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Downloaded by University of Guelph on 28 September 2010 Published on 14 April 2010 on http://pubs.rsc.org | doi:10.1039/B907999H
Conducting polymers for carbon electronics themed issue

Guest editor Professor Yung Woo Park
Please take a look at the issue 7 2010 table of contents to access other reviews in this themed issue
CRITICAL REVIEW
www.rsc.org/csr | Chemical Society Reviews
Electroactive materials for organic electronics: preparation strategies, structural aspects and characterization techniquesw
Adam Pron,*a Pawel Gawrys,b Malgorzata Zagorska,b David Djuradoa and Renaud Demadrillea
Received 13th November 2009 First published as an Advance Article on the web 14th April 2010 DOI: 10.1039/b907999h
This critical review discusses specic chemical and physicochemical requirements which must be met for organic compounds to be considered as promising materials for applications in organic electronics. Although emphasis is put on molecules and macromolecules suitable for fabrication of eld eect transistors (FETs), a large fraction of the discussed compounds can also be applied in other organic or hybrid (organicinorganic) electronic devices such as photodiodes, light emitting diodes, photovoltaic cells, etc. It should be of interest to chemists, physicists, material scientists and electrical engineers working in the domain of organic electronics (423 references). due to the fact that the rst generation of organic conductors and semiconductors, although known for a long time, could not compete with inorganic ones, showing poor processability, illdened chemical structures and inferior electrical parameters. Five important events should be mentioned when discussing the progress in organic electronics and related elds: (i) the rst description of peculiar electrical properties of tetrathiafulvalene-tetracyanoquinodimethane charge transfer complex (TTF-TCNQ) in 1965;1 (ii) the discovery of polyacetylene doping in 1977;2 (iii) the rst report on superconductivity in organic materials, namely radical ion salts of tetraselenafulvalene in 1980;3 (iv) the fabrication of a polymeric light emitting diode in 19904 and (v) the discovery of photo-induced charge transfer in molecular composites of conjugated polymers and fullerenes.5 Intensive research work stimulated by the above mentioned discoveries not only gave rise to a Nobel Prize in chemistry, granted in 2000 to A. G. MacDiarmid, A. J. Heeger and H. Shirakawa, but also
1. Introduction
Quick progress in electrical engineering in the rst half of 20th century and then, in its second half, progress in electronics, has been inherently associated with the development of metallurgy and inorganic chemistry. The application of the Czochralski method to the fabrication of large sized, high quality semiconductor single crystals can be mentioned here as an instructive example. One can even suggest that the spectacular successes in inorganic semiconductor technology somehow impeded the development of organic electronics. This was
a
INAC/SPrAM (UMR 5819 CEA-CNRS-Univ. J. Fourier-Grenoble 1), Laboratoire dElectronique Moleculaire Organique et Hybride, 17 Rue des Martyrs, 38054 Grenoble Cedex 9, France. E-mail: adam.pron@cea.fr b Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00 664 Warszawa, Poland w Part of the Conducting Polymers for Carbon Electronics themed issue.
Adam Pron was born (1951) and educated in Poland. After obtaining his MSc in chemistry and chemical engineering he moved to the USA where in 1980 he completed his PhD at the University of Pennsylvania (under the supervision of Alan G. MacDiarmid). In the same year he started working at Warsaw University of Technology where he became full professor in 1993. In 1998 he moved to Atomic Energy Commission (CEA) in Grenoble Adam Pron (France), where he presently holds the position of research director (directeur de recherches). His research interests involve preparation and characterisation of organic electroactive materials and hybrid organicinorganic electroactive nanomaterials.
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Pawel Gawrys was born in 1983 in Gorzow Wielkopolski (Poland). In 2007 he got his MSc in chemistry from Warsaw University of Technology and started his PhD research under the supervision of Professor Malgorzata Zagorska. His PhD is devoted to the synthesis of solution processable, air operating organic semiconductors for n-channel eld eect transistors (OFETs). Pawel Gawrys
The Royal Society of Chemistry 2010
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drew the attention of a large scientic community interested in technological applications of organic semiconductors and conductors. In the past decade several thousands of papers, devoted to the synthesis, characterization, structural studies and processing of organic semiconductors and conductors, have been published yearly. This includes review articles published in this journal6 and in other scientic periodicals of high impact. In April 2007 a special issue of Chemical Reviews entirely devoted to organic electronics was published.7 Similarly, two special issues of Advanced Materials on organic electronics appeared in 2009.8 Important review papers on organic transistors,9 photovoltaic cells10 or organic materials electroluminescence,11 which became classics, have recently been completed by an increasing number of new reviews focusing on various scientic and technological problems of
Malgorzata Zagorska, a University of Warsaw graduate, obtained her PhD in chemistry from Warsaw University of Technology in 1987. Then she moved to Royal Institute of Technology in Stockholm (Sweden) where she worked as postdoctoral fellow under the supervision of Goran Ahlgren and Bernd Krische. In 19921994 she worked in UNIAX Corporation in Santa Barbara (USA), closely collaborating with Alan J. Malgorzata Zagorska Heeger. In 1994 she returned to Warsaw University of Technology where she became full professor in 2005. Her research interests involve the synthesis, electrochemistry and spectroelectrochemistry of organic semiconductors and conductors as well as their application in organic electronics.
the newest generations of organic transistors12 or solar cells.13 Given the plethora of tutorial, review and experimental papers covering, in detail, various aspects of materials and physical chemistry of low and high molecular weight electroactive organic compounds, it is dicult to prepare a review which would pretend to be exhaustive. We will, therefore, concentrate on these groups of compounds and these types of problems which, in our opinion, deserve a more exhaustive and systematic description and are somehow related to our research interests. This mainly embraces the design and synthesis as well as structural, electrochemical and spectroelectrochemical characterization of new organic materials for eld eect transistors (FETs) but the use of the described materials is not limited to FETs. A large majority of them may also be applied as components of photovoltaic cells, light emitting diodes, photodiodes and various types of electronic sensors. Special emphasis will be put on the development in this eld observed in the last two years since the interest in organic electronics has recently boosted. According to ISI Web of Science, up to the end of October 2009 over 4000 papers were published on various aspects of organic eld eect transistors (OFETs), including the synthesis of semiconducting molecules and macromolecules, their characterization and processing, device fabrication and testing. 40% of these publications appeared in 2008 and 2009! If classied according to the aliation of the researchers, 26% of contributions originated from the USA; 20% from Japan; 11% from South Korea; 10.5% from Germany; 9.5% from China; 6% from England and 6% from France. But not only has this domain of organic electronics grown exponentially, very similar numbers are also obtained for articles devoted to organic and hybrid (organicinorganic) photovoltaic cells (PC). Out of ca. 4000 papers published up to the end of October 2009 slightly over 40% appeared in 2008 and 2009. Again the same countries contributed in the most signicant manner to the scientic literature devoted to this eld with the following share: USA 21.5%; Japan 15%; Germany 11.5%; China 11.5%; France 6%; South Korea 5%; England 5%.
Dr David Djurado has worked at CNRS since 1981. He obtained his PhD in 1981 and defended a so-called State Thesis in Physics in 1987, both at the University of ClermontFerrand (France). Then he moved to a fellowship at the University of Pennsylvania (Philadelphia-USA) working with Prof. J. E. Fischer on the structure of doped polyacetylene (19881989). He moved to Grenoble in 1991, his main elds of interest David Djurado concern the study of the structure and dynamics in low and high molecular weight conjugated systems and their applications in organic electronics.
Renaud Demadrille is an active researcher in the eld of materials chemistry and organic electronics. He earned a degree in organic chemistry in 1997 and a PhD in 2000 from the University of AixMarseille II. He spent one year in an international chemical company and then he joined the Atomic Energy Commission (CEA) as a postdoctoral fellow, before being appointed in 2005 as a permanent researcher in the Renaud Demadrille laboratory of molecular, hybrid and organic electronics. His research focuses on the synthesis and the characterization of new p-conjugated molecules and macromolecules for organic electronics, and energy conversion. He is also interested in surface chemistry and self-assembly of nano-objects.
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The organization of this paper is as follows. In Section 2 and 3 we discuss the requirements of a thermodynamic, structural and morphological nature which the new materials must meet in order to be considered as promising candidates for applications in electronic devices. Section 4 is devoted to the detailed description of the synthetic strategies used in the preparation of low and high molecular weight semiconductors for n-channel FETs. The relationship between molecular, macromolecular (in the case of polymers), supramolecular and morphological parameters of the organic semiconductors and their electrical transport properties will also be discussed. By symmetry, similar problems related to semiconductors suitable for p-channel FETs are presented in Section 5. The paper is completed by the conclusion part which not only focuses on the selection of the best synthetic and processing approaches but also tries to identify less explored areas of organic electronics which seem to be promising.
2. Principles of organic semiconductor synthesis and their chemical, molecular and electronic characteristics
The most characteristic feature of organic semiconductors is their spatially extended pp or pnp bonding system. From the standpoint of a chemist this can be considered as the conditio sine qua non of electronic conductivity. In an organic molecule the s-bonding system assures its integrity, electrons from the s bonds cannot, however, contribute to the electronic conductivity because any type of their displacement would result in the cleavage of the molecule. For these reasons purely s-bonded molecules or macromolecules are insulators. In the presence of a spatially extended conjugated system charge carriers can move in a given molecule because to a rst approximation the s-system remains intact in this process and the molecule identity is preserved. This simple picture explains the formation and stabilization of dierent charge storage congurations in an individual molecule; however the real situation is more complex since in any real sample, including single crystals, charge carriers must move from one molecule to another. In less ordered systems they have to pass barriers when moving from structurally more organized areas to less organized ones. As a consequence their high mobility pathway depends frequently on percolation phenomena. The latter are, in turn, governed by the sample morphology. In hybrid organicinorganic systems the eect of the interface on charge carrier formation and their mobility must additionally be taken into account. This complex picture of electrical charge transport in organic semiconductors may imply dierent conductivity mechanisms depending on the specicity of a given system. Despite this fact, theoretical calculations still constitute an appropriate basis for the elucidation of the electronic structure and electrical transport phenomena in organic semiconductors and can be considered as a good predictive basis for the synthesis of new organic semiconductors.14 In the simplest classication two types of organic semiconductors can be distinguished: low molecular weight semiconductors (LMWSC) and high molecular weight ones (HMWSC). Some of low molecular weight semiconductors
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are oligomeric analogues of the corresponding semiconducting polymers. LMWSC are strictly monodisperse since they are prepared by methods typical of synthetic organic chemistry, sometimes using iterative procedures if longer oligomers are needed. This fact facilitates their 2D and 3D structural organization in thin semiconductor layers which are components of real devices. They sometimes show polymorphism and in this case their structure may depend on the applied processing conditions (vapor vs. solution deposition, temperature, casting method, etc.), being, for example, dierent for single crystals and for thin lms deposited on a substrate.15 Thus, electrical transport properties of thin LMWSC layers depend on their phase purity, size and shape of crystallites, their degree of orientation, layer compactness, the interface between the semiconductor and dielectric layers and the interface between the semiconductor and the electrodes. Presently developed LMWSC synthetic strategies frequently involve the so called building blocks approach. In this approach conjugated segments of diering electron accepting/donating properties are assembled together by appropriate chemical coupling to give a molecule with precisely tuned electronic properties. Semiconducting molecules, prepared using this approach frequently consist of a central unit (CU), surrounded by one of two types of so called intervening units (IU) which modify the p electron density in the central unit. Two terminal units (TU), usually containing long alkyl substituents, are nally attached to improve the molecule solution processability and to facilitate the formation of an ordered supramolecular organization through interdigitation (see Scheme 1). The prepared semiconducting molecule can, in some cases, be polymerized leading to the corresponding polymeric semiconductor (vide infra). Recent preparation of semiconducting naphthalene bisimides with tunable HOMO and LUMO levels can be considered as an instructive example of the building blocks approach (see Scheme 2).16 In these molecules, namely naphthalene bisimides containing an alkylthienyl moiety on their N substituents, the electron density of the central naphthalene unit is diminished by the presence of two electron accepting arylene bisimide groups (IUs). As a result the LUMO level of the molecule is signicantly lowered. Branching two alkylthienyl terminal groups (TUs) induces the solution processability of the molecules and, at the same time, raises its HOMO level. The latter was conrmed by electrochemical studies and DFT calculations which showed, that in this case the HOMO level is mainly located on the thiophene ring.17 In the selected reaction pathway alkylthienyl aniline is rst prepared and then condensed with a naphthalene bisanhydride, assuring in this manner the presence of all building blocks.
Scheme 1 Units of a semiconducting molecule being considered in the building blocks approach.
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Scheme 2 Synthesis of HOMO/LUMO positions.
naphthalene bisimides
with
tunable
Signicant evolution has been observed in the preparation of HMWSCs in the past two decades. In the early stages of organic electronics methods typical of polymer chemistry were used such as, in the case of polyacetylene, ZieglerNatta polymerization of acetylene,18 or metathetical ring opening polymerization.19 More recently, oxidative polymerization and several condensation methods emerged such as Gilch-type condensation, Kumada, Yamamoto, Stille or Suzuki coupling and others. Some of them are very useful in the preparation of polymers from macromonomers prepared according to the building block approach. One must be however aware of the fact that the polymerization of such macromonomers is not trivial since the presence of groups which modify the p-electron density in the conjugated backbone may sometimes perturb the polymerization (polycondensation) process. This eect can be illustrated using alternating copolymers of oligothiophene and oxadiazole as an example.20 In principle, these semiconducting copolymers could be obtained by oxidative electrochemical polymerization of 2,5-bis(3-alkylthien-2-yl)1,3,4-oxadiazole. The oxidative polymerization is initiated, in this case, by the formation of a radical cation in the a position of the thiophene ring. The presence of a strong electron accepting central unit (CU)1,3,4-oxadiazolelowers the p-electron density at the polymerization site and by consequence signicantly increases the potential of cation radical formation. This makes the electrochemical polymerization impossible. Addition of two more alkylthienyl groups by Suzuki coupling is necessary to shield the eect of the central unit and to initiate the electropolymerization, as illustrated in Scheme 3. To summarize, the building block approach facilitates the preparation of molecules (or macromolecules) with controlled electronic properties, however several subtle aspects must be taken into consideration in this case, among them the eect of mutual interactions between the molecule building units.
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Scheme 3 Synthetic pathway to alternating copolymers of oxadiazole and oligothiophene.
HMWSCs are more complex systems than the corresponding LMWSCs and several additional factors must be taken into account when the structureproperty relationship is to be established for these semiconductors. On the level of the structure of an individual macromolecule this is the chain regioregularity which is of dominant importance and should be strictly controlled. Nominally the same polymers may dier in their regioregularity and among a large number of synthetic methods used for the preparation of HMWSC only very few are regiospecic.21 Polydispersity of the HMWSC molecular weight is another point of concern. In the majority of cases the obtained polymerization or polycondensation products are mixtures of oligomers and true high molecular weight compounds. This has a negative impact on the structure of thin HMWSC lms deposited on a substrate since the supramolecular organization of short chain oligomers is frequently incompatible with that found for truly high molecular weight fractions.22 As a result, structurally poorly dened, amorphous layers are formed upon solution processing. It should also be noted that for many polymers the charge carrier mobility in the fabricated OFETs and organic photovoltaic cells (OPCs) is strongly molecular weight dependent, increasing by ca. 45 orders of magnitude for one order of magnitude increase in Mn.23 Thus, appropriate fractionation into sharper fractions is recommended for essentially all polymers used for the fabrication of OFETs or OPCs.24 From the technological point of view solution processability of LMWSC and HMWSC is of crucial importance because this property facilitates the fabrication of transistors using common solution-based printing and patterning techniques easily adaptable to large surface substrates. For this reason
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signicant research attempts have been undertaken in recent years with the goal to improve the solution-based device fabrication techniques and make them competitive with vapor deposition-based ones, as far as the performance of the fabricated devices is concerned.25 Apart from their facile processability, the applicability of LMWSC and HMWSC in a given electronic device is governed by the positions of their highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels with respect to the vacuum level. The determination of these positions is the rst step in establishing the energy-levels alignment at organicmetal and organicorganic interfaces in devices to be designed and fabricated. As already stated, the predictive role of theoretical calculations should be pointed out here. Experimentally the positions of the HOMO level can be determined by photoelectron spectroscopy (PES) and the LUMO level by inverse photoelectron spectroscopy (IPES). An excellent review on this subject has recently been published.26 Other techniques, more readily available than PES, like cyclic voltammetry (CV) or a combination of electrochemical and spectroelectrochemical techniques can also be used for this purpose. They will be described below. One must however be aware of the fact that the HOMO and LUMO energy values determined electrochemically and spectroelectrochemically are sometimes dierent from those obtained by PES. These methods constitute however a powerful tool for the characterization of organic semiconductors and their role in predicting the suitability of a given LMWSC or HMWSC for its application in a particular electronic device should be pointed out. The HOMO, LUMO and so called electrochemical band gap can be determined from cyclic voltammetry (CV) or dierential pulse voltammetry (DPV) investigations. The principles of these measurements can be outlined as follows.
LMWSC and HMWSC semiconductors can undergo a so called doping reaction. In chemical terms p-type (oxidative) doping consists of the transformation of neutral molecules (macromolecules) into radical cations through abstraction of one electron from the HOMO level. For high doping levels the formed radical cations recombine to diamagnetic dications. Radical cations and dications form special charge storage congurations called polarons and bipolarons, respectively. This is schematically depicted in Fig. 1 using polythiophene as an example. By symmetry, n-type (reductive) doping corresponds to the transformation of neutral molecules (macromolecules) into radical anions via introduction of one electron to the LUMO level and eventually to dianions for higher doping levels.
Fig. 2 Cyclic voltammogram of a thin lm of poly[(5,5 0 0 0 -dioctyl[2,2 0 ;5 0 ,2 0 0 ;5 0 0 ,2 0 0 0 ]quaterthiophene)-alt-(2,7-uoren-9-one)] (PQTF8) deposited on an ITO electrode. Electrolyte 0.1 M Bu4NPF6 solution in acetonitrile; Ag/Ag+ reference electrode; scan rate 20 mV s1 [reproduced by permission from R. Demadrille, N. Delbosc, Y. Kervella, M. Firon, R. De Bettignies, M. Billon, P. Rannou, A. Pron, J. Mater. Chem., 2007, 17, 4661].
Fig. 1 Scheme of p-doping of polythiophene together with the evolution of its band gap (a) neutral polymer, (b) p-doped, polaron level (c) p-doped, bipolaron level. q = charge; s = spin.
