A high-mobility organic semiconductor employed as the active material in a field-effect transistor does not guarantee per se that expectations of high performance are fulfilled. This is even truer if a downscaled, short channel is adopted. Only if contacts are able to provide the device with as much charge as it needs, with a negligible voltage drop across them, then high expectations can turn into high performances. It is a fact that this is not always the case in the field of organic electronics. In this review, we aim to offer a comprehensive overview on the subject of current injection in organic thin film transistors: physical principles concerning energy level (mis)alignment at interfaces, models describing charge injection, technologies for interface tuning, and techniques for characterizing devices. Finally, a survey of the most recent accomplishments in the field is given. Principles are described in general, but the technologies and survey emphasis is on solution processed transistors, because it is our opinion that scalable, roll-to-roll printing processing is one, if not the brightest, possible scenario for the future of organic electronics. With the exception of electrolyte-gated organic transistors, where impressively low width normalized resistances were reported (in the range of 10 Ω·cm), to date the lowest values reported for devices where the semiconductor is solution-processed and where the most common architectures are adopted, are ∼10 kΩ·cm for transistors with a field effect mobility in the 0.1-1 cm(2)/Vs range. Although these values represent the best case, they still pose a severe limitation for downscaling the channel lengths below a few micrometers, necessary for increasing the device switching speed. Moreover, techniques to lower contact resistances have been often developed on a case-by-case basis, depending on the materials, architecture and processing techniques. The lack of a standard strategy has hampered the progress of the field for a long time. Only recently, as the understanding of the rather complex physical processes at the metal/semiconductor interfaces has improved, more general approaches, with a validity that extends to several materials, are being proposed and successfully tested in the literature. Only a combined scientific and technological effort, on the one side to fully understand contact phenomena and on the other to completely master the tailoring of interfaces, will enable the development of advanced organic electronics applications and their widespread adoption in low-cost, large-area printed circuits.

Charge injection in solution-processed organic field-effect transistors: physics, models and characterization methods.

Research into organic field effect transistors (OFETs) has made significant advances—both scientifically and technologically—during the last decade, and the first products will soon enter the market. Printed electronic circuits using organic resistors, diodes and transistors may become cheap alternatives to silicon-based systems, especially in large-area applications. A key parameter for device operation, besides long term stability, is the reproducibility of the current–voltage behavior, which may be affected by hysteresis phenomena. Hysteresis effects are often observed in organic transistors during sweeps of the gate voltage (V
 GS). This hysteresis can originate in various ways, but comparative scientific investigations are rare and a comprehensive picture of “hysteresis phenomena” in OFETs is still missing. This review provides an overview of the physical effects that cause hysteresis and discusses the importance of such effects in OFETs in a comparative manner.

Current versus gate voltage hysteresis in organic field effect transistors

Blending organic semiconductors with insulating polymers has been known to be an effective way to overcome the disadvantages of single-component organic semiconductors for high-performance organic field-effect transistors (OFETs). We show that when a solution processable organic semiconductor (6,13-bis(triisopropylsilylethynyl)pentacene, TIPS-pentacene) is blended with an insulating polymer (PS), morphological and structural characteristics of the blend films could be significantly influenced by the processing conditions like the spin coating time. Although vertical phase-separated structures (TIPS-pentacene-top/PS-bottom) were formed on the substrate regardless of the spin coating time, the spin time governed the growth mode of the TIPS-pentacene molecules that phase-separated and crystallized on the insulating polymer. Excess residual solvent in samples spun for a short duration induces a convective flow in the drying droplet, thereby leading to one-dimensional (1D) growth mode of TIPS-pentacene crystals. In contrast, after an appropriate spin-coating time, an optimum amount of the residual solvent in the film led to two-dimensional (2D) growth mode of TIPS-pentacene crystals. The 2D spherulites of TIPS-pentacene are extremely advantageous for improving the field-effect mobility of FETs compared to needle-like 1D structures, because of the high surface coverage of crystals with a unique continuous film structure. In addition, the porous structure observed in the 2D crystalline film allows gas molecules to easily penetrate into the channel region, thereby improving the gas sensing properties.

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Effect of Crystallization Modes in TIPS-pentacene/Insulating Polymer Blends on the Gas Sensing Properties of Organic Field-Effect Transistors

Luminescent films have received great interest for chemo-/bio-sensing applications due to their distinct advantages over solution-based probes, such as good stability and portability, tunable shape and size, non-invasion, real-time detection, extensive suitability in gas/vapor sensing, and recycling. On the other hand, they can achieve selective and sensitive detection of chemical/biological species using special luminophores with a recognition moiety or the assembly of common luminophores and functional materials. Nowadays, the extensively used assembly techniques include drop-casting/spin-coating, Langmuir–Blodgett (LB), self-assembled monolayers (SAMs), layer-by-layer (LBL), and electrospinning. Therefore, this review summarizes the recent advances in luminescent films with these assembly techniques and their applications in chemo-/bio-sensing. We mainly focused on the discussion of the relationship between the sensing properties of the films and their architecture. Furthermore, we discussed some critical challenges existing in this field and possible solutions that have been or are being developed to overcome these challenges.

