Moderate doping leads to high performance of semiconductor/insulator polymer blend transistors
TL;DR: It is shown that blends comprising a small amount of semiconducting polymer mixed into an insulating polymer matrix actually perform very poorly in the undoped state, and that mobility and on/off ratio are improved dramatically upon moderate doping.
Abstract: Polymer transistors are being intensively developed for next-generation flexible electronics. Blends comprising a small amount of semiconducting polymer mixed into an insulating polymer matrix have simultaneously shown superior performance and environmental stability in organic field-effect transistors compared with the neat semiconductor. Here we show that such blends actually perform very poorly in the undoped state, and that mobility and on/off ratio are improved dramatically upon moderate doping. Structural investigations show that these blend layers feature nanometre-scale semiconductor domains and a vertical composition gradient. This particular morphology enables a quasi three-dimensional spatial distribution of semiconductor pathways within the insulating matrix, in which charge accumulation and depletion via a gate bias is substantially different from neat semiconductor, and where high on-current and low off-current are simultaneously realized in the stable doped state. Adding only 5 wt% of a semiconducting polymer to a polystyrene matrix, we realized an environmentally stable inverter with gain up to 60.
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TL;DR: The most successful doping models and an overview of the wide variety of materials used as dopants are presented and the influence of doping on charge transport in the most relevant polycrystalline organic semiconductors is reviewed.
Abstract: Organic field-effect transistors hold the promise of enabling low-cost and flexible electronics. Following its success in organic optoelectronics, the organic doping technology is also used increasingly in organic field-effect transistors. Doping not only increases device performance, but it also provides a way to fine-control the transistor behavior, to develop new transistor concepts, and even improve the stability of organic transistors. This Review summarizes the latest progress made in the understanding of the doping technology and its application to organic transistors. It presents the most successful doping models and an overview of the wide variety of materials used as dopants. Further, the influence of doping on charge transport in the most relevant polycrystalline organic semiconductors is reviewed, and a concise overview on the influence of doping on transistor behavior and performance is given. In particular, recent progress in the understanding of contact doping and channel doping is summarized.
457 citations
TL;DR: Overall, this review brings together important information that aids reliable OTFT data analysis, while providing guidelines for the development of next-generation organic semiconductors.
Abstract: Over the past three decades, significant research efforts have focused on improving the charge carrier mobility of organic thin-film transistors (OTFTs). In recent years, a commonly observed nonlinearity in OTFT current-voltage characteristics, known as the "kink" or "double slope," has led to widespread mobility overestimations, contaminating the relevant literature. Here, published data from the past 30 years is reviewed to uncover the extent of the field-effect mobility hype and identify the progress that has actually been achieved in the field of OTFTs. Present carrier-mobility-related challenges are identified, finding that reliable hole and electron mobility values of 20 and 10 cm2 V-1 s-1 , respectively, have yet to be achieved. Based on the analysis, the literature is then reviewed to summarize the concepts behind the success of high-performance p-type polymers, along with the latest understanding of the design criteria that will enable further mobility enhancement in n-type polymers and small molecules, and the reasons why high carrier mobility values have been consistently produced from small molecule/polymer blend semiconductors. Overall, this review brings together important information that aids reliable OTFT data analysis, while providing guidelines for the development of next-generation organic semiconductors.
452 citations
TL;DR: Recent breakthroughs in molecular doping of organic semiconductors suggest a role for molecular doping not only in device function but also in fabrication-applications beyond those directly analogous to inorganic doping.
Abstract: The field of organic electronics thrives on the hope of enabling low-cost, solution-processed electronic devices with mechanical, optoelectronic, and chemical properties not available from inorganic semiconductors. A key to the success of these aspirations is the ability to controllably dope organic semiconductors with high spatial resolution. Here, recent progress in molecular doping of organic semiconductors is summarized, with an emphasis on solution-processed p-type doped polymeric semiconductors. Highlighted topics include how solution-processing techniques can control the distribution, diffusion, and density of dopants within the organic semiconductor, and, in turn, affect the electronic properties of the material. Research in these areas has recently intensified, thanks to advances in chemical synthesis, improved understanding of charged states in organic materials, and a focus on relating fabrication techniques to morphology. Significant disorder in these systems, along with complex interactions between doping and film morphology, is often responsible for charge trapping and low doping efficiency. However, the strong coupling between doping, solubility, and morphology can be harnessed to control crystallinity, create doping gradients, and pattern polymers. These breakthroughs suggest a role for molecular doping not only in device function but also in fabrication-applications beyond those directly analogous to inorganic doping.