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n-Dopable and p-dopable LMWSC and HMWSC show very characteristic voltammograms (see Fig. 2) in which the anodic peak corresponds to the p-doping process and the cathodic one to n-doping. The potentials of the onset of these peaks reect the position of the LUMO and HOMO levels. To calculate the positions of these levels with respect to the vacuum level one must express the onset potential values on the absolute potential scale.27 If the potentials are given with respect to the Ag/AgCl reference electrode the following expressions can be used:
ELUMO = (Ered EHOMO = (Eox
onset onset
+ 4.4) eV + 4.4) eV
(1) (2)
The energy dierence between the electrochemically determined LUMO and HOMO levels gives the so called electrochemical band gap.28 It should be pointed out that for many groups of organic semiconductors an excellent correlation can be found between the LUMO level determined from IPES measurements and the onset of the rst reduction peak. The correlation between the optical and electrochemical band gaps is usually worse.29 In some research papers the presented cyclic voltammograms and UV-vis spectra are measured for solutions of LMWSC or HMWSC. One must however be aware of the fact that in such studies electronic states of individual molecules are probed. They can be signicantly altered in the solid state via additional intermolecular interactions leading to conformational changes of the molecules (macromolecules) which impose the change in the conjugation length. A strong solvatochromic eect, known for many types of HMWSC, is a clear manifestation of these phenomena.30 In general, planarity and the conjugation length in a macromolecule are higher in the solid state than in solution. This is reected by a bathochromic shift of the pp* band position observed in the solid state UV-vis spectra with respect to that measured for the solution spectra. Signicant dierences in the voltammetric response recorded for solutions and for the solid state can also be observed. For the above mentioned reasons, in all cases where it is possible, the solid state data should be preferred in the elucidation of the electronic structure of LMWSC or HMWSC because they more closely approach the real state of the molecules in an operating electronic device. In this respect, voltammetric determination of the HOMO and LUMO levels of organic semiconductors presents some disadvantages. The voltammetric response of a thin semiconductor layer usually depends on the kinetics of the redox reaction which, in turn, is dependent on the sample morphology. To avoid these problems it is preferable to carry out experiments which probe the equilibrium states. UV-vis and Raman spectroelectrochemical investigations are almost ideally suited for this purpose. In a typical UV-vis-NIR spectroelectrochemical experiment a thin layer of LMWSC or HMWSC is deposited on a transparent ITO electrode which serves as a working electrode. The potential of this working electrode is increased in very small increments. After each potential raise, a wait time is applied until the equilibrium state is reached. Then the UV-vis-NIR spectrum is registered. It is assumed that the equilibrium state is reached when the potential change induced
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Fig. 3 UV-vis spectra of poly[(4,4 0 0 -dioctyl-2,2 0 ;5 0 ,2 0 0 -terthiophene3 0 -yl)ethyl acetate] registered for increasing electrode potentials, electrolyte: 0.1 M Bu4NBF4; in 0.1 M Bu4NBF4acetonitrile solution; E vs. Ag/Ag+ [reproduced by permission from K. Buga, R. Pokrop, A. Majkowska, M. Zagorska, J. Planes, F. Genoud, A. Pron, J. Mater. Chem., 2006, 16, 2150].
current becomes negligible. By this technique the potential of the onset of the doping process can easily be determined since the doping process involves characteristic spectral changes consisting of bleaching of the pp* transition band with simultaneous growth of doping induced bands at higher wavelengths.31 Since the spectra are very sensitive towards extremely small changes in the p electron population, the potential of the n- or p-doping onset can precisely be determined. This is illustrated in Fig. 3 where UV-vis-NIR spectroelectrochemical data, obtained for poly[(4,4 0 0 -dioctyl2,2 0 ;5 0 ,2 0 0 -terthiophene-3 0 -yl)ethyl acetate], are presented. As can be seen no spectral changes are observed up to E = 0.40 V, then upon a potential raise by 25 mV an abrupt decrease of the pp* transition band, characteristic of the neutral (undoped) state, occurs. At the same time a broad peak with a maximum at 770 nm appears, indicative of the p-doped state. By probing the sample in even smaller increments, in the potential range from 0.40 V to 0.425 V, it is possible to detect the potential of the p-doping onset with greater precision and by consequence more precisely determine the HOMO level. The same type of measurements can be carried out using Raman spectroelectrochemistry. The experimental setup is in this case similar; the thin semiconductor layer is however deposited on a platinum electrode. In general, Raman spectra of LMWSC or HMWSC are strongly inuenced by the resonance eect.32 In particular, higher wavelength excitation lines such as 676 nm, 780 nm or 1064 nm are in resonance with the p- or n-doped state of the studied compound and preferentially enhance the bands originating from the vibrations of its doped form. Shorter excitation lines are in resonance with the neutral (undoped) form.33 The onset of the n- or p-doping results in drastic changes of the resonance conditions and, by consequence, gives rise to profound changes in the Raman spectrum.
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properties in thin layers of solid semiconductors. Finally, the positions of the HOMO and LUMO levels must be measured to establish the energy level alignment in all components of the device being designed.
3. Principles of eld eect transistor operation

Field eect transistors play an important role in modern electronics because they are important elements of integrated circuits and other devices. A eld eect transistor consists of a semiconductor layer, a dielectric layer and three electrodes, namely gate, source and drain. There exist four device congurations, depicted schematically in Fig. 5. The bottom gatebottom contact conguration is especially suitable for transistors with a SiO2 dielectric layer because in this case the organic semiconductor layer is deposited at the end of the transistor fabrication, after the growth of the dielectric, modication of its surface and the patterning of the source and drain electrodes. Thus, no risk exists that the technological processes may negatively inuence the structure or morphology of the semiconductor layer or lead to a partial decomposition of the semiconductor. A protective layer is sometimes deposited on the top since many semiconductors are not stable in ambient air operating conditions. In recent years an increasing interest in the fabrication of FETs by solution processing has been observed. Top gate bottom contact is the most appropriate conguration for the fabrication of FETs via solution processing. The procedure usually involves the source and drain electrode patterning on an appropriate substrate followed by consecutive deposition of the semiconductor and dielectric layers and the gate electrode by spin coating or ink jet techniques. The dielectric layer can sometimes serve as a protective layer, eventually an additional protective layer can be deposited at the end. The principles of organic FETs operation have been described is several reviews and experimental papers.34 There will be only briey outlined here, taking n-channel FETs as an example. With no voltage at the gate (VG = 0) and small sourcedrain bias (VDS > 0) no current ows because there are no mobile charge carriers in the semiconductor layer. The transistor is in its OFF state. The application of a suciently high gate voltage (VG > 0) produces an intensive electric eld which results in the formation of negative charge carriers in the semiconductor layer at its interface with the dielectric layer. At VDS higher than the so called threshold voltage (VT), the transistor is switched to the ON state. The concentration of the injected charge carriers can be precisely controlled by small variation of the gate voltage. By electronhole symmetry the operation of p-channel FETs can be described with VG o 0 and VDS o 0 for switching the transistor to its ON state. There are three crucial parameters which describe the functioning of a given FET. These are the charge carrier mobility (me or mh), the threshold voltage (VT) and the ON/OFF ratio. They can be determined from so called transfer and output characteristics of the transistor. The ON/OFF ratio is the ratio of the measured current with the gate voltage switched on and o, respectively. Usually ON/OFF ratios exceeding 106 are required. This ratio is very
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Fig. 4 Raman spectra of poly[(4,4 0 0 -dioctyl-2,2 0 ;5 0 ,2 0 0 -terthiophene3 0 -yl)ethyl acetate] registered for increasing electrode potentials, electrolyte: 0.1 M Bu4NBF4; in 0.1 M Bu4NBF4acetonitrile solution; E vs. Ag/Ag+; lexc = 1064 nm [reproduced by permission from K. Buga, R. Pokrop, A. Majkowska, M. Zagorska, J. Planes, F. Genoud, A. Pron, J. Mater. Chem., 2006, 16, 2150].
This is illustrated in Fig. 4. The studied polymer, poly[(4,4 0 0 dioctyl-2,20 ;50 ,20 0 -terthiophene-30 -yl)ethyl acetate], is, in its neutral form, out of resonance with the applied infrared excitation line (lexc = 1064 nm). This is due to the fact that no electronic transition band of the polymer matches the energy of the excitation line. The resulting weak Raman spectrum, characteristic of the neutral form is dicult to register (see Fig. 4). Upon the onset of p-doping, i.e. above the potential of 0.42 V, the electronic spectrum signicantly changes (see Fig. 3), an increase in the absorbance at the wavelength of 1064 nm can be noticed. This results in a drastic change of the resonance conditions. As a result bands originating from the vibrations of the doped form start to dominate the spectrum (Fig. 4).31 Note that this change of the spectrum occurs within a 10 mV potential range. The potential of the n- or p-doping onset can therefore be determined with high precision in the equilibrium state. Moreover, by Raman spectroelectrochemistry it is possible to detect the presence of the doped form at the levels undetectable by other techniques. To summarize this part of the review, organic semiconductors designed for applications in organic electronics require precise determination of their molecular structure and chemical purity since contaminations are frequently a source of charge carrier trapping. In the case of HMWSC macromolecular parameters such as molecular mass and polydispersity index must also be strictly controlled because they have a strong eect on the type and extent of the 2D and 3D supramolecular organization in the solid state and, by consequence, on the electrical transport
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Fig. 5 Possible congurations of organic eld eect transistors.
sensitive to the purity of the organic semiconductor material being used. Incomplete purication may lead to the presence of residual dopants. They are the origin of permanent charge carriers whose concentration is independent of the gate voltage. The presence of such carriers increases the conductivity in the OFF state and lowers the ON/OFF ratio. Ecient purication is more dicult for HMWSC than for LMWSC. The conductivity in the ON state is, in turn, proportional to the concentration of charge carriers created by the gate voltage and to their mobility. The latter is also strongly dependent on the purity of the organic semiconductor since the contaminations frequently act as charge carrier traps, lowering in this manner the ON/OFF ratio. Thus HMWSC and LMWSC suitable for FET applications should be carefully puried with the goal to attain the highest possible charge carrier mobility and the lowest level of residual charge carriers. In the case of n-channel FETs the creation of gate voltage induced charge carriers requires the lowering of the semiconductor LUMO level which has to become resonant with the Fermi level of the metal contact, whose potential is externally controlled. This means that HMWSC and LMWSC with a low lying LUMO level are the most suitable for the fabrication of such transistors. It has also been experimentally established that for air operating transistors the LUMO level of semiconductors, determined from electrochemical studies, should be below 4.0 eV with respect to the vacuum level.35,36 By analogy it may seem that HMWSC and LMWSC with a high lying HOMO level should be good candidates for p-channel FETs. This is not the case. Such polymers, like polypyrrole or poly(3,4-ethylenedioxythiophene) are much more stable in their doped form than in the neutral (undoped) one that is suitable for FET applications. Their undoping is dicult and they become easily redoped even in the presence
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of minute amounts of contaminants showing slightly oxidizing properties. As a result acceptable ON/OFF ratios are dicult to obtain for these semiconductors even if protecting layers are used. Thus a delicate compromise is needed in this case as far as the energy level alignment is concerned.
4. Organic semiconductors for n-channel eld eect transistors

Semiconductors for n-channel OFETs are becoming increasingly popular and start to compete in the domain of organic electronics with those exhibiting hole conductivity. Their history is briefer due to several reasons.37 First, molecules (macromolecules) of LMWSC (HMWSC) contain polar groups which usually reduce their solution processability. Second, until recent few years transistors based on n-channel semiconductors showed poorer performance than p-channel ones which was caused by their sensitivity to electron trapping by oxygen or water when operating in ambient conditions.38,39 Studies focusing on the chemical nature of these processes were presented by de Leeuw et al.40 The most popular approach for synthesizing n-type semiconductors is the introduction of side or peripheral electron withdrawing groups to a larger p-conjugated moiety. In many cases this also means that compounds which normally work as p-type semiconductors can be converted into n-type ones by appropriate functionalization. What is more, as shown in several examples presented in this review, a balance between electron rich and electron poor units may lead to materials which show ambipolar character, i.e. may exhibit either p- or n-type conductivity depending on the operating conditions. Arylenes vs. arylene bisimides is an instructive example of this approach. Linear or fused polyconjugated aromatic
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compounds are amphoteric in the sense that they can be oxidized and reduced to carbocations and carboanions, respectively.41 If these processes are carried out electrochemically it turns out that their rst reduction peak occurs at very low negative potentials with respect to Fc/Fc+. This dicult reduction is caused by a high p electron density in these molecules (macromolecules) and reects the position of the LUMO level capable of receiving an extra electron or, in other words, indicates their low electron anity (vide supra). Introduction of two imide substituents to the perylene moiety shifts the rst reduction peak towards higher potentials by 0.40.6 V each42 which manifests a strong increase in electron anity. As a result perylene bisimides are excellent molecules for n-channel FET fabrication. The use of additional electron withdrawing substituents can also be envisioned such as cyano, halogen, or peruoroalkyl/aryl groups (see examples of general study43). They not only provide lowering of the LUMO level due to their small size (tight and poorly polarizable valence shell), but also facilitate more dense packing in thin layers of n-type LMWSC as compared to compounds with alkyl or alkoxy groups. This usually drastically limits diusion of oxygen or water which can act as electron traps. As a result, in some cases an air-stable transistor can be fabricated from semiconductors whose LUMO level is above 4 eV.44 More recent research however revealed that air stability of transistors cannot simply be explained by the commonly used combination of thermodynamic and kinetic factors.45,46 Nevertheless, these factors as well as morphological aspects of the thin layers in OFETs can successfully be used for the explanation of the performance of typical devices.
Semiconductors suitable for n-channel FET fabrication can be divided into six groups: fused aromatic compounds, aromatic bisimides, heterocyclic oligomers and polymers, fullerene derivatives and phthalocyanines. Their synthesis will be discussed separately. 4.1 Fused Aromatic Compounds Acenes. Pentacene and its derivatives belong to the most popular group of organic semiconductors, at least if the number of published papers is considered. Unfortunately, neither pentacene nor its compounds can be prepared using a simple synthetic route. Pentacene is poorly soluble in any organic solvent, even reuxing aromatic solvents. Moreover its solutions are unstable, especially in air or upon light exposure due to signicant reactivity of its central ring. Lowering of air sensitivity was at least partially achieved by introducing silylalkenyl groups (for p-type and n-type pentacenes).47 Apart from gaining stability, silylalkenyl substituents make pentacene derivatives solution processable. As denoted earlier, typical compounds bearing aromatic moiety are p-type semiconductors. The general observation why conjugated aromatic moieties are better hole than electron conductors is not yet fully understood.37 On the other hand, for rubrene48 and pentacene49 ambipolar transport has been discovered as well, which is a rare phenomenon.50 The most popular synthetic routes to n-type pentacene derivatives are shown in Scheme 4. Usually functionalized phthalic anhydride or phthalic dialdehyde serve as starting materials.51 They undergo several consecutive reactions, in which, the key stage is the appropriate cyclization step. Depending on the chosen reaction strategy, ring formation is
Scheme 4 General route for synthesis of n-type acenes. Modications leading to asymmetric pentacenes have been skipped for diagram clearance.
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Fig. 6 Views of dierent stacking modes of molecules of a conjugated core and two alkyl substituents: (a) the molecule is viewed from the edge, (b) front view of the molecule, (c) regular stacking with the molecules lying at on the surface, (d) edge-on type stacking of the molecules, (e) molecules in the upright position with no interdigitation of alkyl substituents, (f) upright position with interdigitated alkyl substituents, (g) upright position with interdigitated alkyl substituents and with a tilt angle F with respect to the perpendicular of the surface (in this case the stacking period given by X-ray diraction is shorter than the actual p-stacking distance). The arrows indicate the p-stacking direction.
achieved with FriedelCrafts acylation,51a DielsAlder cycloaddition51b or aldol condensation51c to yield 9,10-pentacenequinone. The latter is then functionalized with silylalkynyllithium reagent to give 9,10-bissilylalkynylpentacene, if functionalization with solubilizing groups is desirable. To prepare unsubstituted pentacene at 9,10-positions, pentacenequinone is reduced with alumina which is then followed by aromatization of the central ring. Finally, to prepare peruoropentacene (N1), the carbonyl group of pentacenequinone is converted into the diuoromethyl one with sulfur tetrauoride and the resulting uorine compound is reduced with zinc. Peruoropentacene (N1) is a dark blue solid, slightly soluble in 1,2-dichlorobenzene. Attaching uorine atoms signicantly lowers the LUMO level of the molecule which can be promptly checked via electrochemical investigations. Tokito et al.51a reported that N1 possesses a very similar reduction peak to fullerene C60 and a similar bandgap to pentacene. Moreover N1 adopts similar crystal packing to pentacene. Transistors fabricated from vacuum deposited N1 lms showed mobility up to 0.11 cm2 V1 s1 and an ON/OFF ratio of 105, however measurements were not carried out in air. Since these parameters are comparable with those of p-type pentacene-based devices, bipolar OFETs were also prepared. The results reveal that a pentacene/N1 couple possesses good properties for bipolar transistors/pn junctions. Thin layers of N1 alone and N1 co-deposited with pentacene on SiO2 substrates have been studied using synchrotron radiation.52 In all cases a high degree of structural order has been evidenced. The structure of typical three layer systems has been found to be very close to that determined for the single crystal. It should also be noted that in all cases the molecules of N1 are in an upright orientation with respect to the substrate (see Fig. 6) as has also been found for pentacene molecules.
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Synthesis of a less uorinated pentacene (N2) derivative, which is soluble, has been reported.51b Since obtaining intermediate pentacenequinone was unfavorable with popular aldol condensation of phthalaldehyde and 1,4-cyclohexadienone, an alternative route via cycloaddition reaction was developed. However, N2 showed p-type conductivity in air. Moreover several bromopentacenes were synthesized and subsequently converted to cyanopentacenes (N3).51c Pentacene properties can be tuned by introducing from one to four cyano groups in combination with various solubilizing groups. Each cyano group lowered the LUMO level by ca. 0.14 eV with respect to that of 9,10-bis(triisopropylsilylethynyl)pentacene (3.35 eV). For N3, the estimated LUMO was 3.90 eV. Anthracene derivatives of similar molecular structure were also prepared (N4a, N4b, N5). 9,10-dichloro-1,2,3,4,5,6,7,8octauoroanthracene (N4b) was synthesized as a starting building block for more sophisticated n-type semiconductors. However, 1,2,3,4,5,6,7,8-octauoro-anthracene (N4a) was found unpromising for further functionalization.53 Using palladium-catalyzed coupling, soluble anthracene derivatives (N5) were synthesized,54 containing branched moieties attached to the triple bond, like in N2 or N3. 2,9-bisperuorobutylpentacene (N8) (Scheme 5), despite its simple structure, also required a multistep preparation, starting from pyromellitic bisanhydride and including two bisacylation steps.55 N8 is somewhat stable in the solid state but its solutions quickly bleach. In this respect it resembles pentacene. Its LUMO level was estimated to be 2.96 eV, which may be the reason why OFETs fabricated from N8 fail to operate in air. N-channel behavior is however observed under vacuum (me = 1.7 103 cm2 V1 s1, ON/OFF ratio = 104, VT = 33 V).
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Scheme 5 Various fused aromatic hydrocarbons as n-type semiconductors discussed in this review.
Similar observation was made while analyzing OFETs fabricated from N9. This compound was prepared from dibromoanthracene via Suzuki coupling.56 The fabricated devices operated under relatively high threshold voltage (me = 3.4 103 cm2 V1 s1, ON/OFF ratio = 104, VT = 75 V).
