder and consequently the charge transport. Due to the fact that organic diodes often comprise of multiple organic layers, understanding device behaviour at the organic-organic interfaces is of critical importance. Electrons and holes accumulate close to these interfaces and they are therefore more likely to recombine and emit light. The Coulomb interactions between the charge carriers and the energy disorder are at the origin of complex processes taking place at these accumulation regions. I studied these processes through a 3D multi-particle Monte Carlo simulation. The short-range Coulomb repulsion forbids the double-occupancy of the sites and shifts the energy level for injection of carriers across the interface upward, thus increasing the electric current of the diode. The long-range Coulomb interactions increase the electric field and the current at the interface although this increase is less important than suggested by 1D models. Effects related to the hopping process such as the effect of the exact form of the hopping law and backward or return hop at the interface are clearly discussed. The Monte Carlo simulations are cross-compared with an analytical model for hopping transport across the interface. This comparison made it possible to understand other aspects of the physical processes at organic-organic interface and supports the Monte Carlo simulations. The study of the electron-hole recombination showed a decrease of the cross-section with an increase of the applied electric field, but this decrease is less than what can be expected by the classical Langevin theory. In spite of their efficiency, Monte Carlo simulations are not attractive when modelling complex multi-layer diodes. The 1D models are better suited in this case. A 1D model called MOLED, which was developed at Laboratoire d'Optoélectronique des Matériaux Moléculaires (LOMM) for the simulation of the organic diodes, is used and described in detail in this thesis. We used MOLED to explore the effect of the energy correlations on the electric field dependence of the mobility. In fact we simulated the time-of-flight experiment, a common method used to determine of the carrier mobility. The crystalline organic semiconductors achieve mobility performances close or even better than amorphous silicon. Their use for the fabrication of field-effect transistors is thus a good choice. The models for charge transport in crystalline organic materials differ much from their counterparts for amorphous organic materials. Indeed band models are more appropriate to describe charge transport in crystalline organic materials. However it is very important to take into account the effects of electronic polarization in these models. I developed a method of calculation of these effects of polarization in the bulk of the organic semiconductor and I extended it to the case of the interface with a dielectric insulator, a situation encountered in the channel of the organic transistor. These calculations showed that when the polarity of the dielectric increases the inter-molecular transfer integral decreases. This is confirmed by experimental measurements showing increasingly low values of mobility when the permittivity of the insulator increases.

EPFL2006

Contact Effects in Organic Transistors

Frederik Sebastian Ante

Organic thin-film transistors (TFTs) are of interest for applications that require electronic functionality with low or medium complexity distributed over large areas on unconventional substrates, such as flexible polymeric films. Generally these are applications in which the use of silicon devices and circuits is technically or economically not feasible. Examples include flexible displays and large-area sensor arrays. The static and dynamic performance of state-of-the-art organic p-channel transistors is already sufficient for applications in which the transistors operate with frequencies of a few tens of kilohertz. Strategies to improve the performance of organic TFTs include improvements in the field-effect mobility of the charge carriers in the organic semiconductor layer and more aggressive scaling of the transistor dimensions. Additional advances are also required in the environmental and operational stability of organic TFTs and in the application of controlled contact doping for the reduction of the contact resistance of organic TFTs. In this thesis, high-resolution silicon stencil masks are introduced to pattern top-contact organic TFTs with lateral dimensions as small as 0.8 µm. Taking advantage of the recently synthesized high-mobility air-stable organic semiconductor dinaphtho[2,3-b:2'3'-f]thieno[3,2-b]thiophene (DNTT), polycrystalline organic p-channel TFTs with excellent air-stability and an intrinsic mobility of 3.4 cm2/Vs were fabricated. The transistors employ an ultra-thin gate dielectric based on a plasma-grown oxide layer in combination with an organic self-assembled monolayer (gate capacitance ∼1 µF/cm2), allowing the TFTs to operate with low voltages of about 3 V. Transistors with dimensions of less than 100 nm were manufactured using polymer resist shadow masks that have been fabricated by electron-beam lithography. Thanks to the 5 nm thick gate dielectric the TFTs show no short-channel effects. The subthreshold swing, the on/off current ratio, and the threshold voltage are comparable to long-channel TFTs with lateral dimensions of ∼100 µm. However, organic transistors with reduced dimensions are often limited by the energy barrier at the interface between the semiconductor and the source/drain contacts. One approach to reduce this energy barrier is the introduction of a strong electron acceptor into the contact area that acts as a dopant. With contact doping, the contact resistance is reduced and the effective mobility of short-channel TFTs increases by more than 200%. Transistors (without doping) with lateral dimensions of ∼1 µm have a transconductance of about 1 S/m, so that the TFTs operate at frequencies of several megahertz. The influence of strongly reduced lateral dimensions on the contact resistance and the maximum operation frequency is investigated and scaling limitations are discussed.

EPFL2011

Dimensional scaling of high-speed printed organic transistors enabling high-frequency operation

Vivek Subramanian

Printed electronics has promised to deliver low-cost, large-area and flexible electronics for mass-market applications for some time; however, so far one limiting factor has been device performance. Over the last decade, great progress has been made in terms of materials, processing and printing resolution for printed transistors. In this article, we review dimensional scaling of printed organic thin-film transistors, which has enabled high-frequency operation. We review different device architectures that require different dimensions to be scaled with accompanying tradeoffs in performance and complexity. Various printing methods have been used to print scaled transistors. Inkjet and gravure printing have seen the greatest improvements. We will focus on gravure printing here as it not only enables high-resolution features but also high-speed printing for low-cost manufacturing. Operating voltage has been scaled down less aggressively due to difficulties with scaling down the thickness of printed gate dielectrics. The performance of organic semiconductor materials has also improved substantially. When processing the semiconductor, the scaling of other device dimensions needs to be considered to optimize performance. Based on these advances, transistor switching frequency has increased dramatically over the last decade with several reports of high-speed printed inverters operating at high kHz to low MHz frequencies, which are promising results for emerging applications of printed electronics.