363 citations
TL;DR: Important general processing guidelines for the continued development of doped semiconducting polymers for thermoelectrics are introduced.
Abstract: The electrical performance of doped semiconducting polymers is strongly governed by processing methods and underlying thin-film microstructure. We report on the influence of different doping methods (solution versus vapor) on the thermoelectric power factor (PF) of PBTTT molecularly p-doped with F n TCNQ (n = 2 or 4). The vapor-doped films have more than two orders of magnitude higher electronic conductivity (σ) relative to solution-doped films. On the basis of resonant soft x-ray scattering, vapor-doped samples are shown to have a large orientational correlation length (OCL) (that is, length scale of aligned backbones) that correlates to a high apparent charge carrier mobility (μ). The Seebeck coefficient (α) is largely independent of OCL. This reveals that, unlike σ, leveraging strategies to improve μ have a smaller impact on α. Our best-performing sample with the largest OCL, vapor-doped PBTTT:F4TCNQ thin film, has a σ of 670 S/cm and an α of 42 μV/K, which translates to a large PF of 120 μW m-1 K-2. In addition, despite the unfavorable offset for charge transfer, doping by F2TCNQ also leads to a large PF of 70 μW m-1 K-2, which reveals the potential utility of weak molecular dopants. Overall, our work introduces important general processing guidelines for the continued development of doped semiconducting polymers for thermoelectrics.
250 citations
TL;DR: In this paper, the reproducibility of the mobility of organic semiconducting materials was investigated using the space-charge limited current (SCLC) method and the authors found that mobility measured on nominally identical devices could vary by more than one order of magnitude with the largest sources of variation being poor electrodes and film thickness variation.
243 citations
References
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TL;DR: In this article, the authors used thin-film, field effect transistor structures to probe the transport properties of the ordered microcrystalline domains in the conjugated polymer poly(3-hexylthiophene), P3HT.
Abstract: Self-organization in many solution-processed, semiconducting conjugated polymers results in complex microstructures, in which ordered microcrystalline domains are embedded in an amorphous matrix1. This has important consequences for electrical properties of these materials: charge transport is usually limited by the most difficult hopping processes and is therefore dominated by the disordered matrix, resulting in low charge-carrier mobilities2 (⩽10-5 cm2 V-1 s-1). Here we use thin-film, field-effect transistor structures to probe the transport properties of the ordered microcrystalline domains in the conjugated polymer poly(3-hexylthiophene), P3HT. Self-organization in P3HT results in a lamella structure with two-dimensional conjugated sheets formed by interchain stacking. We find that, depending on processing conditions, the lamellae can adopt two different orientations—parallel and normal to the substrate—the mobilities of which differ by more than a factor of 100, and can reach values as high as 0.1 cm2 V-1 s-1 (refs 3, 4). Optical spectroscopy of the field-induced charge, combined with the mobility anisotropy, reveals the two-dimensional interchain character of the polaronic charge carriers, which exhibit lower relaxation energies than the corresponding radical cations on isolated one-dimensional chains. The possibility of achieving high mobilities via two-dimensional transport in self-organized conjugated lamellae is important for applications of polymer transistors in logic circuits5 and active-matrix displays4,6.
4,306 citations
TL;DR: A highly soluble and printable n-channel polymer exhibiting unprecedented OTFT characteristics under ambient conditions in combination with Au contacts and various polymeric dielectrics is reported and all-printed polymeric complementary inverters have been demonstrated.
