Organic thin-film transistors (OTFTs) have lived to see great improvements in recent years. This review presents new insight into conduction mechanisms and performance characteristics, as well as opportunities for modeling properties of OTFTs. The shifted focus in research from novel chemical structures to fabrication technologies that optimize morphology and structural order is underscored by chapters on vacuum-deposited and solution-processed organic semiconducting films. Finally, progress in the growing field of the n-type OTFTs is discussed in ample detail. The Figure, showing a pentacene film edge on SiO2, illustrates the morphology issue.

Organic Thin Film Transistors for Large Area Electronics

Since the discovery of highly conducting polyacetylene by Shirakawa, MacDiarmid, and Heeger in 1977, π-conjugated systems have attracted much attention as futuristic materials for the development and production of the next generation of electronics, that is, organic electronics. Conceptually, organic electronics are quite different from conventional inorganic solid state electronics because the structural versatility of organic semiconductors allows for the incorporation of functionality by molecular design. This versatility leads to a new era in the design of electronic devices. To date, the great number of π-conjugated semiconducting materials that have either been discovered or synthesized generate an exciting library of π-conjugated systems for use in organic electronics. 11 However, some key challenges for further advancement remain: the low mobility and stability of organic semiconductors, the lack of knowledge regarding structure property relationships for understanding the fundamental chemical aspects behind the structural design, and realization of desired properties. Organic field-effect transistors (OFETs) are a kind of device consisting of an organic semiconducting layer, a gate insulator layer, and three terminals (drain, source, and gate electrodes). OFETs are not only essential building blocks for the next generation of cheap and flexible organic circuits, but they also provide an important insight into the charge transport of πconjugated systems. Therefore, they act as strong tools for the exploration of the structure property relationships of πconjugated systems, such as parameters of field-effect mobility (μ, the drift velocity of carriers under unit electric field), current on/off ratio (the ratio of the maximum on-state current to the minimum off-state current), and threshold voltage (the minimum gate voltage that is required to turn on the transistor). 17 Since the discovery of OFETs in the 1980s, they have attracted much attention. Research onOFETs includes the discovery, design, and synthesis of π-conjugated systems for OFETs, device optimization, development of applications in radio frequency identification (RFID) tags, flexible displays, electronic papers, sensors, and so forth. It is beyond the scope of this review to cover all aspects of π-conjugated systems; hence, our focus will be on the performance analysis of π-conjugated systems in OFETs. This should make it possible to extract information regarding the fundamental merit of semiconducting π-conjugated materials and capture what is needed for newmaterials and what is the synthesis orientation of newπ-conjugated systems. In fact, for a new science with many practical applications, the field of organic electronics is progressing extremely rapidly. For example, using “organic field effect transistor” or “organic field effect transistors” as the query keywords to search the Web of Science citation database, it is possible to show the distribution of papers over recent years as shown in Figure 1A. It is very clear

Semiconducting π-conjugated systems in field-effect transistors: a material odyssey of organic electronics.

About Supramolecular Assemblies of π-Conjugated Systems

Synthetic Principles for Bandgap Control in Linear pi-Conjugated Systems.

During the past decade, enormous progress has been made in growing ultrathin organic films and multilayer structures with a wide range of exciting optoelectronic properties. This progress has been made possible by several important advances in our understanding of organic films and their modes of growth. Perhaps the single most important advance has been the use of ultrahigh vacuum (UHV) as a means to achieve, for the first time, monolayer control over the growth of organic thin films with extremely high chemical purity and structural precision.1-3 Such monolayer control has been possible for many years using well-known techniques such as Langmuir-Blodgett film deposition,4 and more recently, self-assembled monolayers from solution have also been achieved.5 However, ultrahighvacuum growth, sometimes referred to as organic molecular beam deposition (OMBD) or organic molecular beam epitaxy (OMBE), has the advantage of providing both layer thickness control and an atomically clean environment and substrate. When combined with the ability to perform in situ highresolution structural diagnostics of the films as they are being deposited, techniques such as OMBD have provided an entirely new prospect for understanding many of the fundamental structural and optoelectronic properties of ultrathin organic film systems. Since such systems are both of intrinsic as well as practical interest, substantial effort worldwide has been invested in attempting to grow and investigate the properties of such thin-film systems. This paper is a review of recent progress made in organic thin films grown in ultrahigh vacuum or using other vapor-phase deposition methods. We will describe the most important work which has been published in this field since the emergence of OMBD in the mid-1980s. Both the nature of thin-film growth and structural ordering will be discussed, as well as some of the more interesting consequences to the physical properties of such organic thin-film systems will be considered both from a theoretical as well as an experimental viewpoint. Indeed, it will 1793 Chem. Rev. 1997, 97, 1793−1896

Ultrathin Organic Films Grown by Organic Molecular Beam Deposition and Related Techniques.

In order to analyze the correlation between charge transport and structural properties in conjugated oligomers, sexithiophene, 6T, was substituted by hexyl groups, both on the terminal α positions (α,ωDH6T) and as pendant groups in the β position (β,β'DH6T). Structural characterizations by X-ray diffraction show that vacuum-evaporated thin films of 6T and α,ωDH6T consist of layered structures in a monoclinic arrangement, with all-trans planar molecules standing on the substrate. When compared to 6T, α,ωDH6T is mainly characterized by a very large increase of molecular organization at the mesoscopic level, evidenced by a much longer range ordering

Molecular engineering of organic semiconductors: design of self-assembly properties in conjugated thiophene oligomers

The influence of deposition temperature on structure, orientation, and morphology of vacuum-evaporated sexithiophene films has been studied by using X-ray diffraction, UVvisible spectroscopy and scanning electron microscopy. We correlate this with the mobility of these films as measured in field-effect transistors. The X-ray study based on meridional 001 reflections shows evidence for various crystalline phases depending on the substrate temperature during vapor deposition. A high degree of orientation can be achieved even in several-micrometer-thick films deposited above 190 "C. It is shown that the field-effect mobility is substantially enhanced for deposition temperatures close to the melting point (290 "C), which is associated with a suitable orientation (002 being the single contact plane) and eventually a favorable crystalline structure and coalescent lamellae morphology.

Polymorphism and Charge Transport in Vacuum-Evaporated Sexithiophene Films

X-ray determination of the crystal structure and orientation of vacuum evaporated sexithiophene films†

Dipolar orientation is measured in two kinds of PVF2 films, the first obtained by successive rolling and poling, and the second by simultaneous rolling and poling. The x‐ray pole figure changes, followed from zero applied field to saturation, show a threshold at a critical field of 300 kV/cm, and are consistent with a 60° switching of the β‐phase molecular dipoles. IR attenuated total reflection shows larger critical fields at the films surfaces; the best dipolar orientation homogeneity is achieved using the simultaneous poling and rolling process.

Simone Ries

Papers

Molecular engineering of organic semiconductors: design of self-assembly properties in conjugated thiophene oligomers

Polymorphism and Charge Transport in Vacuum-Evaporated Sexithiophene Films

X-ray determination of the crystal structure and orientation of vacuum evaporated sexithiophene films†

Bulk and surface dipolar orientation induced by two poling techniques in rolled PVF2 films