Heteroacenes. Benzothiophene derivatives (N6, N7) can be obtained by modications of the procedures used for the preparation of N1N5. Functionalizing the heteroacene core is a very convenient way for tuning the properties of these semiconductors. Acenes with a fused thiophene ring seem to be very good candidates for semiconducting materials since, depending on their specic chemical structure, purely p-type, ambipolar or n-type charge carrier transport can be observed. Tang et al. described partially uorinated tetracenothiophenes N6a and N6b.57 N6a exhibited poor hole/electron mobilities under nitrogen probably due to morphological reasons, i.e. the formation of disconnected lms, to quote the authors. N6b was found to possess excellent ambipolar properties in inert atmosphere (N2) but n-channel behavior was not observed in ambient conditions. At the same time, p-type properties were improved after exposure to air. Further research in this domain,58 has mostly aimed at the comparison of dierent types of acenes. Transistors based on N7a and N7b showed poor ambipolar behavior (mobilities o 104 cm2 V1 s1). According to the authors, unsymmetrical substitution aects the crystal packing and may cause polyphasic thin layers to be formed, which is unfavorable for the OFET performance. Chen et al. designed an interesting synthetic route to dithienothiophene substituted with peruorobenzoyl groups59 which involved FriedelCrafts acylation or lithiation of dithieno[2,3-b:3 0 ,2 0 -d]thiophene. Transistors fabricated from this heteroacene exhibited good mobility of 0.03 cm2 V1 s1 and an excellent ON/OFF ratio of 107.
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While sulfur containing acenes are often obtained by simple modications of known reactions, literature examples of incorporating other heteroatoms in acenes are rarer. Unfortunately, preparation of many of these compounds should be considered as a synthetic challenge, most of which probably cannot be overcome by the present solutions due to specic reactivity of their heteroaromatic constituents. Therefore, it is not surprising that several aspects concerning their properties can be discussed on the basis of theoretical studies only.60 Computational investigations with reference to azaacenes (and their application for n-type OFETs/photovoltaic devices) have been carried out61 with comparison to already known peruoropentacene. Peruoropentacene is rather unsuitable for tuning its properties via appropriate functionalization and its OFETs are not completely air-stable.62,63 However, initial calculations showed that some azapentacenes and chlorinated derivatives are very promising LMWSC because of more favorable (small) reorganizing energy and large electron anities. Similar conclusions were reported for branched and cyanated oligoacenes where the role of intermolecular CNHC interactions has been exposed.64 Most recently, particularly interesting diazatetrachloropentacene was found to possess p-type mobility when placed on a pentacene buer layer on pretreated silicon dioxide. No activity has been detected when semiconductor was deposited directly on the dielectric.65 Synthesis and characterization of shorter azaacenes have already been described to some extent. A brief overview shows that the key step in the preparation of such compounds (N10N13) is the condensation of polyfunctional anilines and ketones, i.e. cyclic imidization which is combined with aromatization at the same time. Tonzola at al. prepared a series of diphenylanthrazolines66 (N10) and oligoquinolines67 obtained via condensing 2,5-dibenzoyl-1,4-aryldiamine and methyl-aryl ketone. In the same manner, o-benzenediamime or 1,2,4,5benzenetetramine may be used for two/four-fold imidization
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of 1,2-diketones to yield quinoxaline/pyrazinoquinoxaline derivatives as well as longer molecules with repeated 1,4-diazanaphthalene or 1,4,5,8-tetrazaanthracene units.68 Cyclic voltammetry experiments show that the majority of compounds with one (or more) azaacene unit separated with a polyaromatic moiety undergo a quasi-reversible reduction and their LUMO level approaches 3.80 eV. Interesting bisindoloquinoline was used for fabrication of single crystal FETs (me = 1 cm2 V1 s1, ON/OFF ratio = 104, VT = 0.58 V).66b Very recently, a spectacular synthesis of soluble tetraazapentacene (N11) was reported.69 In order to overcome specic reactivity of nitrogen atoms and the central ring, aromatization of the last saturated ring was achieved with manganese dioxide oxidant. Applying aminophenol hydrochloride instead of diaminobenzene leads to two isomeric triuoromethyltriphenodioxazines (N12a, N12b).70 Both isomers show excellent n-channel behavior in ambient conditions. Better mobility was recorded for N12a (me = 0.07 cm2 V1 s1, ON/OFF ratio = 106, VT = 60 V). Despite the fact that the electron anity of N12a or N12b is ca. 3.67 eV, which is not as high as required for the best n-type semiconductors, the devices retained only slightly diminished mobility after one month to air exposure. The authors claim that dense crystal packing of the semiconductor molecules could prevent oxygen from intrusion. For thin layers obtained by vapor deposition they found highly ordered structures with the same short pp stacking distance of 3.44 A as found in the single crystal. Apart from OFETs, N12a was also tested for photovoltaic applications.71 Azacenes discussed so far had heteroaromatic rings separated from each other, Yamashita reported the synthesis of acenes with two pyrazine rings fused.72 Dicyanopyrazinoquinoxalines (N13) were prepared with two fold aromatic nucleophilic substitution between dichloropyrazines and substituted diaminobenzenes, which was followed by oxidation of the resulting compound with DDQ. While having remarkably low reduction potentials, N13-based OFETs exhibited poor performance, showing mobility of 3.6 106 cm2 V1 s1 and an ON/OFF ratio of 103.
uorinated substituents (N15) have also been synthesized.75 Another interesting feature of phosphorus containing semiconductors is the fact that this atom can bind to metals which is of importance for the semiconductorelectrode interface. Kikuzawa et al. developed the synthesis of 2,5,8,11,14,17hexauoro-hexa-peri-hexabenzocoronene76 (N16) from hexakis(4-uorophenyl)benzene. This uorinated compound is also suitable for the fabrication of n-channel transistors77 showing a mobility of 1.6 102 cm2 V1 s1 and an ON/OFF ratio of 104. Finally, Knoevenagel condensation of truxenone and ethyl cyanoacetate resulted in the preparation of N17, whose electron anity was estimated to be 3.9 eV.78 With the use of a similar reaction, soluble and polymerizable semiconducting compounds based on the indenouorenebis(dicyanovinylene) core (N18) were prepared and applied in the fabrication of devices showing mobilities up to 0.16 cm2 V1 s1 and exceptionally high ON/OFF ratios (108). These solution processed devices retained their stability for at least 5 months.79,80 Thin layers (6065 nm) of N18 and its polymeric analogue form highly crystalline structures when deposited on a OTS (octadecyltrichlorosilane) treated silicon substrate and then annealed at 150 1C for 30 min under vacuum. In both cases the X-ray diraction analysis reveals a lamellar like structure with a period of 25.6 A for N18 and 21.4 A for the polymer. The molecules of N18 stand upright on the substrate while the polymer has the so-called edge-on arrangement (see Fig. 6e and d respectively). It should be noted that a 3.1 A pp stacking distance has been found in the structure of N18 which is one of the shortest measured for conjugated molecular semiconductors in which the p-stacking distance is usually in the range of 3.43.8 A.79 It should be noted that N18-related dihalogenated precursors are also very promising building blocks for polymeric semiconductors or introducing solubilizing groups.81 4.2 Aromatic bisimides From the formal point of view, aromatic bisimides belong to fused aromatic compounds; however the number of papers concerning their application in organic electronics exceeds that of articles devoted to any other family of n-type semiconductors. For this reason we discuss them here as a separate group. Bisimides show some signicant advantages with respect to other organic semiconductors used in the fabrication of n-channel FETs. This results from a combination of several factors, which not only are limited to excellent charge carriers mobility in bisimide thin layers and chemical stability of these compounds in transistors operating in air after appropriate functionalization of their aromatic core but also extend to their excellent thermal stability and interesting optical properties. Moreover, in most cases they can be prepared from cheap commercial reagents. The very rich literature on luminescent properties of these compounds and their application for solar cells is, however, beyond the scope of this paper. Aromatic bisimides may be divided into two classes of compounds, namely 6-membered ring arylene bisimides and 5-membered ring acene bisimides. The latter are represented by a few examples only and will be discussed at the end of this subsection.
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Miscellaneous aromatic compounds. The search for compounds showing easily tunable electronic properties, led Dienes et al. to the synthesis of dithieno[3,2-b:2 0 ,30 -d]phosphole (N14)a heteroacene with a phosphorus atom.73 A similar pyrrole derivative was also recently described.74 N14 was prepared by coupling bis(3-bromo-2-benzothienyl) with phenyldichlorophosphane. Probably the most important feature of a phosphole is the rather versatile reactivity of the phosphorus atom, which may be oxidized or alkylated. Taking into account their redox properties and some aspects of their crystal packing mode, materials based on phosphole derivatives may exhibit high charge carrier mobility after their optimization. In the solid state structure of N14 and its derivatives the p stacking distance of neighboring molecules ranges from 3.46 to 3.78 A which is favorable for the carriers mobility in the resulting transistors. Initial theoretical and electrochemical data indicate that N14 and its related compounds are promising materials for n-channel and ambipolar semiconductors. Apart from that, phospholes with
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Scheme 6
Synthesis of core-unsubstituted naphthalene and perylene bisimides.
Simple naphthalene and perylene bisimides can be prepared from commercially available bisanhydrides and primary amines (Scheme 6). Condensation is typically carried out at elevated temperature in high boiling solvents like DMF, NMP or m-cresol (see for example82). Alternatively molten solids (imidazole, isoquinoline or quinoline) may be used as reaction media, which is more suitable for amines with steric hindrance and some electron decient amines where the reaction in solvents like NMP may give low yields. To catalyze the reaction and to enhance the solubility of the bisanhydride, zinc acetate dihydrate is added. The same can also be achieved when a proton donor is applied. In this case a carboxylic acid is used as a co-solvent or amine is replaced by its hydrochloride. This strategy is useful for electron decient amines. Bisimides are resistant to hydrolysis and in the case of their reaction with reactive primary amines the process can be carried out in water. In opposite to most other classes of compounds described in this section, the behavior of arylene bisimides in transistors is purely n-type, regardless of the type of N-substituent with only two exceptions, to best of our knowledge. In the rst case, the p-type behavior was governed by bulky dehydroabietyl substituents.83 In the second one, ambipolar behavior was observed for thiophene core-substituted naphthalene bisimides (N24b, n = 2, 3).84 Time of ight measurements on the other hand show both hole and electron mobility.85 This is in agreement with theoretical simulations which show that aromatic bisimides could even be better hole than electron transporters provided that their ionization potentials would not be so high.86 Solution processability of arylene bisimides is of crucial importance for their application in OFET fabrication. For this reason solubilizing alkyl or alkylaryl groups are frequently introduced as N-substituents. The redox behavior of aromatic bisimides with cores larger than naphthalene is, in this case, only weakly dependent on the type of N-substituent (alkyl or alkylaryl). Two reduction peaks are characteristic for these compounds which originate from consecutive reductions of the two imide groups to give a radical anion in the rst reduction and a dianion in the second one.42 The position of the rst peak, whose onset determines the LUMO level, is essentially independent of the size of the core and leads to the electrochemically determined LUMO level of ca. 3.8 eV with respect to the vacuum level, for nearly all compounds of this group, with an exception of naphthalene bisimides.15 On the contrary, the spacing between the rst and the second reduction peak decreases with increasing core size. Larger cores diminish Coulombic repulsion between two negative charges, and for terrylene and quaterrylene bisimides the two reductions occur at the same potential.42
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It should also be noted that the N-substituents have relatively little eect on the optical properties of bisimides and more particularly the UV-Vis bands originating from the core transitions. In the case of alkylaryl substituents, this implies a rather poor conjugation between the core and the aromatic ring of the substituents.87 Electrochemical and optical properties of these compounds are however strongly aected by core functionalization with electron withdrawing groups. A signicant lowering of their LUMO level can be achieved in this manner (for a representative study see ref. 88). n-Type behavior of aromatic bisimides was rst reported for N,N 0 -diphenyl-3,4,9,10-perylenetetracarboxylic bisimide by Horowitz et al.39 The fabricated transistors were tested in air and stopped operating after 23 days due to oxygen intrusion. A strong eect of the semiconductor purity and oxygen exposure on charge carrier mobility in perylene bisimide thin lms was also demonstrated.89 Inuence of other gas molecules on overall performance of the devices was reported as well.90 Perylene and naphthalene bisanhydrides also show semiconducting properties, but their performance in real devices is rather poor. However, it should be noted that the rst results reported for naphthalene bisanhydride (N19a) were among the best at that time.91 In the test transistor the mobility of the charge carriers, initially equal to 3 103 cm2 V1 s1 diminished 10100 times upon exposure to air or moisture. Its perylene analogue (N19b) was found to be even worse (me = 105104 cm2 V1 s1) because of poorer overlap of the p-systems in the adjacent molecules, however many additional interesting features were noted.92 OFETs based on this semiconductor operated in vacuum or dry air. N-type behavior disappeared upon action of moisture, even if only traces of water were introduced to the N2 environment. However the eld eect in the n-type conguration was slowly regained upon drying the device in vacuum. Perylene bisimides. Perylene bisimides (PBIs) have been known since 1913 and due to their intensive red color and uorescent properties became popular dyes.93 They are usually poorly soluble due to strong interactions between aromatic cores originating from their p stacking. Bisimides with n-alkyl substituents show rather limited solubility, cycloalkyl and aryl derivatives are also sparingly soluble. The problem can be resolved either by introducing branched alkyl substituents or by adding solubilizing/electron withdrawing groups at cost of a longer synthetic path. As demonstrated by electrochemical investigations the rst reduction potential of perylene bisimides is little aected by
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ordinary alkyl or aryl substituents. The LUMO level, however, of such bisimides is slightly too high to provide full air stability. Nevertheless, commercially available N,N 0 -dioctyl3,4,9,10-perylenetetracarboxylic bisimide (N20a, PBI-C8) and N,N 0 -ditridecyl-3,4,9,10-perylenetetracarboxylic bisimide (N20b, PBI-C13) are among the most studied n-type semiconductors. Initial studies94 of three alkyl perylene bisimides encouraged to test their carrier mobility in OFETs. N20a-based devices were found95 to exhibit excellent mobility under N2 (0.6 cm2 V1 s1; ON/OFF ratio > 105, VT = 75 V), but ceased to operate in air. Concerning the structure of N20a layers deposited on the substrate, a lamellar arrangement with a period of 20 A is observed in symmetrical reection geometry of X-ray diraction, revealing a high anisotropy of the structure. The found period suggests that the molecules are signicantly interdigitated and tilted with respect to the substrate while the pp stacking direction is parallel to the surface (see Fig. 6). It should be noticed, in addition, that the oriented structure exhibits the same crystallographic distances as those found by powder X-ray diraction measurements, indicating that the crystalline structure is not modied during the process of the layer deposition. Transistors made of pentyl N-substituted perylene bisimide deposited on Al2O3 dielectric show similar chemical and electrical behavior to N20a. In this case, the mechanism for the threshold voltage shift due to oxygen intrusion was proposed.96 Continuation of the research97 revealed the importance of the lm-growth rate. Under well established conditions the carrier mobility up to 1.7 cm2 V1 s1 with the ON/OFF ratio exceeding 107 was achieved for N20a deposited on SiO2 surface covered with a thin layer of hydrophobic poly(a-methylstyrene). Using polymer electrolyte dielectric gave much lower mobility values.98 N20b (a longer analogue of N20a), was rst reported as used in an ambipolar heterostructure OFETs as a counterpart of pentacene,99 pentathiophene100 and later as a counterpart of oligophenylenevinylene derivatives.101 The last two are also examples of molecules used in light emitting devices. The performance of the pentacene/N20b junction transistors was improved about 3 orders of magnitude in recent years.102 Recently, successful application of CYTOPTM (a commercially available peruorinated polymer) dielectric was reported for the same pn junction.103 Comparable improvement is denoted for n-channel N20b-based transistors. In a transistor with the poly(methylmethacrylate) (PMMA) dielectric layer, the measured mobility was 1.7 102 cm2 V1 s1, with a very low threshold voltage of 0.2 V, but also very poor ON/OFF ratio of 30.104 By adjusting the device annealing temperature it was possible to increase the mobility to 0.6 cm2 V1 s1 (ON/OFF ratio = 107, VT = 44V)102a and nally to remarkable 2.1 cm2 V1 s1 (ON/OFF ratio = 4.2 105, VT = 60 V).105 This improvement can be rationalized by high crystallinity of N20b layers which exhibit a period of 25.7 A perpendicularly to the substrate. This distance corresponds exactly to the c period of the bulk triclinic crystalline structure. The crystallinity is improved under annealing at 140 and 200 1C giving few micrometres thick crystals whose morphology changes from an ellipsoidalball-like to a tile-like one. New applications of bisimides
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described in this paragraph such as constructing logic circuits were also reported.106 Recent research devoted to the application of N-alkyl perylene bisimides in the fabrication of electronic devices focuses mainly on the optimization of thin semiconductor layers deposition and the modication of the semiconductor/ dielectric interface. The latter also involves the search for new dielectrics not only for improving the eld eect but also for the sake of air stability. In the case of the N20b lms, which are obtained by organic vapor phase deposition (OVPD), slow growth rates seem to be crucial for increasing the ON/OFF ratio and lowering the voltage threshold of the transistor107 which is in agreement with earlier report.97 In particular, the morphology of crystals signicantly changes as a function of the growth rate; for slow rates large crystalline needles are obtained on top of the layered structure while for faster ones, small and uniform grains are formed. It is evident that the rate of the thin layer growth has a profound inuence on the size of the crystallites and the compactness of the layer. It has recently been demonstrated that an appropriate sequence of applied growth rates may lead to a signicant improvement in the device stability in air.108 Semiconductors performance is also dependent on temperature of their deposition or thickness of the layer.109 Optimization of the semiconductor/dielectric interface seems to be of equal importance. Typically used n-type organic semiconductors seem incompatible with untreated silicon dioxide surface as a result of the presence of electron trap sites on its surface. Kumaki et al.110 pointed out the necessity of investigating water and oxygen inuence not only on the semiconductor but also on the dielectric. It was found that water deprotonates SiOH groups (in an acidbase reaction) more eciently than O2 does (in an electrochemical reaction). The presence of SiO groups is responsible for positive shifting of the threshold voltage. In the worst case it may even lead to a total disappearance of the n-channel behavior.110,111 This issue is also valid for p-type transistors. Nowadays, it seems that appropriate modifying of the dielectric surface may have a very benecial eect on the device performance. Popular surface treatment reagents like OTS or others also enable a better contact between the dielectric and the semiconductor. It was also proven, that on the treated SiO2 surface, the orientation of semiconductor molecules may be more uniform than on the untreated one. To illustrate this point we can refer to a recent study focused on layers of 3,4,9,10-perylenetetracarboxylic bis-benzimidazole.112 According to the authors, the stacking mode of the molecules is dierent depending whether the oxide substrate has been treated or not with OTS molecules. Moreover, the degree of orientation of the molecules can be highly improved when the OTS sublayer is itself fully ordered. The best performances of the resulting transistors are obtained when the molecules are deposited at 150 1C on the ordered OTS treated oxide surface. In such a case ca. 90% of the molecules stand upright on the substrate (Fig. 6e) and no trapping of charge occurs due to possible leaks with untreated oxide or due to interactions with dangling silanol groups in case of a disordered OTS layer.