Luminescent films for chemo- and biosensing

Surface and interface analytical studies have generated critical insight of the fundamental processes at interfaces involving organic semiconductors. I will review surface analytical studies of interface formation of organic semiconductors with different materials. Metal/organic interface is a focus of both device engineering and basic science, since it is a key factor in nearly all important aspects of device performances, including operation voltages, degradation, and efficiency. I will discuss metal–organic interface dipole formation, charge transfer, chemical reaction, energy level alignment, in-diffusion, quenching of luminescence and possible recovery of it. The effect of the insertion of ultra-thin interlayers such as LiF and doping by alkali metals will also be discussed. In organic/organic interface, the energy offset between the two dissimilar organic materials is vitally important to efficient device operation of organic light emitting diodes (OLED), as well as change separation at donor–acceptor interface in organic photovoltaic devices (OPV). I will discuss the interface energy level alignment, band bending, Debye screening, and charge separation dynamics as observed in surface analytical studies, and the implications to OLED and OPV. The interfaces of OSCs with other inorganic materials are also important. For organic thin film transistors (OTFT), the electronic properties of the interface formed between the organic and the dielectric strongly influences the current–voltage characteristics, as the electronic activity has been shown to occur primarily at the interface between the dielectric and the organic materials. I will review the interface formation of OSCs with dielectric materials and with indium-tin-oxide (ITO), a material whose transparency and conductivity make it indispensable for a number of opto-electronic applications and whose electronic properties and energy level alignment with organics have proven dramatically altered by surface treatments.

Surface analytical studies of interfaces in organic semiconductor devices

Effect of water in ambient air on hysteresis in pentacene field-effect transistors containing gate dielectrics coated with polymers with different functional groups

Reducing the contact resistance in organic thin-film transistors by introducing a PEDOT:PSS hole-injection layer

The effects of spin speed and an amorphous fluoropolymer (CYTOP)-patterned substrate on the crystalline structures and device performance of triisopropylsilylethynyl pentacene (TIPS-PEN) organic field-effect transistors (OFETs) were investigated. The crystallinity of the TIPS-PEN film was enhanced by decreasing the spin speed, because slow evaporation of the solvent provided a sufficient time for the formation of thermodynamically stable crystalline structures. In addition, the adoption of a CYTOP-patterned substrate induced the three-dimensional (3D) growth of the TIPS-PEN crystals, because the patterned substrate confined the TIPS-PEN molecules and allowed sufficient time for the self-organization of TIPS-PEN. TIPS-PEN OFETs fabricated at a spin speed of 300 rpm with a CYTOP-patterned substrate showed a field-effect mobility of 0.131 cm2 V–1 s–1, which is a remarkable improvement over previous spin-coated TIPS-PEN OFETs.

High-performance triisopropylsilylethynyl pentacene transistors via spin coating with a crystallization-assisting layer.

To obtain selectively self-organized active layers of organic field-effect transistors (OFETs) and inverters from a solution-phased triisopropylsilylethynyl pentacene (TIPS-PEN) semiconductor, we locally patterned an oxide dielectric, covered with a hydrophobic fluoropolymer, using O2 plasma etching. Drop-cast TIPS-PEN molecules were selectively crystallized on the O2-plasma-etched area, where a hydrophilic oxide surface was produced. Modification of the patterned oxide dielectrics with hexamethyldisilazane led to a field-effect mobility of the TIPS-PEN OFETs of 0.185 cm2 V−1 s−1, a substhreshold swing of 0.738 V/decade and an on/off ratio of 107. Moreover, an inverter composed of two of these OFETs showed good device operation and inverter gain of 5.6.

High-performance solution-processed triisopropylsilylethynyl pentacene transistors and inverters fabricated by using the selective self-organization technique

We investigated the effects of microstructural (crystallization and molecular orientation) and morphological alternation (grain boundary) of poly(3-hexylthiophene) (P3HT) films on the field-effect mobility (μ) before (as-spun P3HT) and after (melt-crystallized P3HT) melting of P3HT films. Although grazing incidence X-ray scattering shows that melt-crystallized P3HT has a more highly ordered edge-on structure than as-spun P3HT, the melt-crystallized P3HT reveals μ = 0.003 cm2 V−1 s−1; this is an order of magnitude lower than that of as-spun P3HT (μ = 0.01 cm2 V−1 s−1). In addition, the interfacial morphologies of the bottom surfaces of P3HT films, which are attached to the gate dielectric, were investigated using a film transfer technique. The melt-crystallized P3HT at this interface consists of well-developed nanowire crystallites with well-defined grain boundaries that act as trap states, as verified by analysis of the temperature-dependence of μ. The remarkable reduction of μ in low-molecular-weight P3H...

Danbi Choi

Papers

Effect of water in ambient air on hysteresis in pentacene field-effect transistors containing gate dielectrics coated with polymers with different functional groups

Reducing the contact resistance in organic thin-film transistors by introducing a PEDOT:PSS hole-injection layer

High-performance triisopropylsilylethynyl pentacene transistors via spin coating with a crystallization-assisting layer.

High-performance solution-processed triisopropylsilylethynyl pentacene transistors and inverters fabricated by using the selective self-organization technique

Direct Observation of Interfacial Morphology in Poly(3-hexylthiophene) Transistors: Relationship between Grain Boundary and Field-Effect Mobility