Abstract: Printed electronics is a revolutionary technology aimed at unconventional electronic device manufacture on plastic foils, and will probably rely on polymeric semiconductors for organic thin-film transistor (OTFT) fabrication. In addition to having excellent charge-transport characteristics in ambient conditions, such materials must meet other key requirements, such as chemical stability, large solubility in common solvents, and inexpensive solution and/or low-temperature processing. Furthermore, compatibility of both p-channel (hole-transporting) and n-channel (electron-transporting) semiconductors with a single combination of gate dielectric and contact materials is highly desirable to enable powerful complementary circuit technologies, where p- and n-channel OTFTs operate in concert. Polymeric complementary circuits operating in ambient conditions are currently difficult to realize: although excellent p-channel polymers are widely available, the achievement of high-performance n-channel polymers is more challenging. Here we report a highly soluble ( approximately 60 g l(-1)) and printable n-channel polymer exhibiting unprecedented OTFT characteristics (electron mobilities up to approximately 0.45-0.85 cm(2) V(-1) s(-1)) under ambient conditions in combination with Au contacts and various polymeric dielectrics. Several top-gate OTFTs on plastic substrates were fabricated with the semiconductor-dielectric layers deposited by spin-coating as well as by gravure, flexographic and inkjet printing, demonstrating great processing versatility. Finally, all-printed polymeric complementary inverters (with gain 25-65) have been demonstrated.
2,769 citations
TL;DR: New semiconducting liquid-crystalline thieno[3,2-b ]thiophene polymers are reported on, the enhancement in charge-carrier mobility achieved through highly organized morphology from processing in the mesophase, and the effects of exposure to both ambient and low-humidity air on the performance of transistor devices.
Abstract: Organic semiconductors that can be fabricated by simple processing techniques and possess excellent electrical performance, are key requirements in the progress of organic electronics. Both high semiconductor charge-carrier mobility, optimized through understanding and control of the semiconductor microstructure, and stability of the semiconductor to ambient electrochemical oxidative processes are required. We report on new semiconducting liquid-crystalline thieno[3,2-b ]thiophene polymers, the enhancement in charge-carrier mobility achieved through highly organized morphology from processing in the mesophase, and the effects of exposure to both ambient and low-humidity air on the performance of transistor devices. Relatively large crystalline domain sizes on the length scale of lithographically accessible channel lengths (∼200 nm) were exhibited in thin films, thus offering the potential for fabrication of single-crystal polymer transistors. Good transistor stability under static storage and operation in a low-humidity air environment was demonstrated, with charge-carrier field-effect mobilities of 0.2–0.6 cm2 V−1 s−1 achieved under nitrogen.
2,011 citations
TL;DR: In this paper, the electrical characteristics of field effect transistors using solution cast regioregular poly(3-hexylthiophene) are discussed and the authors demonstrate that both high field effect mobilities (ca. 0.045 cm2/V) and relatively high on/off current ratios (greater than 103) can be achieved.
Abstract: The electrical characteristics of field‐effect transistors using solution cast regioregular poly(3‐hexylthiophene) are discussed. We demonstrate that both high field‐effect mobilities (ca. 0.045 cm2/V s in the accumulation mode and 0.01 cm2/V s in the depletion mode), and relatively high on/off current ratios (greater than 103) can be achieved. We find that the film quality and field‐effect mobility are strongly dependent on the choice of solvents. In addition, treating a film with ammonia or heating to 100 °C under N2 can increase the on/off ratio without decreasing the mobility.
1,669 citations
TL;DR: It is shown that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid–air interfaces.
Abstract: Printing electronic devices using semiconducting 'ink' is seen as a promising route to cheap, large-area and flexible electronics, but the performance of such devices suffers from the relatively poor crystallinity of the printed material. Hiromi Minemawari and colleagues have developed an inkjet-based printing technique involving controlled mixing on a surface of two solutions — the semiconductor (C8-BTBT) in its solvent and a liquid in which the semiconductor is insoluble. The products of this antisolvent crystallization technique are thin semiconductor films with exceptionally high and uniform crystallinity. The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science1. Whether based on inorganic2,3,4,5 or organic6,7,8 materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. ‘Printed electronics’ is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials9,10,11. However, because of the strong self-organizing tendency of the deposited materials12,13, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization14 with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid–air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4 cm2 V−1 s−1. This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.
1,505 citations