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Modication of the SiO2 dielectric surface may also lead to a change of grains size in the deposited lms as it was demonstrated for N20a.113 In this example enlarging the grain size limited the semiconductor contact with ambient environment and therefore the device of moderate mobility of 5.6 103 cm2 V1 s1 was air stable with no necessity of additional passivation. What is more, surface of small-grained semiconductor more easily absorbs water or oxygen. Excellent results were obtained with the use of hexamethyldisilazane (HMDS) or thermal surface treatment.114 It seems that promising increase of air stability may also be achieved by simple casting of an additional hydrophobic polymer113b,115 like polystyrene or PMMA on the SiO2 surface. Thanks to these modications N20a- and N20b-based devices retained reasonable mobility after at least 3090 days of air storage, whereas transistors with poly(vinyl alcohol) or poly(vinyl phenol) dielectrics showed total loss of activity after 20 days of air exposure. The state of art was reached by combining dielectric surface treatment with OTS, gold electrode modication with thiols and application of an appropriate 3-step growth rate of the semiconductor lm to fabricate N20a devices exhibiting mobility over 0.1 cm2 V1 s1 after 70 days of air exposure.108 Another example worth to be mentioned concerns the application of the hole transporting interfacial layer between SiO2 and semiconductor layer.116 Much fewer studies are devoted to PBIs with branched alkyl substituents as n-type materials, but these compounds are very interesting for their uorescent properties (see for example ref. 117). Branched substituents are responsible for the decrease of the intermolecular p-stacking interactions and therefore the solubility of PBIs containing these substituents is usually high.82c This increased distance between aromatic cores is however mostly unfavorable, from point of view of vapor depositing of a thin layer in transistor, since the intrusion of oxygen is theoretically even faster than in N-alkyl substituted PBIs and gives no possibility of the device regeneration.118 Moreover PBIs with branched substituents may be prone to form disoriented lms similarly as in the case of a more planar cyclohexyl analogue which also failed to operate in air.119 Despite these inconveniences, the discussed derivatives can be used as solution processable n-type materials not only for transistors fabrication (see for example ref. 120). Examples of PBIs with symmetrical83 or unsymmetrical15 substituents are rare. In both cases the devices were fabricated in air and in the case of the latter also studied in air. Branched substituents are also used in poly(perylene bisimide acrylate) and block copolymers of unsymmetrical PBIs with styrene, obtained with living radical polymerization.121 Thin lms of these polymeric semiconductors show, after annealing, moderate charge carriers mobilities.122 Experiments concerning perylene bisimides attached to much more rigid polyisocyanopeptide arrays were also carried out.123 PBIs with phenyl capped longer alkyl groups are seldom discussed as n-type materials.85b Examples of air stable pn junctions transistors based on N,N 0 -bis(2-phenylethyl)3,4,9,10-perylenetetracarboxylic bisimide were reported (me = 0.11 cm2 V1 s1; ON/OFF ratio = 3.3 105, VT = 29V).124 It is worth to note their air stability since the
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device parameters barely changed after over 80 days of their air exposure, despite the lack of electronwithdrawing groups in these molecules. This result may be assigned to favorable grain size of the deposited semiconductor. Aryl bisimides seem inferior to linear alkyl counterparts. Nevertheless, some features regarding these molecular semiconductors are denitely worth mentioning like being used for single molecule transistor125 or fabrication of air-stable single crystal OFET from N,N 0 -bis(2,4-diuorophenyl)-3,4,9,10perylenetetracarboxylic bisimide126 with the mobility of 0.006 cm2 V1 s1. Modications of the phenyl group are a quite simple choice for lowering the LUMO level of the molecule without necessity of core functionalizing. Applying pentauorophenyl substituent instead of the phenyl one in PBIs lowers the LUMO level by ca. 0.14 eV127 and, at the same time, increases their solubility, thus allowing the fabrication of transistors with a spin-coated active layer.128 Detailed studies on uorinated aryl substituents were carried out by Bao et al. showing superiority of bisimides with a higher number of uorine substituents.129 Valence electronic properties of monouorophenyl PBIs were also analyzed.130 Finally, low charge carrier mobilities of perylene bisimides with pyridyl substituents were reported.131 The power of electron withdrawal via nitrogen substituent is signicantly limited if the goal of adjusting LUMO level is concerned. Highly uorinated alkyl groups lower the LUMO level by ca. 0.15 eV to approximately 3.95 eV when based on rst reduction potential onset.132 However, the advantage of more dense crystal packing must also be taken into account in this case. Thus transistors based on N,N 0 -bis(1H,1H-peruorobutyl)-3,4,9,10-perylenetetracarboxylic bisimide show high mobilities (up to 0.72 cm2 V1 s1; ON/OFF ratio = 2 105, VT = 27 V) little aected by air exposure.132 Interestingly, heptauorobutyl substituent seems optimal as compared to its shorter or longer analogues.133 This applies also to bisimides with cyanated core.46 Electron anity, sucient for air stability, is also achieved with triuoromethylbenzyl44,134 or triuoromethoxybenzyl group.135 Nevertheless, the number of air stable bisimides without core functionalization is small. The search for more ecient and environmentally stable semiconductors led to the necessity of functionalization of the core with electron withdrawing groups (examples depicted on Scheme 7). This procedure also leads to a signicant solubility enhancement in comparison to the parent compounds. For example, N20a is barely soluble in any solvent whereas N21a (PBI-8CN2) is suciently soluble to be puried with chromatographic or crystallization techniques.136 The obvious drawback of such derivation is a longer synthetic path36 which involves bromination of bisanhydride under harsh reaction conditions, which in addition is not completely selective.137 Therefore, after subsequent imidization, regioisomers need to be separated. Finally introduction of cyano or peruoroalkyl groups proceeds with copper mediated reactions which are known to be sensitive to reaction conditions. Large synthetic versatility of the approach described above must be pointed out since electron donating substituents may also be introduced from the same halogenated precursor (for the synthesis and mobility studies see for example ref. 138).
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Scheme 7 Functionalization of the core in perylene bisimides.
Dicyanated N-octyl perylene bisimide (N21a) was tested in n-channel136 and heteroambipolar139 OFETs. The former operated in air showing mobility of 0.14 cm2 V1 s1; ON/OFF ratio = 1.2 103 and VT = 1.6 V. Solubility of PBI-8CN2 allowed fabricating thin layers by spin-coating, drop-casting or jet-patterning techniques.140 In a recent study, layers of N21a have been deposited from solution by jet patterning. It is noticeable that the structural organization of the obtained layers is quite similar to that found in layers fabricated by vapor deposition. The only marked dierence is the degree of orientation which is lower when the solution processing is applied (o scans lead to FWHM (full width at half maximum) of 0.071 instead of 0.031). Anyhow in both cases the orientation is remarkable. This makes solution processing a very promising method taking into account its simplicity as compared to OVPD. The measured mobilities were however about an order of magnitude lower as compared to transistors with evaporated layers which was a consequence of less ordered supramolecular organization as detected by XRD investigations. Very similar values were obtained for the devices with CYTOPt dielectric after gold electrode treatment.141 Dicyanated bisimide with 1H,1H-peruorobutyl N-substituent (N21b, PBI-FCN2) was reported by Jones et al. as solution processable, highly ecient n-type semiconductor.142 OFETs fabricated with vapor deposited lm of this semiconductor showed very high mobility of 0.64 cm2 V1 s1 (ON/OFF ratio = 104 and VT = between 20 and 30 V). Recently, N21b was examined in transistors obtained by solution processing143 and was found about ten times superior to N21a in terms of carrier mobility.140b Another interesting report discussed the use of the single crystal of N21b on SiO2PMMA dielectric.144 Mobilities from 1 to 6 cm2 V1 s1 in vacuum and up to 3.6 cm2 V1 s1 in ambient conditions were observed. These excellent values could be rationalized by the lack of grain boundaries present in vapor/solution deposited layers and random crystallite orientation. OFETs with low threshold voltage, based on N21b semiconductor and selfassembled dielectric monolayer were also described.145 Both N21a and N21b are commercially available from Polyera Corporation under the trade name ActiveInkt N1200 and ActiveInkt N1100, respectively.
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Inuence of the core substitution on electrical properties of PBIs was also investigated for halogen substituents.36 Dierences in overall electrical transport properties, measured for these derivatives, originate mainly from morphological aspects and crystal packing of the molecules.146 In general cyano substituted PBIs are clearly superior to tetrachloro and dibromo ones. Bisimides with dibrominated cores (i.e.; N22a, PBI-8Br2) are direct precursors for the electronwithdrawing group introduction, but fail to act as highly eective semiconductors. In fact, their low mobility of ca. 105 cm2 V1 s1 is a result of poor quality of the deposited lms whose X-ray diractograms show only rst order reections with essentially no texture eect. Moreover these compounds are prone to substantial decomposition during sublimation. Interestingly, the tetrachloro derivative, despite a bigger core torsional angle, is more densely packed, and the lm quality matches that of cyanated derivatives. The mobilities measured for N-octyl tetrachlorinated bisimide (N22b, PBI-8Cl4, Scheme 9) layers of the order of 103 cm2 V1 s1 are somewhat satisfactory, conrming expectations from previous studies.147 Studies on dicyano core-substituted PBIs, with various uorinated N-substituents were carried out by Schmidt et al.133 and Weitz et al.46 In addition the former research group examined bisimides with uorinated cores.148 Transistors fabricated from these semiconductors showed exceptional ON/OFF ratios approaching 107. Fluorination of the core was achieved by Halex process from dibromo- or tetrachlorinated precursors. Rather low nucleophilicity of uoride anion led, however, to formation of many partially uorinated side products, resulting in low yields. Synthetic problems connected to other halosubstituted bisimides were caused by low reactivity of some uorinated amines and low solubility of amic acid intermediates.133 The new halogenated PBIs were again found inferior because of the core plain twisting. However the performance OFETs, based on N,N 0 -bis(1H,1H-peruorobutyl)-3,4,9,10-perylenetetracarboxylic bisimide, was improved to 1.42 cm2 V1 s1; ON/OFF ratio of 106 and VT of 3947 V, after treating of SiO2 surface with OTS. Finally, functionalization of the core with peruoroalkyl groups resulted in air-stable PBIs with unusual unsymmetrical core twisting (N21c).149
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Naphthalene and other arylene bisimides. At the beginning, naphthalene bisimides (NBIs) have been less frequently studied than PBIs as far as the number of published papers is considered. However, they have recently gained increasing attention, mainly due to their better processability. Typical naphthalene bisimides are white or yellow solids for N-alkyl and N-aryl substituents respectively and in opposite to their perylene analogues do not posses strong uorescent properties. Their synthesis does not require as harsh conditions as that of PBIs because of higher reactivity and solubility of their parent bisanhydride. The LUMO levels of NBIs with alkyl substituents are close to the LUMO levels of the corresponding PBIs. However, unlike for arylene bisimides of larger size, inuence of the nature of the N-substituent (alkyl vs. aryl) on the rst reduction potential is clearly distinguishable.15 The history of alkyl NBIs semiconductors started unfavorably despite excellent n-type behavior under vacuum because of complete air inoperability of N-alkyl derivatives (N23a) in contrast to their uorinated counterparts as reported by Katz et al.150 Such observation was assigned to poor packing density of hydrocarbon tails, allowing oxygen intrusion and immediate deactivation of the transistors. Again tight 1H,1Hperuoroalkyl groups served as a barrier preventing from contamination and in the same time lowered the LUMO level of the molecule by about 0.14 eV in comparison to N-alkyl NBIs. In subsequent years the interest in NBI-based OFETs was rather scarce151,152 although their promising applications as components of sensors or biosensors have been proposed.153 This however changed in 2007, when Jones et al. reported optically transparent OFETs based on mono and dicyanated N-octyl naphthalene bisimides (N24a, NBI-8CN2).154 The synthesis was based on the same procedures as in the case of PBIs (Scheme 8). The LUMO level of N24a was ca. 0.3 eV lower than that of the monocyanated derivative, as determined by electrochemical studies. Transistors fabricated from N24a exhibited high carrier mobility both when operating in vacuum and in air (0.15 cm2 V1 s1 and 0.11 cm2 V1 s1, respectively) and ON/OFF ratio of 103. OFETs based on monocyanated derivative showed limited stability upon air exposure in terms of IV characteristic, but under vacuum showed the ON/OFF ratio of 105. In the N24a-based devices the o current intensity was signicant. Both cyano derivatives were used in a comparative study with their PBIs analogues.36,146 Interesting, highly soluble, thienyl core substituted bisimides (N24b) were also prepared via Stille coupling and used for fabricating of n-type or ambipolar FETs.84 A signicant LUMO shift was gained with relatively mild electron acceptors.
Devices fabricated from these semiconductors exhibited however low parameters. No explanation was provided by the authors for this weak performance; however it may be associated with a poor supramolecular organization of the layer. In the same year, attention towards N-benzyl type NBIs was risen which resulted in several papers on these compounds in 2008. Kao et al. synthesized N,N 0 -bis(4-triuoromethoxybenzyl)-1,4,5,8-naphthalenetetracarboxylic bisimide (N23b) and tested it in bottom contact transistors.155 They showed reasonable mobility of 1.6 102 cm2 V1 s1, ON/OFF ratio of 8.6 105, VT of 5.5 V and good air stability without any surface treatment. Some parameters were improved with application of molybdenum source/drain electrodes.156 Comparable devices were fabricated from solution processed NBI with unsymmetrical uorinated benzyl N-substituent.157 Further, remarkable results were obtained by See et al. who studied uorinated alkyl benzyl bisimides.158 A benzyl type NBI derivative with very long uorocarbon chain (N23c) was used to construct air stable OFETs even without dielectric surface treatments. The highest measured mobility was 0.57 cm2 V1 s1 and ON/OFF ratios exceeding 108 are ones of the best ever reported. The compound with two triuoromethyl groups on the benzyl part of the molecule gave slightly worse transistor parameters. It was implied that in the case of benzyl type NBIs the key parameter to improve the charge carriers mobility in thin layers lies in the optimization of the crystal packing rather than in adjusting of electronic factors. These conclusions seem dierent than the ones resulting from the studies of its triuoromethylaryl analogue (N23d).159 Later, very good results were reported for exible OFETs based on uorophenylethyl substituted NBIs.160 Sun et al. constructed bottom contact OFETs based on NBIs substituted with dierent peruorinated moieties and investigated the surface treatment eect on the device performance.161 More sophisticated naphthalene bisimides bearing 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical group were also reported.162 Recently, exceptional results were gained for N,N0 dicyclohexyl-1,4,5,8-naphthalenetetracarboxylic bisimide-based transistors.163 Mobilities up to 6 cm2 V1 s1; ON/OFF ratio of 6 108 and VT of 58 V (slightly worse when recorded in air), were achieved with careful optimization of the thin lm morphology. Other than PBI and NBI arylene bisimides are much rarer in literature. Their structures are shown on Scheme 9. Terrylene and quaterrylene bisimides were prepared through coupling of two monoimide units in molten alkali.164 N,N 0 -dipentyl3,4,11,12-terrylenetetracarboxylic bisimide (N25) was used for transistors fabrication (me = 7.24 102 cm2 V1 s1;
Scheme 8
Functionalization of the core in naphthalene bisimides.
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Scheme 9 Miscellaneous aromatic bisimides studied as active components of n-channel OFETs.
ON/OFF ratio = 1.22 104; VT = 16 V).165 From structural and morphological points of view, the best compromise leading to regular uniform morphology and improved crystallinity, as checked by AFM and X-ray diraction measurements, was to vapor-deposit the molecules on a substrate heated at 140 1C. In these conditions layers with a period of 15.8 A, showing good crystallinity were obtained. In a recent study charge carrier mobility in N25 was also examined as a function of temperature.166 High mobility in coronene bisimides (N26) was established by space-charge-limited current (SCLC) experiments167 and by pulse-radiolysis time-resolved microwave conductivity technique.168 Synthesis of these bisimides was achieved with biscyclization of parent dialkynyl perylene bisimides with diazabicycloundecene (DBU) as a base. The largest reported arylene bisimidetriperylene bisimideconsisting of 19 six-membered carbon rings in its core and six imide groups at the edges can be considered as a model compound of n-type graphene ribbons.169 Smaller analogues,170 including bisanthracene bisimides171 which are dyes with near-infrared absorption properties are also examples of compounds which were discovered in the most recent years. Bisimides with 5-membered imide rings are also scarce. Anthracene bisimides were prepared by two-fold cycloadditions between octabromodurene and maleimides upon action of sodium iodide, followed by aromatization.172 Route for light sensitive, methoxy core substituted counterparts was also introduced.173 Modications leading to dicyano anthracene bisimide (N27) were proposed by Wang et al.174 This compound was found suitable for fabricating air stable OFETs with mobility up to 0.02 cm2 V1 s1; ON/OFF ratio = 2 107; VT = 15 V. Small core pyromellitic bisimides (N28) exhibited similar charge carrier mobilities.175 4.3 Heterocyclic oligomers and quinoidal compounds
Thiophene is a heterocyclic compound whose ring can withstand harsh reaction conditions (for example strongly acidic media) in which other heterocycles decompose or polymerize, therefore thiophene derivatives are very versatile reagents. In addition, the presence of the sulfur atom does not induce a signicant decrease in the solubility of thiophene oligomers. These two factors combined also enable easy tuning of the thiophene oligomers properties. As a result hundreds of papers on oligo- and polythiophene-based semiconductors have been published.176 Appropriate functionalization may lead to either p-type or n-type or even ambipolar thiophene derivatives. Studies on other than thiophene-based n-type semiconducting heterocyclic oligomers are scarce as it will be shown, often due to their dicult solution processability and poor performances as far as the charge carriers mobility is concerned. In addition to oligomers, other related conjugated small molecules will be presented in this subsection. Thiophene oligomers. Oligomers of thiophene are widely known as excellent p-type semiconductors. However, by introducing appropriate electron withdrawing groups it is possible to switch their hole-type conductivity to the electrontype one. In selected cases their ambipolar character can be maintained. In general n-type oligomers of thiophene are synthesized via Stille coupling and to a lesser extend through Suzuki coupling. Both reactions are known for their versatility, although the Stille coupling is a more favorable choice for coupling two thiophene units possessing electron withdrawing substituents whereas the Suzuki coupling for merging phenyl and thiophene units, as judged from the analyzed literature data. Co-oligomers of thiophene with other heterocycles and benzene will be described in next subsection. General procedure for synthesis of these derivatives is illustrated in Scheme 10. One of the rst investigations on n-type thiophene mono/ dicyano dimers and trimers were reported by Hapiot et al.177 In subsequent works it was demonstrated that introducing cyano groups to hexathiophene implied tuning of the oligomer electrical transport properties towards n-type conductivity.178 The obtained compounds were characterized in detail by NMR. In addition their crystallographic structure was established.179 The cyano group can also be used as a part of di- or tricyanovinyl moiety. a,o-tricyanovinyl substituted oligothiophenes are prepared upon action of dilithiated
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This class of semiconductors has been very extensively studied as clearly reected by the available literature data. Availability of precursors, possibilities of their functionalization in view of precise tuning of the electronic properties makes them attractive candidates for application in organic electronics and related disciplines. Papers on n-type oligomeric semiconductors are, in their overwhelming majority, devoted to thiophene oligomers. This is caused by several reasons of crucial importance.
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Scheme 10 General route to thiophene oligomers via CC coupling reactions. The most popular ways of introducing electron withdrawing groups to terminal thiophene units are also denoted. Construction of oligomers is illustrated with Stille coupling reaction.
oligothiophene on tetracyanoethene (TCNE). Such derivatives have low lying LUMO levels, suitable for n-channel FETs, as calculated from the onset of their rst reduction potential. In the case of longer oligomers they also exhibit low band gaps.180 More recent studies have demonstrated that trimers and tetramers show moderate n-type charge carriers mobility whereas hexamer is an ambipolar semiconductor.181 According to the available literature data, the most popular way to induce n-type charge carrier transport in thiophene oligomers is the use of peruoroalkyl or peruoroaryl substituents. Basically the introduction of peruorinated substituents is achieved in a similar manner as the introduction of cyano groups via copper mediated reactions with aryl halide in DMF or DMSO. Then subsequent bromination with N-bromosuccinimide (NBS) is carried out. The electron decient thienyl bromide unit is then coupled with a trialkylstannylthiophene unit to yield an oligomer, usually tetramer or hexamer. One of the rst derivatives obtained in this way with high yields was a,o-peruorohexylhexathiophene which showed the mobility of 0.02 cm2 V1 s1 measured in the n-channel FET conguration.182 Transistors based on a series of oligomers with the same substituent (from dimer to hexamer) exhibited a slightly better performance, reaching the mobility of 0.048 cm2 V1 s1 for the tetramer (N29a).183 Unfortunately the retrieved data suggested that despite the presence of electronwithdrawing groups and dense crystal packing a,o-peruoroalkyloligothiophenes transistors could not be prevented from destabilization in air. This nding was then independently conrmed.184 The performance of N29a has later been optimized185 and transistors prepared by vacuum
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deposition showed mobilities up to 0.22 cm2 V1 s1 (ON/OFF ratio = 106) whereas those processed from solution 103 cm2 V1 s1. In the same work the eect of substitution regiochemistry has also been studied. Peruoroalkyloligothiopenes showed a high thermal and chemical stability, similar positions of the LUMO levels (ca. 3.3 eV) and strong p stacking of the molecules. At this point, it is interesting to more deeply discuss the structural characteristics of ordered layers obtained with functionalized oligothiophenes which are deposited on substrates either by evaporation or solution casting. First of all it must be noted that there are not big changes in the resulting arrangement, independently of the type of the substituents (peruorated or hydrogenated). The obtained layers are highly ordered with a lamellar stacking mode along the crystallographic a-axis, in which the oligothiophenes cores and the substituent tails are organized in alternate and distinct regions. Accordingly, the obtained period along the a-axis is quite large not only because of the respective length of the molecules but also due to the fact that the structure of each sublayer is organized in a herringbone like arrangement. All these compounds give highly textured structures. The crystallinity and orientation can be further improved by increasing the deposition or annealing temperatures. However, these temperatures have to be optimized, because in some cases at temperatures higher than 70 1C, the crystallographic structure and the morphology may start to degrade. Phenylene-thiophene oligomers, terminally functionalized with peruorinated groups also show good OFETs performance.37 In particular, the devices based on N30 exhibited excellent transistor memory eect.
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In the case of peruoroaryl substituent, n- and p-type activities have been observed within the same series.186 If this group is attached to two terminal positions of the oligothiophene moiety, the resulting compound acts as n-type semiconductor in the FET conguration. To the contrary, inserting a tetrauorophenylene spacer between the two thiophene units (which become terminal in that case) leads to a p-type semiconductor, despite the fact that both types of molecules have very similar LUMO levels (from 2.81 eV to 2.85 eV). Apart from aecting the crystal packing and intermolecular orbital overlaps, it seems that the terminal electron withdrawing groups better shield the channel from water/oxygen intrusions. Moreover, the electronic nature of the end groups may also facilitate appropriate charge separation, i.e. the negative charge for peruoroaryl and the positive one for thienyl end groups. It should be noted that such regiochemical switching has not been observed for peruoroalkyl substituents.185 The nature of this phenomenon is still not totally clear.187 Transistors based on N29b exhibit excellent parameters when tested in argon atmosphere (m = 0.43 cm2 V1 s1, ON/OFF ratio > 108). They may be, however, drastically aected by the temperature of the substrate deposition. Shorter oligomers with larger peruoroaryl groups have also been reported,188 showing essentially the same LUMO levels. The presented examples show that uorine or peruorinated substituents alone have a limited electron withdrawing ability since even in peruoropentacene the electrochemically measured LUMO level is barely below 3.5 eV.51a This may be due to mainly inductive character of such electron withdrawal. In peruoroalkylgroups and peruoropentacene the inductive withdrawing eect is also partially compensated by the donating eect from the uorine atom lone electron pairs. Further studies189 revealed the advantage of acyl group substituents. Carbonyl group is a very strong electron decient unit, but in opposite to peruoroalkyl group, it conjugates with p bonds which make the electron withdrawing eect even stronger. It has been reported that a,o-diheptanoyltetrathiophene (N29c) has LUMO level at 3.78 eV while its peruorinated analogue (N29d)at 3.96 eV. The introduction of a carbonyl group, being in conjugation with the oligothiophene p-system (N31), lowered the LUMO level to 4.19 eV. These electrochemically determined positions of the LUMO level clearly reect satisfactory stability in air of transistors fabricated from the described three derivatives. N29c shows very good ambipolar properties (me/mh = 0.1/0.01 cm2 V1 s1), also N29d is ambipolar but after iodine doping. Similar compounds with peruorobenzoyl substituents (N29e) were reported.190 Interestingly non-uorinated analogue behaves only as p-type material, despite similar reduction potentials. The reason probably lies in dierent angles between thiophene and phenyl moieties in the solid state. This factor can be considered as negligible in solution, during electrochemical measurements. What is even more interesting, transistors based on drop-cast lms from N29e showed mobility under argon (0.21 cm2 V1 s1; ON/OFF ratio = 105) close to those obtained by vapor deposition (0.45 cm2 V1 s1; ON/OFF ratio = 108).80 It is worth to be mentioned, that N31 can be obtained from a soluble precursor (central carbonyl group was protected with
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ethylene glycol) using an idea of solution casting followed by deprotection.191 Finally, Ie et al. described a series of thiophene oligomers with peruorinated bridges. Usually the precursor under action of a uorinating agent is transformed to the corresponding uorinated derivative which then undergoes the coupling reactions already mentioned. Depending on the selected strategy, the uorinated alkyl bridge (with (N32) or without additional carbonyl groups) may be closed within the thiophene unit192 or between them (N33).193 In the latter case, a similar uorenone-like precursor as for N31 was used. The best FET behavior was observed for end-functionalized oligomers, with mobility of order up to 0.013 cm2 V1 s1 and ON/OFF ratio up to 105 (for N32). Thiophene co-oligomers and other heterocyclic oligomers. The reason for the use of other than thiophene heterocycles is attributed to greater electronegativity of compounds having more than one heteroatom. Most of n-type semiconductors presented in this subsection are prepared in a similar manner as thiophene oligomers. Desired heterocyclic units like thiazolothiazole or oxadiazole are synthesized with typical procedures known from heterocyclic ring formation reactions194 like i.e. PaalKnorr reaction. Alternatively, commercially available compounds may be used for direct coupling. Representative n-type oligomers are shown on Scheme 11. Literature search has revealed that oligomers with nitrogen containing central unit are semiconductors of good performance but they operate under high threshold voltages (>60 V). Practically in all cases transistors were fabricated with the use of SiO2 dielectric and vapor deposition of the semiconductor. Recently, nitrogen rich oligomers were extensively studied.195 In one of the rst papers on this topic,196 transistors from oligomers with thiazolothiazole central unit and thiophene/triuoromethylphenyl side units were fabricated. These semiconductors along with their thiophene analogue exhibited very similar n-channel performance with the best device made from N34 (me = 0.3 cm2 V1 s1, ON/OFF ratio = 106, VT = 60 V in vacuum). The shortest oligomer without thiophene rings did not show n-type semiconductor properties because of disordered orientation of the molecules. Further studies197 revealed interesting dependence of the charge carriers mobility on the regiochemistry of the central bithiazole unit. 2,2 0 -bithiazole unit in the semiconductor molecule, in spite of lowering its reduction potential, either diminishes the mobility or even disables the n-channel behavior. To the contrary, the molecule based on 5,5 0 -bithiazole unit (N35) was used to construct OFETs with mobility up to 1.83 cm2 V1 s1, depending on the dielectric surface treatment (0.21 cm2 V1 s1 for untreated surface). Interestingly, such high mobilities were accompanied with rather moderate ON/OFF ratios of ca. 104. Unfortunately, the devices failed to operate in air. Signicant parameters improvement for N34 was also achieved by modication of the SiO2 surface (1.2 cm2 V1 s1, ON/OFF ratio = 107, VT = 67 V in vacuum).198 In later research, application of the same surface treatment compound (OTS) led to a signicant improvement of the performance of the N34 analogue199 in which thiazole rings replaced the
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Scheme 11 Thiophene co-oligomers and quinoidal oligomers.
thiophene ones. Again electrical properties strongly depended on the type of the thiazole units linking, in favor of more separated heteroatoms. The authors, aware of high threshold voltages of previously reported devices, lowered this parameter 3 times by switching conguration from the bottom contact to the top one. Low band gap oligomer based on benzothiadiazole200 (N36) was used for fabrication of OFETs with very low threshold voltage of 3 V (me = 0.19 cm2 V1 s1, ON/OFF ratio = 106) as well as for studies of water inuence on the n-channel OFETs behavior.110 Oligomers based on phenyl,201 pyrazine202 or anthraquinone203 middle units were found to have moderate electron mobility. Interestingly, pyrimidine co-oligomers turned out to be p-type materials in opposite to the expectations of the authors.204 Oxadiazole is another planar aromatic unit that conjugates with other p-bonds. Due to the presence of an oxygen atom it is more electronegative than similar heterocyclic compounds. Oligomers based on oxadiazole were reported over 10 years ago.205 In a later work,206 peruorinated groups were attached to the oxadiazole moiety. However, new oligomers were too volatile to be vacuum-deposited or failed to exhibit n-type semiconductor behavior. Inserting bithienyl link between two peruorophenyloxadiazole moieties resulted in air stable p-type semiconductors. Recently,207 it was proposed to apply two peruoroalkyloxadiazole groups as terminal units and thiophene, uorenone or dicyanovinyl as linkers. The key step of this synthesis was based on Suzuki coupling. Oxadiazole core oligomers were inactive in transistors. The compound with terminal peruorobutyloxadiazole units and tetrathienylene core acted as p-type semiconductor only. Other oxadiazole oligomers were also inactive except the one with the dicyanovinyl central unit (N37). This puts usage of oxadiazole for OFETs construction under serious doubt.
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TCNQ and quinoidal oligomers. The last group of the described heterocyclic oligomers, which from the formal point of view can be considered as heterocycles, consists of conjugated polyenes. Their double bonds are distributed in a manner that resembles structure of quinone; therefore they are often called quinoidal. The simplest quinoidal semiconductor, tetracyanoquinodimethane (TCNQ, N38) is actually not an oligomer, but a simple derivative of quinone obtained from condensation of 1,4-cyclohexanedione with dicyanomethane, followed by oxidation of the resulting adduct with bromine.208 TCNQ like TCNE is easily reduced. Its reduction potential is +0.17 vs. SCE,209 which leads to the LUMO level of 4.57 eV, according to eqn (1). TCNQ forms complexes with tetrathiafulvalenes (TTFs) which are highly conducting organic charge-transfer salts sometimes called organic metals. Many of these salts were studied i.e. by Wheland who also developed synthetic strategies for substituted quinodimethanes.210 In these complexes TCNQ acts as an acceptor. Typical TTFs are donors due to electron rich structure, but examples of high performance n-type TTFs are also known (N39).211 Behavior of TTF-TCNQ salts enables their usage as alternative material for electrodes in OFETs. Example of such use, with compound similar to TCNQ as semiconductor has been reported.212 More importantly, from the point of view of this section, TCNQ was one of the rst semiconductors that not only exhibited n-channel conductivity but also air stability.213 After doping, the measured mobility was 3 105 cm2 V1 s1 and the ON/OFF ratio increased upon air exposure from 4 to 450. Unfortunately, TCNQ and similar compounds exhibit in most cases poor performance in thin-lm transistors, despite good molecular orbitals overlapping even for derivatives with long alkyl chain.214 Noteworthy improvement is observed for single crystal transistors with SiO2 dielectric.215 Mobility (0.20.5 cm2 V1 s1) is among the highest measured for n-type materials operating in air. In an earlier paper,216 higher
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mobility was reported (1.6 cm2 V1 s1) but with applying vacuum space as dielectric, whereas using polymer dielectric diminished the mobility to 3 103 cm2 V1 s1. Few examples of quinoidal oligomers present in the literature are mostly thiophene-based and all have terminal double bonds possessing two nitrile groups. Preparation is similar to the synthesis of TCNQ, malodinitrile anion is coupled with ordinary dibrominated oligomer, and this adduct is oxidized to yield polyquinone. First studies217 of thiophene trimer (N40) showed easiness of the reduction of these compounds as well as the presence of p stacking in the solid state. Indeed these factors resulted in one of the rst reasonably good mobilities for n-type materials reported. Mobility based on vapor deposited layers was 0.005 cm2 V1 s1 and 0.002 cm2 V1 s1 for the solution deposited ones, the latter showing ca. 5 times greater threshold voltage. Later,218 mobility was improved to 0.2 cm2 V1 s1 by adjusting the growth of the lm and weak ambipolar character was also observed if the semiconductor was deposited at higher temperatures. In the single crystal structure of N40 a regular alternated p stacking could be evidenced. However, when deposited on the SiO2 substrate in a transistor conguration, a dierent regular stacking is found. It corresponds to a regular p stacking of dimers oriented with the long axis of the molecules tilted by 25.31 with respect to the direction perpendicular to the surface. Ambipolar behavior was reported for longer oligomers219 which were found tunable in not only electronic terms but also magnetic and optical ones.220 Other quinodimethane oligothiophenes derived from N40 with dierent substituents have been studied in terms of their crystallographic and electronic structures. All these systems crystallize in a triclinic unit cell in which the p conjugated core stays essentially at while the substituents are directed out of this plane. However the inter-molecular p-stacking is found quite strong in all cases
with typical inter-molecular face to face intermolecular stacking distances ranging from 3.33 to 3.5 A. Examples of solution processed derivatives were lately introduced.221 Finally, a comparison of quinoidal compounds with i.e. tricyanovinylcapped oligomers or cross-conjugated tetracyanoquaterthiophene which is excellent n-type material (me = 0.34 cm2 V1 s1, ON/OFF ratio = 6 103, VT = 35 V, under vacuum) was carried out by Ortiz et al.222 Rare examples of miscellaneous quinoidal compounds such as n-type biselenophene,223 soluble ambipolar heteroquinoid derivative224 or dithienopyrrolebased low band-gap derivative225 have been also reported. 4.4 Polymeric n-type semiconductors Typical n-type high molecular weight semiconductors (HMWSC) contain, in their main chain, either aromatic or heteroaromatic moieties in direct connection with electron withdrawing groups. Taking into account their molecular weight, thin layers of these polymers cannot be vapor deposited. Thus their solution processability is of crucial importance for the applications in organic electronics. There exist two approaches concerning the improvement in this processability: (i) sti backbone semiconductor polymers can be solubilized by complexation with an appropriate Lewis acid or by protonation with a functionalized Brnsted acid, provided that appropriate complexation and/or protonation sites are present in their repeat unit; (ii) alternatively exible, alkyl type side groups are introduced to the conjugated main chain in order to facilitate the polymer dissolution in common solvents. Poly(oxo-benz[de]imidazobenzimidazoisoquinoline) (Np1) (Scheme 12), is a typical example of a macromolecular compound which is solubilized via complexation or protonation. This ladder-type polymer, synthesized more than 40 years
Scheme 12 Polymers used in n-channel transistors.
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ago via condensation of naphthalene tetracarboxylic acid and tetraaminobenzene,226 turned out to be a very promising n-type semiconductor. In the fabrication of transistors it can be solution processed227 from methanesulfonic acid solutions showing mobilities in the OFET conguration up to 0.1 cm2 V1 s1. Recently, highly anisotropic, beltlike nanostructures of Np1, showing a very high aspect ratio, have been prepared.228 In these so-called nano-belts, the long axis of the nano-objects and that of the polymer chains are parallel. Probably due to the very high stiness of such chains, the growth mechanism forces the p stacking direction to be perpendicular to the long axis of the nano belt with a stacking distance of 3.36 A. This is the reverse situation to that found for example in the structure of P3HT brils.229 Ambipolar transistors were also fabricated from blends of Np1 and p-type semiconductor polymers, namely poly[(thiophene-2,5-diyl)alt-(2,3-diheptylquinoxaline-5,8-diyl)] and poly[(10-hexylphenoxazine-3,7-diyl)-alt-(3-hexyl-2,5-thiophene)]230 or from mixtures of Np1 with copper phthalocyanine.231 Phenanthroline-based homopolymers were also tested as semiconductors in n-channel OFETs.232 Poly(3-nonyl-1,10phenanthroline-3,8-diyl) and poly(1,10-phenanthroline-3,8diyl) showed no eld eect when uncomplexed. Upon complexation (1 : 1) with RuII(bpy)2 (Np2) they could be applied as n-type semiconductors showing FET mobilities of 5.5 103 cm2 V1 s1 and 1.9 103 cm2 V1 s1, respectively. Other n-type macromolecular compounds involve polymers containing alternating aromatic and oxadiazole units. Despite interesting electrochemical properties,233 they are poor materials for the fabrication of FETs which show very low mobilities,234 similarly as already discussed short oxadiazole oligomers. A large group of organic semiconductors suitable for the fabrication of n-type or ambipolar transistors embraces macromolecular compounds which can formally be considered as copolymers consisting of alternating oligothiophenes units and conjugated, electron decient groups. Terpolymers consisting of aromatic, thiophene and electronwithdrawing units have also been synthesized, usually by Suzuki or Stille coupling. In general, electrical behavior of these co- or terpolymers depends on the ratio of thiophene units to electron decient ones. For 2 : 1 and higher ratios they are rather p-type semiconductors. Some of these compounds are also interesting from the point of view of their potential application in photovoltaics, especially those which show a low band gap as a consequence of the alternation of electron withdrawing and electron donating units since low band gaps better match the solar spectrum (see for example ref. 235). The semiconducting behavior of copolymers with the 1 : 1 thiophene/electron decient unit ratio depends on the electron withdrawing power of the latter. This may lead to either ambipolar or n-type conductivity. Copolymers containing weak electron accepting moieties, like the copolymer of thiophene and thiadiazole, are clearly ambipolar.236 On the other hand highly electron anitive triazine/thiophene copolymer clearly shows its n-type behavior as demonstrated by time-of-ight drift (TOFD) mobility studies.237 More sophisticated adjustments of both the band gap and
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the type of charge carriers can be achieved by the design of a terpolymer in which a strong donor of dithienopyrroletype is combined with a strong acceptor (thiadiazole derivative) via a thienylene linker. The resulting polymer shows a very low band gap and ambipolar semiconducting properties.238 Polymers containing oligothiophene and indenouorenebis(dicyanovinylene) segments seem to be promising semiconductors. Np3, which can be prepared from an already presented polymerizable precursor (N18), exhibits ambipolar behavior with comparable hole and electron mobilities.79 This proves that electron withdrawing properties of indenouorenebis(dicyanovinylene) units are suciently strong to assure n-type semiconductor behavior, despite the fact that they are separated with tetrathiophene segments. In a detailed paper Usta et al.81b discuss the synthetic strategy used in the preparation of such polymers and report several derivatives of Np3 prepared either by Stille or Yamamoto coupling whose electrical and structural properties can be tuned. Those polymers exhibit electron and hole mobilities of 1 1032 104 cm2 V1 s1, representing the rst examples of ambipolar semiconductors to function in air.81b Semiconducting copolymers of arylene bisimides and bithiophenes were prepared from core-dibrominated bisimides and various thiophene tin derivatives via Stille coupling.239,240 For applications in the fabrication of transistors naphthalene bisimide copolymer (Np4) seems to be much more promising than its perylene analogue240 in terms of its processing, performance and air-stability.241 Np4 is already available as commercial product of Polyera (ActiveInkt N2200). Examples of polymeric bisimides, conjugated through nitrogen atom are also known.242 A copolymer containing alternating perylene bisimide and dithienothiophene units has been prepared by Stille coupling of N,N-dialkyl-1,7-dibromo-3,4,9,10-perylene bisimide with distannylated dithienothiophene (Np5).243 In this case the fused nature of the oligothiophene segments favors the chain planarity. Np5 combines solution processability with promising electron mobility of 1.3 102 cm2 V1 s1 in the FET conguration. The discussed macromolecular compounds can be considered as donoracceptor polymers. As a result their band gaps are low and they exhibit interesting optical properties, which foretell their potential use in solar cells.243,244 Bithiophenedicarboximide-based (Np6) homopolymer is also soluble in various organic solvents yielding highly crystalline thin lms upon casting or other type of solution processing.245 Devices fabricated from Np6 exhibit an exceptionally high ON/OFF ratio. 4.5 Fullerene derivatives After the discovery of fullerene C60 in 1985,246 for the following 5 years only minute amounts of this carbon allotrope could be prepared. However, since the report of the rst synthesis of fullerenes on a larger scale247 several hundreds papers on the functionalization of C60 and C70 appeared. It is known that C60 has a very strong electron anity and may undergo up to six reversible reductions. At the same time
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Scheme 13 Fullerene derivatives and metal complexes used in n-channel FETs.
it is dicult to oxidize. This makes fullerene and its derivatives good candidates for n-type semiconducting compounds. Fullerene is soluble in aromatic solvents such as toluene or dichlorobenzene; however its functionalization usually involves attaching solubilizing groups as well, with the goal to improve its processability in a larger variety of suitable solvents. This may be essential for the sake of casting of the active semiconductor layers, since many fullerenes adducts show limited thermal stability (decomposition or cycloreversion at elevated temperatures) which limits the possibility of the application of vacuum deposition techniques. Selected fullerene derivatives, used for fabrication of the n-type transistors, are depicted in Scheme 13. Another important matter for transistor fabrication with C60 compounds is applying polymer dielectric since devices based on SiO2, i.e. in the bottom gate conguration, often fail to operate in air.38,248 One of possible reasons is probably too high LUMO level249 of these compounds (ca. 3.60 eV).250 One of the most popular fullerene derivative is PCBM (methanofullerene [6,6]-phenyl C61-butyric acid methyl ester, N41, Scheme 13) which is commercially available. Thus, it is often used as standard in comparative studies involving new semiconductors. Transistors fabricated from PCBM, operate in N2 atmosphere with 4.5 103 cm2 V1 s1 mobility when an organic resin dielectric is applied. One-week exposure in ambient conditions slightly lowers the mobility but also reduces the threshold voltage. Applying polyvinylphenol derivative dielectric in all-solution processed OFET resulted in raising the mobility up to 0.1 cm2 V1 s1, however the ON/OFF ratio remained rather low (4 103).251 By modifying the devices with a similar dielectric, ON/OFF ratios were improved when measured in an inert gas atmosphere.252 Field eect mobility of N41 was raised even higher, to 0.21 cm2 V1 s1, after changing the dielectric to polymerised divinyltetramethyldisiloxanebis(benzocyclobutene).253 The same group reported OFETs from C70 analogue of N41, with good performance (me = 0.1 cm2 V1 s1). With standard SiO2 dielectric the mobility of N41 in transistors operated in vacuum was 0.023 cm2 V1 s1 (ON/OFF ratio = 7 104).254 However such transistors are unstable upon exposure to air
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due to intrusion of O2 and water.250 Other compounds similar to N41, have also been described.255 A derivative with a more bulky ester group was found to provide lower mobility (1.04 102 cm2 V1 s1), because of less favorable crystal packing. The acid resulting from the hydrolysis of N41 gives OFETs of even lower mobility (1.59 103 cm2 V1 s1), probably because the carboxyl group may, in this case, act as an electron trap. Fullerene functionalized with triazole moiety256 was shown to exhibit similar properties to N41. Recently, N41 was applied to solution processed ambipolar FETs.257 Some heteroanalogues of N41 are also known.255 One of the issues regarding N41 is the fact that it often tends to form amorphous lms which is unfavorable for the electrical transport. Chikamatsu et al. focused on soluble C60-fused N-methylpyrrolidynes N42, obtained with the use of Prato reaction, that provide highly ordered crystalline lms.254 The devices based on N42 presented interesting electrical parameters (me = 0.067 cm2 V1 s1; ON/OFF ratio = 1.6 105), however even regular structure of the thin lm did not assure stability of the device in air. Further research,258 enabled improving the transistor parameters which reached the mobility of 0.09 cm2 V1 s1 and ON/OFF ratio of 4 105. Other isomers of N42 exhibited somewhat inferior charge transport properties. Finally replacing the dodecyl group for the peruorophenyl one led to devices (with SiO2 dielectric) operating in air, showing, however, much lower mobilities.250 Upon exposure to air a two-fold increase of voltage threshold was observed. Despite the fact that the change of the substituent barely aected the LUMO level of the molecule, introducing peruoroakyl chain resulted in a more dense packing of the molecules and limited intrusion of oxygen or moisture. Transistors fabricated by inkjet printing from thiophene substituted C60 fused pyrrolidine have also been reported.259 In inert atmosphere, they showed the mobility of 2.8 102 cm2 V1 s1, the ON/OFF ratio of about 106, and the threshold voltage of 7 V. Another example of interesting derivation of fullerene with the goal to obtain semiconductors of high performance has recently been reported.260 Transistors made from fullerene containing peruoroalkyl groups (with SiO2 dielectric) showed mobilities
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up to 6.7 102 cm2 V1 s1 and an exceptionally high ON/OFF ratio of 5 107. 4.6 Phthalocyanines
indicated. In Table 2 similar data are presented for HMWSCs together with their macromolecular characteristics.
This group of compounds has been known for over 100 years.261 Phthalocyanines can be synthesized from many starting compounds such as phthalimide or 1,2-benzenedicarbonitrile.262 Depending on the type of substitution phthalocyanines may act as p- or n-type semiconductors. Introducing electron withdrawing groups like uorine or chlorine results in the latter type. Phthalocyanines are also rst materials for which n-channel OFETs were fabricated, in 1990.263 Lutetium and thulium bisphthalocyanines exhibited n-type conductivity in vacuum and p-type in air. Advantages of using phthalocyanines involve their commercial availability, easy purication with sublimation techniques and air-stability since the LUMO level of n-type phthalocyanines is remarkably low (o4 eV).264 Unfortunately mobilities obtained for phthalocyanine-based devices rarely exceed 102 cm2 V1 s1 in n-type or ambipolar transistors, also in these few cases when polymeric dielectric is used.265 Phthalocyanines are also interesting candidates for transistors with pn junctions, where unsubstituted phthalocyanine266 or another suitable semiconductor267 stand for the p-semiconductor and hexadecauorophthalocyanine (N43a, F16CuPc) is used as the n-type semiconductor. The latter compound is very popular and several investigations regarding the morphology of its thin lms have been carried out.268 Notable feature of phthalocyanines, among n-type semiconductors described in this work, is the presence of metal in their structure, usually copper (see Scheme 13). In one of the rst papers about n-channel air stable transistors, based on these metal complexes, published by Bao et al.,269 phthalocynanines with iron, cobalt and zinc have also been described. Unfortunately, their OFETs performance was at least about 10 times worse than that of transistors fabricated from N43a (me up to 0.03 cm2 V1 s1, ON/OFF ratio = 3 105). Recently reported transistors, based on non-functionalized tin phthalocyanine (N43b), exhibited however constant electron mobility of about 0.3 cm2 V1 s1 (ON/OFF ratio = 107) for 5 days.270 Applying other than uorine substituents in almost all cases led to semiconductors which could not be tested due to decomposition of the sublimed compounds or lack of the eld eect in the fabricated devices. Successful use of Cl16CuPc (N43c) has been reported later,271 as well as improving N43a-based OFETs272 which showed the mobility of 0.08 cm2 V1 s1. Literature on related metal complexes such as nickel bis(dithienolates)273 N44 is scarce, probably due to the fact that the performance of the fabricated transistors is rather poor when semiconductor is not in doped state. On the other hand bis(1,2-benzoquinonedioximato)platinum(II)274 (N45)-based single-crystal OFETs show sensible mobility of 0.2 cm2 V1 s1 and are air stable. Data concerning the LUMO level of LMWSCs described in chapter 4, their processability and the parameters of the transistors fabricated from them are collected in Table 1. Semiconductors yielding air operating transistors are clearly
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5. Organic semiconductors for p-channel eld eect tranistors

5.1 Low molecular weight compounds Low molecular weight semiconductors (LMWSCs), suitable for application in p-channel OFETs have been subject of signicant research interest for the past two decades which even intensied in the last two years (see Introduction). There are several features which make these compounds attractive for chemists and physicists. First, prepared by organic chemistry methods they are strictly monodisperse and regiochemically well dened. As a result they more easily form ordered supramolecular structures than their high molecular weight counterparts. Single crystals or oriented polycrystalline layers of LMWSCs can be obtained on various types of substrates. Second, their solution processability is better than that of the corresponding polymers, nevertheless to be solution processed they have to contain solubilizing, usually alkyl-type substituents. Their presence facilitates, in many cases, the formation of ordered supramolecular organization in the solid state. Even relatively small unsubstituted conjugated molecules are dicult to dissolve and are usually deposited by evaporation. Vapor deposition of a uniform layer on a large surface area is however dicult. For this reason several soluble precursor routes have been developed in the processing of unsubstituted LMWSCs to enable preparation of the layers by casting. For example, insoluble a,o-distyryl oligothiophenes can be solution processed via casting of precursors containing labile ester groups which leave upon thermal annealing275 (see Scheme 14). Soluble precursors were also prepared in the case of pentaceneanother important LMWSC. Pentacene reacts as diene in a DielsAlder reaction with N-sulnylacetamide to yield a soluble precursor. This precursor can be reconverted into pentacene in a retro-DielsAlder reaction carried out at T > 120 1C.276 Other pentacene precursors have also been proposed.277 In recent years, however, signicant research eorts have been undertaken to avoid the necessity of the application of the precursor route in the solution processing of LMWSCs. This resulted in the preparation of soluble semiconductors exhibiting excellent electrical transport properties. P-type LMWSCs can be classied into several groups which will be discussed separately. The selection of a convenient classication pattern for these molecules is not easy because they frequently consist of conjugated segments of dierent chemical nature. In the classication adopted in this paper the chemical nature of the molecules central unit is considered as decisive in the ascription of a given compound to a given family of organic semiconductors. This classication works well for symmetric compounds which constitute a large majority of the discussed LMWSCs. However, it sometimes fails for asymmetric molecules and molecules of more complicated topologies. It is also inconvenient for aromatic (heteroaromatic) compounds containing multiple bond spacers (vinylene- or ethynylene-type). In these few exceptions dierent classication criteria had to be introduced.
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Table 1 Semiconductors for n-channel FETs; position of the LUMO level, transistors parameters, processing techniques and stability in air operating conditions Compound N1 N6a N6b N7a N7b N8 N9 N12a N12b N13 N16 N18 N20a N20b N21a N21b N21c N22a N22b N23a N23b N23c N23d N24a N24b N25 N27 N28 N29a N29b N29c N29d N29e N30 N31 N32 N33 N34 N35 N36 N37 N38 N39 N40 N41 N42 N43a N43b N43c N44
a
LUMO/eV 3.65 3.20 3.35 3.09 3.18 2.96 3.67a 3.67a 3.2 4.32 3.8 3.8 4.3 4.5 4.0 4.2 3.8 4.09 4.5 4.48 3.26b 3.87 3.31 2.85 3.78 3.96 4.19 3.38 3.18 4.57 3.81 3.6 4.4 4.6
b
me/cm2 V1 s1 1.6 10 104 2.16 101 o104 o104 1.7 103 3.4 103 7 102 3 102 3.6 106 1.6 102 1.6 101 1.7 2.1 1.4 101 6.4 101 5.3 101 3 105 4 103 1.6 101 3.58 102 5.7 101 1.5 101 1.5 101 8.6 106 7.24 102 2 102 7.4 102 2.2 101 8 102 1 101 6 101 4.5 101 7.4 102 8 102 1.3 103 1.8 102 1.2 1.83 1.9 101 2 103 3 105 1.1 101 2 101 2.1 101 6.7 102 8 102 3 101 1 102 9 105
1
ON/OFF ratio 10 3 105 Low ON currents Low ON currents 104 104 106 106 103 104 108 107 4.2 105 1.2 103 104 3.4 107 103 104 100 5.2 105 107 2 105 102 104 1.22 104 2 107 106 106 >105 >107 >107 108 6 106 107 9.9 104 1.3 103 107 104 106 104 4450c 106 >104 1.6 105 105 107 1.57 105 30
5
SC deposition technique operating conditions Vapor deposition Vapor deposition Vapor deposition Vapor deposition Vapor deposition Vapor deposition Vapor deposition Vapor deposition [a.o.] Vapor deposition [a.o.] Vapor deposition Vapor deposition Solution deposition [a.o.] Vapor deposition Vapor deposition Vapor deposition [a.o.] Vapor deposition [a.o.] Vapor deposition [a.o.] Vapor deposition [a.o.] Vapor deposition [a.o.] Vapor deposition Vapor deposition [a.o.] Vapor deposition [a.o.] Vapor deposition [a.o.] Vapor deposition [a.o.] Solution deposition Vapor deposition Vapor deposition Vapor deposition [a.o.] Vapor deposition Vapor deposition Vapor deposition Vapor deposition [a.o.] Vapor deposition Vapor deposition Vapor deposition [a.o.] Vapor deposition Vapor deposition Vapor deposition Vapor deposition Vapor deposition Vapor deposition Vapor deposition [a.o.] Vapor deposition Vapor deposition Solution deposition Solution deposition Vapor deposition [a.o.] Vapor deposition [a.o.] Vapor deposition [a.o.] Vapor deposition [a.o.]
Ref. 50a,61 57 57 58 58 55 56 70 70 72 77 79 97 105 128 142 149 36 36 148b 158 159 154 84 165 174 175 185 186 189 189 190 37 191 192b 192 198 197 200 208 213 211 218 253 254 272 270 271 273b
Electron anity.
Calculated. c ON/OFF ratio increased upon air exposure. [a.o.] - air operating.
Table 2 Polymeric semiconductors for n-channel FETs; Mn, polydispersity, position of the LUMO level, transistors parameters, processing techniques and stability in air operating conditions Compound Np1 Np2 Np3 Np4 Np5 Np6 Mn (Da)/PD 6688/3.48 51000/5.5 10000/1.5 3600/2.2 LUMO/eV 4.5 4.15 3.91 3.9 3.47 me/cm2 V1 s1 1 10 5.5 103 2 104 8.5 101 1.3 102 1.1 101
1
ON/OFF ratio 5 10 3.3 104 104 107 >104 2 107

5
SC deposition technique operating condition Solution Solution Solution Solution Solution Solution deposition deposition deposition deposition deposition deposition [a.o.] [a.o.] [a.o.] [a.o.]
Ref. 227 232 80b 241 243 245
[a.o.] - air operating.
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Scheme 14 Transformation of soluble precursor into a,o-distyryloligothiophenes through thermal treatment.
Condensed aromatic hydrocarbons and their derivatives. Several condensed aromatic compounds from linear acenes to two-dimensional coronenes show p-type semiconductor properties. Some of them (P1P18) are shown in Scheme 15. Compounds of this family show the highest charge carriers mobility with m = 20 cm2 V1 s1 measured for a single crystal of rubrene (P2) in the FET conguration278 and m = 40 cm2 V1 s1 in contactless measurements.279 Polycrystalline pentacene (P1) and tetracene also show surprisingly high mobility approaching 5 cm2 V1 s1 for the former. Picene (P3)280 which is iso-atomic and by consequence iso-electronic with pentacene shows mobilities up to 1 cm2 V1 s1. Solubility inducing functionalization is a convenient method for the preparation of processable pentacenes. Pentacenes substituted with alkylethynyl or trialkylsilylethynyl groups at positions 6 and 13 combine solution processability with excellent charge carriers mobility in solution cast lms.281 For example thin layers of 6,13-bis(triisopropylsilylethynyl)pentacene (P5), deposited by casting, show FET mobilities approaching 2 cm2 V1 s1.282 The presence of ethynyl spacer is in this case necessary because direct attachment of alkyl solubilizing groups to the aromatic core signicantly perturbs the structural organization in the solid state which, in turn, leads to diminishing of pp interactions between adjacent molecules. The presence of alkylethynyl or trialkylsilylethynyl substituents changes the crystal structure of pentacene which is transformed from herring bone like to more two dimensional brick wall onethe latter being more favorable for charge transport. Recent studies have shown that the presence of methyl groups directly attached to the aromatic core in bis(trialkylsilylethynyl)pentacene (P5A) further improves its solution processability yielding solution cast thin layers of excellent charge carriers mobility comparable to that of P5.283 Diaza derivatives of pentacene like for example 6,13-dihydro-6,13-diazapentacene (P6) show improved solution processability as compared to unmodied pentacenes, especially if solvents capable of interacting with this molecule via hydrogen bond are used. Moreover, devices based on P6 show much better stability when operating in ambient conditions. Initial reports on the performance of P6-based OFETs indicated, however, a rather low charge carriers mobility5 orders of
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magnitude lower than that reported for the best pentacene devices.284 In a recent paper, focused on the elucidation of the structure-properties relationship in this family of semiconductors, mobilities approaching 0.45 cm2 V1 s1 have been reported.285 P6 is polymorphic and only one of three polymorphs shows crystal packing favorable for charge transport, thus the electrical properties are in this case very sensitive to phase purity. Soluble hexa-peri-benzocoronenes containing 2D aromatic core and radially attached solubilizing alkyl groups (P4) thermotropically develop discotic columnar liquid crystalline phases whose presence improves their solid state organization. As a result strongly anisotropic electrical properties are measured with enhanced mobility along the column.286 Coronene-based OFETs, in which the semiconducting layer was prepared by so called zone casting method.287 exhibit mobilities up to 0.01 cm2 V1 s1.288 Anthracene and other acene derivatives constitute another large group of p-type semiconductors suitable for p-channel OFETs fabrication. Among them anthradithiophenes terminally substituted with alkyl solubilizing groups (P7) have been studied for more than decade.289 They are obtained as a mixture of syn- and anti-isomers which are dicult to separate. Thin layers of these LMWSCs can be fabricated either by vapor deposition or by solution processing, the former technique leading to mobilities of the order of 0.1 cm2 V1 s1 whereas the latter yields materials of one order of magnitude lower mobility. Various derivatives of these compounds have been synthesized in recent years including those containing uorinated substituents.290 An alternative route to solution processable anthradithiophenes involves their substitution with (trialkylsilyl) groups as in the case of pentacenes (P8A).291 FET mobilities in solution processed layers of P8A reached 1 cm2 V1 s1 being, however, very sensitive to the alkyl substituents.292 It turns out that introduction of uorine as terminal substituent (P8B) enhances crystallinity of these derivatives and makes its supramolecular organization less sensitive to the applied processing conditions.293 This eect was rationalized by the halogenhalogen or halogensulfur noncovalent interactions which, although being very weak in nature, could promote the formation of ordered supramolecular organization. Asymmetric organic semiconductors, namely anthra[2,3-b]thiophene (P9A) and its tetraceno amalogue (P9B) were synthesized mainly with the goal of improving the structural organization by avoiding the formation of inseparable synand anti-isomers (vide supra).294 Although it would intuitively seem that asymmetric molecules may show inferior charge carriers mobility as compared to their centrosymmetric counterparts, it is not the case for anthrathiophene derivatives since P9A and P7, processed in similar conditions, show comparable mobility. Another asymmetric derivative of anthracene, anthra[2,3-b]benzo[d]thiophene (P10) has been prepared and tested as p-type semiconductor in OFETs exhibiting charge carriers mobilities approaching 0.45 cm2 V1 s1.295 New X-shaped semiconducting molecules consisting of anthrylene core with alkylaryl and alkylthienyl groups attached to it through an ethynylene spacer have recently been described (see Scheme 15 (P11A and P11B)).296 They are
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Scheme 15 Fused aromatic compounds used in p-channel FETs.
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highly soluble in common solvents and exhibit lm forming properties. The presence of alkyl groups not only facilitates solution processing but also induces highly ordered 2D structural organization. The FET mobilities, measured for solution processed layers, reached 0.24 cm2 V1 s1 for P11B. Other anthrylene-ethynylene-based semiconducting molecules have also been synthesized and tested in OFETs (P12 and P13) showing mobilities of 7 102 cm2 V1 s1 for P12297 and 2.5 103 cm2 V1 s1 in the case of P13.298 Tetrathienoanthracenes with alkyl solubilizing groups (see Scheme 15) were synthesized and studied as promising semiconductors for OFETs (P14).299 They can be prepared in a two step procedure involving Stille coupling of stannylated thiophene derivative with tetrabromobenzene, followed by oxidative cyclization. They are solution processable although thin layers can also be prepared by vapor deposition. Mobilities in unoptimized devices prepared by vapor deposition reached 7.4 cm2 V1 s1 and 1.9 cm2 V1 s1 for P14A and P14B, respectively. In OFETs fabricated by solution casting one order of magnitude lower mobility values were measured. Somehow similar heteroarene compounds with chrysene core (P15) have recently been reported.300 They are soluble in common solvents such as chloroform or toluene which may enable the fabrication of OFETs by solution processing. Compounds with anthracene central part connected to alkylthienyl or alkylthienyl vinyl groups, namely dithiophen2 0 -yl-2,6-anthracene (P16) and 2,6-bis(2-thienylvinylanthracene) (P17) also show p-type semiconducting properties. P16 can be synthesized from pinacolatoboronic ester derivative of 2,6anthracene and 2-bromo-5-hexylthiophene via Suzuki coupling.301 P17 is prepared by HornerEmmons coupling between 2,6-bis(diethylphosphorylmethyl)anthracene and aldehyde derivative of alkylthiophene (see Scheme 16). The preparation of the phosphonate precursor is however complicated and involves ve steps.302 Although both molecules are solution processable the reported FET mobility data (0.50 cm2 V1 s1 for P16 and 0.15 cm2 V1 s1 for P17) relate to layers obtained by vapor deposition. Conjugated molecules with condensed aromatic core and peripheral solubilizing alkyl groups exhibit very good performance in OFETs due to the following specic features: (i) excellent molecular planarity; (ii) good intermolecular packing, frequently assured by interdigitation of the alkyl chains and (iii) alignment of the molecules with respect to the substrate surface. The last feature strongly facilitates the charge carriers transport. However similar eects can be achieved in non condensed systems if the rotation of the s-bonded units, such as biphenyl ones, is blocked by appropriate bridging. 2,7-bis-(5 0 -hexyl-2,2 0 -bithien-5-yl)-9,10-dihydrophenanthrene reported by Cho et al. (P18) is an instructive example of this
Scheme 17 Oligothiophenes and co-oligomers with selenophene or oxadiazole used in p-channel FETs.
approach.303 P18 was prepared from 2,7-diiodo-9,10-dihydrophenanthrene and 5 0 -hexyl-2,2 0 -bithiophene-5-boronic acid by palladium catalyzed Suzuki coupling reaction. It combines solution processability with the facility of forming highly oriented polycrystalline layers on dierent substrates. The highest measured FET mobility in P18-based transistors exceeded 0.4 cm2 V1 s1. Oligothiophenes and their derivatives. Linear oligothiophenes (P19, P20, see Scheme 17) as semiconductors for p-channel OFETs have been studied for more than two decades.304 Since excellent reviews appeared recently on the chemistry of these oligomers 305 and their application in OFETs7,34a the earlier works will be discussed only briey and focus will be put on newly developed molecules. Thin layers of unsubstituted oligothiophenes in OFETs are usually prepared by vapor deposition because they are extremely dicult to be solution processed. Terminally substituted linear oligomers i.e. a,o-dialkyloligothiophenes are solution processable however their dissolution requires the use of high boiling solvents and their processing must frequently involve substrate warming. Some of them like a,o-dialkylthienoselenophenes (P21)306 or dimethyl-t-butylsilyl substituted oligothiophene (P22)307 are vapor deposited. Among a,o-disubstituted oligothiophenes 5,5 0 0 0 -bis(5-peruorobutyl-1,3,4-oxadiazole-2-yl)-2,2 0 :5 0 ,2 0 0 :5 0 0 ,2 0 0 0 -quaterthiophene (P23) is an interesting case. This molecule was synthesized from distannylated bithiophene and 2-(5-bromo2-thienyl)-5-(peruorobutyl)-1,3,4-oxadiazole by Stille coupling. It was prepared with the goal to obtain a new semiconductor for n-channel OFETs since it contained strongly electron
Scheme 16 Final step of the synthesis of P17.
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Scheme 18 Selected examples of star-shaped molecules containing oligothiophene radial substituents.
withdrawing substituents. Contrary to the expectations P23 revealed p-channel behavior.207 Star-shaped molecules containing oligothiophene radial substituents. As it has already been stated, dicult solution processability is the main problem impeding the use of oligotiophenes as semiconductors. In this respect changing their molecular shape towards more three-dimentional one should be benecial. Several hybrid molecules, consisting of benzene (P24)308 truxene (P25)309 or triphenylamine cores (P26)310 to which oligothiophene groups are radially attached, have been prepared (see Scheme 18). Indeed, they show improved solution processability with respect to linear oligothiophenes. One may expect the formation of a columnar-type, ordered supramolecular organization in solution cast thin layers of P24 or P25 i.e. molecules with the aromatic core. In fact, in the case of P25 the cristallinity decreases with the length of the radial thiophene moietythe molecule with terthiophene radial groups is amorphous. Thin layers of P26 are also amporhous which results from the molecular shape of this compound. Its amine group, present in the core, forces the molecule out of planarity which makes the crystallization dicult. It should also be pointed out that P26 shows a
surprisingly high, for an amorphous material, mobility of 0.011 cm2 V1 s1.310
Fused oligothiophenes. Compounds with the central part consisting of fused thiophene rings like dierent types of thienothiophenes constitute a large family of semiconductors suitable for applications in p-channel OFETs. Within this family P27A and P27B (Scheme 19) can be considered as examples of a thoughtful design of molecules which should combine solution processability with increased stability in air operating conditions. They consist of thieno[3,2b]thiophene core to which alkylthiophene rings are attached to assure solubility. Phenyl or naphthyl group are used as end capping substituents with the goal to lower the HOMO level and make the molecule more resistant towards the oxidation.311 The synthetic procedure consists of Stille coupling of 2,5dibromothieno[3,2-b]thiophene and stannylated derivative of thiophene, followed by the bromination of the intermediate and its subsequent reaction with aryl boronic acid (Suzuki coupling). As revealed by STM investigations these molecules form highly ordered domains on HOPG. Preliminary tests show moderate FET mobilities which probably can be improved by device optimization.
Scheme 19 Examples of fused thiophene derivatives and some selenium analogues.
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Thienoacenes of higher length (up to heptathienoacenes) were also synthesized and tested as semiconductors for p-type OFETs.312,313 Using similar design approach as that applied in the synthesis of P27, aryl groups capped thienoacenes (P28) were prepared to improve the thermal stability and the resistance against oxidation of this group of compounds.314 P28 derivatives readily form single crystals or highly oriented polycrystalline layers, however they must be processed by vapor deposition. Their FET mobility reaches 0.14 cm2 V1 s1. Thienoacenes capped with benzoyl or thienyl carbonyl groups (P29) also exhibit p-type transport properties however the measured mobilities are moderate.59 Other members of the thienothiophene family, namely [1]benzothieno[3,2-b][1]benzothiophenes containing alkyl substituents (P30) deserve a special attention because they combine excellent solution processability with high mobility in FET conguration, reaching 2.7 cm2 V1 s1. This high performance has its origin in their highly ordered supramolecular organization.315 Its selenophene analogue (P31) also shows interesting semiconducting, although the measured FET mobilities are one order of magnitude lower.316 Heterocirculenes synthesized by Chernichenko et al.317 such as octathio[8]circulene (P32A) or tetrathiotetraseleno[8]circulene (P32B) are an interesting example of fused oligothiophenes (selenophenes). Showing high resistance against oxidation, associated with low lying HOMO level (see Table 3) these compounds can be considered as promising candidates for air operating semiconductors. High symmetry of circulene molecules is favorable for dense columnar solid state packing. FET mobilities approach 102 cm2 V1 s1 in the case of P32A but could probably be improved after optimization.318 Heteroacenes with aromatic central ring. Coplanar heteroacenes with aromatic central ring and solubilizing alkyl end groups (see Scheme 20) such as, for example, dithieno[2,3-d:2 0 3 0 -d 0 ]benzo[1,2-b:4,5-b 0 ]dithiophene (P33) combine solution processability with excellent electrical transport properties, reaching the FET mobility of 1.7 cm2 V1 s1.319 They can be easily obtained in a form of single crystals or highly oriented polycrystalline layers. As demonstrated by X-ray investigations the molecule of P33 is almost planar with alkyl chains slightly out of the plane of the heteroaromatic core. Showing low lying HOMO level they are promising candidates for air operating semiconductors. Somehow similar compoundsbenzo[1,2-b:4,5-b]bis[b]benzothiophenes with alkyl solubilizing terminal groups (P34)in which thiophene and aromatic rings alternate, show more than two orders of magnitude lower FET mobility, but it can probably be improved by optimization since physicochemical properties of both groups of compounds are similar.320 Aromatic (heteroaromatic) compounds containing vinylene or ethynylene spacers. Introduction of a vinylene spacer between fused thiophene rings results in a reduction of the overall aromatic character of the planar structure and an increase of p-electrons localization. As a consequence the HOMO level of the molecule is down shifted which should lead to better device stability in air. Several groups used this approach with the goal to prepare organic semiconductors of improved performance.
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Zhang et al.321 prepared a series of solution processable trans-1,2-(dithieno[2,3-b:3 0 ,2 0 -d]thiophene)ethene derivatives (see Scheme 21), among them alkyl, phenyl or thienyl capped compounds (P35A, P35B, P35C). P35B and P35C have their HOMO levels in almost the same position (see Table 3), as well as a very similar band gap, however their crystallographic structure is strikingly dierent. P35B, which packs in herring bone geometry similar to that of pentacene, shows FET mobility over three orders of magnitude higher than that measured for P35C. In thin layers deposited on octadecyltrichlorosilane treated silicon substrate molecules of P35B are highly oriented, being nearly perpendicular to the substrate surface. This orientation is very favorable for charge transport and, as a result, FET mobilities up to 2.0 cm2 V1 s1 are measured. Very high operating stability of P35B was conrmed by 7 months long tests. Liu et al. have recently reported on the synthesis of new liquid-crystalline semiconducting molecules namely 2,5 0 -bis[2-(4-alkylphenyl)vinyl]thieno(3,2-b)thiophene (P36A) and 2,5 0 -bis-[2-(4-alkylphenyl)vinyl]-2,2 0 -bithiophene (P36B).322 The compounds were prepared by Suzuki coupling from dibromoderivative of thieno(3,2-b)thiophene (or 2,20 -bithiophene) and commercially available 2,5 0 -bis-[2-(4-pentylphenyl)vinyl]4,4,5,5-tetramethyl-1,3,2-dioxaborolane. Being trans isomers, both molecules are linear and show highly ordered structural organization in thin layers. FET mobilities measured for P36A reach to 0.15 cm2 V1 s1(see Table 3). P36B shows one order of magnitude lower mobility, similar as that measured for its analogue not containing alkyl substituents.323 Molecules with a fused thiophene central unit frequently show better performance than those with a bithiophene one. This is caused by the fact that free rotation in the bithiophene segment is not blocked and can induce a signicant chain torsion which, in turn, has an important structural consequence in the solid state. In an attempt to block this rotation Didane et al. synthesized a molecule with a bridged bithiophene central unit, namely styryl capped benzo[2,1-b:3,4-b 0 ]bithiophene (P37).324 Molecules of P37 in thin, vapour-deposited lms show high degree of orientation with their long axis parallel to the substrate surface, as revealed by X-ray diraction studies. Recently synthesized 2,7-distyryl[1]benzothieno[3,2-b][1]benzothiophene (P38) is somehow similar to P37, however its fused central unit is more extended.325 Thin layers of this semiconductor show a lamellar-type ordered structure which gives rise to satisfactory mobility values reaching 0.4 cm2 V1 s1. The main problem of P37 and P38 (but also other conjugated molecules which do not contain solubilizing substituents) is their extremely dicult solution processing. Fortunately they are thermally stable and can be deposited by evaporation. Semiconductor molecules consisting of phenylene and bithiophene units separated by ethynylene spacers have recently been synthesized by Meng et al. using palladium catalyzed Sonogashira coupling reaction326 (P39A, P39B, P39C). The introduction of alkynylene spacers eliminates steric distortion between aromatic (heteroaromatic) rings and improves solution processability of the obtained compounds. X-ray studies of P39C indeed showed that this molecule is planar with a very small torsion angle between the bithiophene
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Table 3
Semiconductors for p-channel FETs; position of the HOMO level and transistors parameters HOMO/eV 5.50 5.19 4.63 5.1 5.4 5.30 5.17 5.35 5.21 5.21 5.44 5.23 4.83 4.92 5.35 5.42 5.20 5.99 5.25 5.43 5.9 5.32 5.7 5.2 5.42 5.4 5.36 5.41 5.42 5.18 5.20 5.56 5.45 5.45 5.56 5.30 5.44 5.35 5.28 5.09 5.06 4.98 5.09 5.06 5.02 5.0 5.2 5.38 5.59 5.41 5.40 m/cm2 V1 s1 1.1 2.5 4.5 101 1 101 1.0 1.5 1.6 101 3.1 101 4.5 101 4 102 2.4 101 7 102 2.5 103 7.4 102 3.5 103 1.9 102 2.5 104 4 101 5 101 4.4 101 1.5 101 4.2 101 1.6 101 2 104 1.8 101 2 104 1.03 103 1.1 102 1 105 3.1 102 1.4 101 1 102 2.7 2.3 101 3 102 9 103 103 1.7 1 102 3.8 102 2.0 2 103 1.5 101 5 102 1 101 4.4 101 5.6 102 8.4 102 2.8 102 1.2 102 3.4 101 1.8 104 3 103 6.7 105 8.7 105 1.8 105 6.1 105 2.3 103 2.0 103 104 104 2.2 101 8 102 6.0 103 8.1 102 9.8 101 ON/OFF ratio 1.6 10 >107 106 103 107 4.4 105 1.3 106 105106 2.8 105 5.4 106 6 106 6 104 108 104 106 104 2.8 107 4.8 105 2 107 106 6 106 >103 5 105 102 103 2 102 4.5 104 106 107 108 106 105 106 106 107 105 104 108 104 106 105 106 107 1.3 106 1.9 104 3.9 105 105 107 105 105 105 105 105 105 105 2 105 104 105 2 106 3 104 6 102 5 104 4 104
5
Compound P3 P5A P6 P7 RQCH3 P8A P8B P9A P9B P10 P11A P11B P12 P13 P14A RQhexyl P14B RQhexyl P15 P16 P17, RQH P17, RQhexyl P18 P21 P22 P23 P24 P25 P26 P27A P28 P29 P30 P31 P32A P32B P33 P34 P35A P35B P35C P36A P36B P37 P38 P39A P39B P39C P40A P41A P41B P41C P42A P42B P42C P42D P43A P43B P44A P44B P45A P45B P45C P46A P47 [a.o.]-air operating.
SC deposition technique; operating condition Vapor deposition; [a.o.] Solution deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition Solution deposition; [a.o.] Solution deposition; [a.o.] Vapor deposition Vapor deposition Vapor deposition; [a.o.] Solution deposition; [a.o.] Solution deposition; [a.o.] Solution deposition; [a.o.] Solution deposition Vapor deposition Solution deposition Vapor deposition Solution deposition Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition Vapor deposition Vapor deposition; [a.o.] Vapor deposition; [a.o.] Solution deposition; [a.o.] Solution deposition; [a.o.] Vapor deposition Solution deposition Solution deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition Solution deposition; [a.o.] Vapor deposition; [a.o.] Solution deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Solution deposition Solution deposition Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Solution deposition; [a.o.] Solution deposition; [a.o.] Solution deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.] Vapor deposition; [a.o.]
Ref. 280 283 285 290 292 293 294a 294a 295 296 296 297 298 299 299 299 299 300 301 302 302 303 306 307 207 308 309 310 311 314 59 315 316 317 317 319 320 321 321 321 322 322 324 325 326 326 326 328 330 330 330 334 334 334 334 335 335 336 336 341 341 341 345 346
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Scheme 20 Heteroacenes with aromatic central ring used in p-channel FETs.
unit and the phenyl ring. Low lying HOMO level of P39 molecules assures their good stability in air operating condition with FET mobilities values approaching 0.1 cm2 V1 s1. Miscellaneous heterocyclic compounds. Pyrrole-based oligomers or polymers (see Scheme 22) usually show too high lying HOMO level which limits the possibility of their application as semiconductors in p-channel OFETs. Even the presence of a rather small amount of pyrrole rings in alternating copolymers of dithienopyrrole and alkylthiophene results in signicant raising of the polymer HOMO level with respect to its all thiophene analogue.327 However, it has recently been demonstrated that small molecules consisting of a dithienopyrrole central part and two fused aromatic rings (P40A, P40B) show the HOMO level well below 5.0 eV328 with respect to the vacuum level, which makes them suitable candidates for air operating OFETs. Evidently the presence of aromatic rings in these pentacyclic fused molecules results in lowering of the HOMO level. P40A and P40B are anti and syn isomers, respectively.
Scheme 22 Miscellaneous nitrogen and sulfur containing aromatic compounds used in p-channel FETs.
Both isomers are soluble and their single crystals can be grown from solution. Thin layers for OFETs were however vapordeposited. Out of two isomers only anti showed the eld eect, exhibiting the FET mobility of the order of 102 cm2 V1 s1. Benzothiazine analogue of P40 namely 6H-pyrrolo[3,2:4,5-b0 ]bis[1,4]benzothiazine (P41A) and its N-substituted derivatives (P41B, P41C), although known since 1969329 only recently have been tested as semiconductors for p-channel OFETs.330 They can be obtained from 2-aminothiophenol and 2,3dichloromaleimide (or its N-functionalized derivative) in a one step reaction. As evidenced from X-ray investigations the adjacent molecules form dimers through intermolecular hydrogen bonds. These dimers are packed into columns.
Scheme 21 Examples of compounds containing multiple linking bonds used in p-channel FETs.
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Scheme 23 Triarylamines used in p-channel FETs.
Thin, vacuum deposited lms show high degree of orientation with P41A molecules almost perpendicular to the surface of the substrate. P41A shows more than one order of magnitude higher mobility than P40A. Arylamines. Triarylamines (Scheme 23) and their derivatives are known as good hole transporting materials and for this reason were used in several types of organic electronic and optoelectronic devices.331 Since they form stable radical cations they are also investigated as potential molecular magnets.332,333 Their crystallization is dicult due to their molecular shape but they form stable glasses. N,N,N 0 N 0 -tetraphenylbenzidine (P42A) N,N,N 0 N 0 -tetrakis-(4methylphenyl)-benzidine (P42B), N,N 0 -bis(3-methylphenyl)(1,1 0 -biphenyl)-4,4 0 -diamine (P42C), N,N 0 -diphenyl-N,N 0 bis(1-naphtyl)-1,1 0 -biphenyl-4,4 0 diamine (P42D) were used as active layers in p-channel OFETs,334 showing very moderate saturated mobility approaching 104 cm2 V1 s1. Moreover, the transistors based on P42 lack morphological stability upon extended storage in ambient conditions which results in vanishing eld eect. More recently cyclic analogues of the above described triarylamines were synthesized by McMurry coupling reaction (P43A, P43B).335 Contrary to the P42 series cyclic arylamines
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crystallize and even single crystals of P43A could be grown from dichloromethane solution. Materials of dierent morphological features, including highly oriented nanobers, can be obtained by changing the processing conditions. FETs based on vapour deposited layer of P43A and spin-coated lm of P43B showed the mobility of ca. 103 cm2 V1 s1. Star-shaped semiconducting compounds consisting of triphenylamine core and carbazole or uorene side arms were
Scheme 24 Structure of indolo[3,2-b]carbazole-based compounds used in p-channel FETs.
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prepared from tris(4-iodophenylamine) and borolane derivatives of carbazole or uorene using a three-fold Suzuki coupling reaction (P44A, P44B).336 Similarly as P42 series star-shaped arylamines are amorphous in the solid state and their thin layers form molecular glasses. The measured mobilities in air operating FETs showed moderate mobility, slightly exceeding 104 cm2 V1 s1, however the devices showed good stability. Indolocarbazole derivatives. Indolo[3,2-b]carbazole is an interesting molecule. Its functionalization gives rise to a series of solution processable derivatives with tunable electronic properties and diversied supramolecular organization.337 Some of these compounds (Scheme 24) are very promising candidates for applications in organic electronics. Soluble inodolocarbazoles containing long alkyl chains as N-substituents such as 5,11-dioctyl-6,12-dimethylindolo[3,2-b]carbazole338 showed moderate FET mobilities of the order of 103 cm2 V1 s1. Two orders of magnitude higher mobilities were reported for indolo[3,2-b]carbazoles in which alkyl substituents were replaced by alkylaryl ones or halogen groups were introduced into the aromatic core.339 Extension of the conjugated core by branching thiophene or phenyl groups at the 2,8 or 3,9 positions and introducing alkyl N-substituents yields semiconductors whose FET mobility (0.2 cm2 V1 s1) is comparable to that measured for leading solution processable semiconductors.340 Recently, indolocarbazoles with alkylphenyl, alkylphenylvinyl or alkylthienyl groups attached to the aromatic core have been reported (P45A, P45B, P45C).341 They can be obtained by Stille or Suzuki coupling from t-butyloxycarbonyl (Boc) protected dibromoindolocarbazole and stannyl derivative or alkylthiophene or borolane derivative of alkylbenzene. P45 are good candidates for air operating FETs taking into account the position of their HOMO level (in the range of 5.3 to 5.6 eV) and the FET mobility exceeding, in some cases, 0.2 cm2 V1 s1. Unfortunately their solution processing is dicult and they are usually deposited by vapor deposition. Moreover their supramolecular organization is very sensitive to the conditions of the deposition. For lower deposition temperatures the obtained layer are amorphous; for higher ones the molecules self-organize standing almost perpendicular to the substrate surface. Tetrathiafulvalene derivatives. Tetrathiafulvalene and its derivatives have been subject of signicant research interest since the discovery of peculiar electrical properties of TTF-TCNQ complex in 1965.1 Since that time several thousands papers appeared on TTF derivatives based charge transfer conducting and superconducting complexes and radical cation salts. However TTF draws also a certain attention as a semiconductor for p-channel OFETs. For transistor application TTF derivatives can be solution deposited in a form of highly oriented polycrystalline layer but also can be grown as single crystals.342 The main problem of tetrathiafulvalene is its too high lying HOMO level which makes this molecule very fragile in operating conditions. To stabilize it several strategies are used like, for example, fusing electron withdrawing moieties such as dinaphto groups. Its stability is even more improved if electron decient
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Scheme 25 Tetrathiafulvalene derivatives used in p-channel FETs.
heterocycles are present in the molecule.343 Another approach involves insertion of a conjugated spacer between the two dithiafulvalenyl moieties (examples shown on Scheme 25).344 A series of such derivatives of dibenzofulvalene have recently been reported (P46A, P46B). In an elegant way it was demonstrated that the HOMO position can precisely be tuned by the nature of the spacer.345 Pyrrole and thiophene spacers increased the HOMO level whereas the benzene ring spacer signicantly decreased it. As a result transistors fabricated from the derivative containing the benzene ring spacer show improved air operating stability and better electrical parameters (see Table 3). Stability can also be assured by close crystalline packing in compounds which should be unstable in operating conditions, i.e. for molecules whose HOMO levels lies too high. In a recent paper346 it has been reported that hexamethylene tetrathiafulvalene derivatives containing linear and branched alkyl substituent (P47) show uniformly dense stacking structures. Stable in air transistors are obtained for both single crystals and thin polycrystalline layers despite that fact that P47 compounds are easy to oxidize. To summarize this part of the paper, several new interesting molecules from dierent families of organic semiconducting compounds have been synthesized in the last decade (a large fraction of them in the past two years!). Presently available, carefully designed molecular semiconductors combine solution processability with high charge carriers mobility and air operating stability. Solution processing of LMWSC on large surface areas is still a challenge because these materials have limited lm forming properties. This problem can be overcome either by appropriate blending of LMWSC with commodity polymers or by the use of macromolecular semiconductors. For this reason research directed towards the development of new semiconducting polymers is carried out in parallel, frequently by the same research groups which are active in the LMWSCs research. 5.2 High molecular weight compounds Many of electroactive polymers designed and synthesized with the goal to use them in OFETs are high molecular weight analogues of small semiconducting molecules described above.
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Fig. 7 Possible nonequivalent triads in nonregioregular poly(alkylthiophene). Each particular triad can be identied by 1H NMR on the basis of the chemical shift of the singlet corresponding to the only aromatic proton (indicated above). The degree of regioregularity is dened as (Shtht/(Shtht + Sttht + Shthh + Stthh)) 100%, where S = integrated surface area under the NMR peak corresponding to a given triad.
This puts some limits in the selection of polymers appropriate for fabricating OFETs. First, if the position of the HOMO level of a given small molecule is on the borderline of air operating stability, the HOMO level of the corresponding polymer will be too high because this level is being raised with increasing molecular weight. Second, solution processing is, in general, much more dicult in the case of polymers as compared to the corresponding small molecules. Polymers and co-polymers containing thiophene moieties. Strong pp interactions render unsubstituted polythiophenes insoluble. Inducing solubility in this type of macromolecular compounds is a delicate matter. In the overwhelming majority of conjugated polymers introducing solubilizing alkyl side groups to the conjugated main chain has a negative impact on the polymer conformation which becomes less planar. As a result the polymer band gap widens and the LUMO and HOMO levels are shifted to undesirable positions. From this point of view poly(thiophene)s represent several advantages since in many cases their interesting electronic properties are not lost upon their functionalization with side alkyl groups. Poly(alkylthiophene)s are soluble in many common solvents suitable for thin lm casting and other solution processing operations, among them in THF, chloroform, toluene, chlorobenzene and dichlorobenzene, the latter being commonly used for thin lms depositions.
Synthetic procedures developed in the past two decades resulted in the preparation of several regiochemically well dened poly(alkylthiophene)s with electrochemically determined HOMO levels in the vicinity of 4.9 eV with respect to the vacuum level. Given the position of their HOMO level, poly(alkylthiophene)s are more stable in the neutral state and much less susceptible to accidental redoping than polymers with higher lying HOMO levels such as polypyrrole or poly(ethylenedioxythiophene) (PEDOT).347 As a consequence, high ON/OFF ratios can be obtained for poly(alkylthiophene)-based OFETs. Among poly(alkylthiophene)s, poly(3-hexylthiophene) is probably the most extensively studied as a p-type semiconductor for p-channel OFETs applications. Initially used methods of poly(3-alkylthiophene) preparation, like oxidative polymerization of 3-hexylthiophene348 or Kumada-type condensation of diiododerivatives349 were not regiospecic and led to a non-regioregular chain in which four types of triades could spectroscopically be distinguished (see Fig. 7). Chain regioregularity, turned out to be a key parameter determining the performance of poly(3-hexylthiophene)-based transistors. Its lowering from 96% to 70% resulted in a decrease of the FET charge carrier mobility by more than three orders of magnitude.350 For this reason strict control of chain regioregularity is of primary importance. Several methods of the synthesis of regioregular poly(3-alkylthiophene)s, leading to regioregularity >98%, have been proposed in the past 20 years21 including the initial two proposed by McCullough351 and Rieke352 and a very recent one in which thienylmanganese halides were used in the presence of Ni(dppe)Cl2 catalysts to yield highly regioregular poly(hexylthiophene) (P3HT).353 From the practical point of view the Grignard metathesis (GRIM) method354 deserves a special interest since it enables a larger scale synthesis in relatively mild conditions. It can be briey outlined as follows. In the rst step 2,5-dibromo-3alkylthiophene is converted into the corresponding Grignard reagent in the metathesis reaction with, for example, t-butylmagnesium chloride. Out of two isomers formed only isomer A undergoes condensation to regioregular poly(3-alkylthiophene) (Pp1) (see Scheme 26). Poly(alkylthiophene)s of dierent type of regioregularity, for example hh-tt coupled polymers (Pp2), which can be obtained starting from 3,3 0 -dialkyl-2,2 0 -bithiophenes355 or 4,4 0 -dialkyl-2,2 0 -bithiophenes through chemical or electrochemical oxidative polymerization356 (see Scheme 27), are poorly conjugated and for this reason not suitable for applications in organic electronic devices. This is caused by the fact that planar tt coupled dimers are twisted with respect to each other as a result of their hh coupling. This induces a
Scheme 26 Synthesis of regioregular poly(3-alkylthiophene)s (Pp1) via Grignard metathesis (GRIM) method.
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Scheme 27 Synthesis of poly(3,3 0 -dialkyl-2,2 0 -bithiophene)s and poly(4,4 0 -dialkyl-2,2 0 -bithiophene)s (Pp2).
signicant non-planarity of the macromolecular chain as evidence by spectroscopic and structural studies.357 Large number of regiochemically well dened, solution processable polythiophene derivatives have been prepared with the purpose of their use in organic electronics. The majority of the applied polymerization methods can be classied into ve groups (see Scheme 28). Oxidative, Yamamoto and Kumada couplings involve one type of macromonomers and the type of repeat units in the polymer is pre-dened by the chemical constitution of the macromonomer. In Suzuki and Stille couplings two types of end functionalized monomers are used necessarily yielding alternating copolymers. However in these procedures the main polycondensation reaction may be accompanied by homocoupling side reactions which result in the introduction of
defects to the polymer chain.358 It should also be noted that Suzuki and Stille couplings are sometimes used in the preparation of macromonomers with one of the monomers being monofunctionalized in this case. The above listed methods can be applied in the synthesis of regiosymmetric poly(dialkylterthiophene)s which can formally be considered as alternating copolymers of thiophene and dialkylbithiophene. Although they contain a smaller number of solubilizing groups than poly(3-alkylthiophene)s (two alkyl groups per three thiophene units) they still show good solution processability and can be used for OFETs fabrication via solution processing.359 Poly(3,3 0 0 -dialkyl-2,2 0 :5 0 ,2 0 0 -terthiophene)s, (Pp3) were rst reported by Gallazzi et al.360 The monomer was synthesized by coupling of 3-alkyl-2-iodothiophene (in a form of a Grignard reagent) with 2,5-diiodothiophene in the presence of Ni(dppp)Cl2 catalyst. It was then oxidatively polymerized to give the corresponding polymer. More recently, the monomer is usually synthesized from 2-bromo-3-alkyl thiophene and diboroderivative of thiophene through Suzuki coupling because in this case the purication process is simpler. The same oxidative coupling is then applied to yield the polymer (see Scheme 29).361 Alternatively poly(3,3 0 0 -dialkyl-2,2 0 :5 0 ,2 0 0 tertiophene)s (Pp3) can be obtained by Stille-type polycondensation of 5,5 0 -dibromo-4,4 0 -dialkyl-2,2 0 -bithiophene with distannylated thiophene.362 Poly(3 0 ,3 0 0 0 -dialkyl quaterthiophene)ssolution processable poly(thiophene)s containing one alkyl per two thiophene rings (Pp4)were
Scheme 28 Most common preparation methods used in the synthesis of thiophene-based polymers and co-polymers.
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Scheme 29 Synthetic route to Pp3.
Scheme 30 Oxidative polymerization of 3 0 ,3 0 0 0 -dialkyl quaterthiophene.
prepared by oxidative polymerization of the corresponding monomer (see Scheme 30) and tested as components of OFETs.363 OFET active layers were fabricated from structurally ordered nanoparticles of poly(3 0 ,30 0 0 -didodecylquaterthiophene)s yielding transistors of very high performance (see Table 4). Its selenophene derivative i.e. poly(5,5 0 -bis(3-dodecylthiophen-2-yl)-2,2 0 -bisselenophene) (Pp5) (Scheme 31), has more recently been prepared either by microwave assisted Stille coupling of 5,5 0 -bis(trimethylstannyl)-2,2 0 -biselenophene and 5,5 0 -dibromo-4,4 0 -didodedecyl-2,2 0 -bithiophene or by oxidative polymerization of 5,5 0 -bis(3-dodecylthiophen-2-yl)2,2 0 -biselenophene.364 The same authors also synthesized a selenophene polymer containing two additional alkylthiophene groups in the repeat unit, namely poly(5,5 0 -bis(4,4 0 -didodecyl2,2 0 -bithiophen-5-yl)-2,2 0 -biselenophene) (Pp6). Pp5, similarly as Pp4, is structurally well organized whereas Pp6 is amorphous. Poor supramolecular organization is in this case caused by a signicant torsion angle between the adjacent repeat units which originates from hh coupling of alkylthiophene rings as in Pp2. Such torsion makes interlayer packing and pp stacking more dicult and as a result Pp6-based transistors exhibit much lower charge carriers mobilities as compared to Pp5 ones (see Table 4). Regioregular polythiophenes containing electron withdrawing dialkylcarboxylate substituted bithiophene groups alternating with non-substituted bithiophene ones have been prepared by Stille coupling (Pp7). These macromolecular compounds can be considered as donoracceptor polymers with unsubstituted bithiophene groups as the electron donating units.365 Polythienothiophene-type polymers constitute one of the most promising group of semiconductors for p-channel OFETs application.12a Poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)s (Pp8) were prepared via Stille coupling of 5,5 0 -dibromo-4,4 0 -dialkyl-2,20 -bithiophene with distannylated thieno[3,2-b]thiophene).366 The same method was applied in the
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synthesis of their thieno[2,3-b]thiophene) analogues (Pp9).367 Similar polymers, with alkyl solubilizing groups attached to the fused thiophene ringspoly(2,5-bis(2-thienyl)-3,6-dialkylthieno[3,2-b]thiophene)s (Pp10)were prepared by Yamamoto coupling of 2,5-bis(5-bromo-2-thienyl)-3,6-dialkylthieno[3,2-b]thiophene,368 by oxidative polymerization of 2,5-bis(2-thienyl)3,6-dialkylthieno[3,2-b]thiophene)s369 or by Stille coupling.12a The crystallographic structure of Pp8 and other polymers of this group, in which the chain conformation is all anti, is basically similar to that of regioregular poly(3-alkylthiophene)s (vide infra). This facilitates the formation of very ordered supramolecular organization of so called p-stacked lamella and as a result high OFET mobilities are measured for these compounds (see Table 4). Oxidative polymerization was used to prepare derivatives containing alkyl substituents both in the quaterthiophene unit and the thienothiophene unit, namely poly(2,5-bis(3-dodecylthiophene-2,2 0 -bithiophen-5-yl)-3,6-dimethylthieno[(3,2-b]thiophene) and its selenium analoguepoly(5 0 5 0 0 -(3,6-dimethylselenopheno[3,2-b]selenophene-2,5-diyl)bis(3-dodecyl2,2 0 -bithiophene) (Pp11, Pp12).370 The presence of a spacer (unsubstituted thiophene ring) between the fused aromatic core and dodecylthiophene is necessary in this case because polymers without such spacers exhibit less ordered supramolecular organization and very poor performance in thin layer OFETs.370 As in the case of Pp2 and Pp6 this is caused by hh coupling of the adjacent alkyl substituted aromatic rings rendering the chain out of planarity. Semiconducting compounds, which formally can be considered as alternating copolymers of bithiophenes and tri-, tetra- or pentathienoacenes, containing alkyl solubilizing groups either in the thienoacene unit (Pp13, Pp14, Pp15)371 or in the bithiophene one (Pp16),372 have recently been synthesized via Stille coupling. Polythiophene derivatives with trithienoacenes randomly distributed along the polymer backbone have also been reported (Pp17).373 Copolymers of dialkylthienoacene
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Table 4
Polymeric semiconductors for p-channel FETs; Mn, polydispersity, position of the HOMO level and transistors parametersa Mn(Da)/PD 13000/2.23 17300/1.32 22100/1.47 12800/1.63 6000/1.25 2500030000/2 29000/2 12400/1.58 13300/1.89 15200/1.83 26285/1.94 13142/1.23 9287/1.15 22922/2.28 7900/1.3 38000/1.15 40000/1.26 62000/1.4 59000/1.47 50000/1.7 32000/1.7 16000/1.9 10300/2.9 13700/3 16300/3.9 18000 22000 21000 21000 17000 45000/2.4 20000 22000 4100/1.5 7200/2.4 8700/1.8 10000/1.8 35000/1.93 9000/1.87 18300/1.8 15800/1.7 6250/1.6 9250/2.47 4911/1.57 36000/3.1 34000/3.7 10000/3.5 17000/2.6 15000/1.7 4700/1.39 6200/1.71 11325/2.1 11000/2.2 18600/2.3 12300/1.65 45500/2.12 13100/1.76 7200/2.84 8300/2.81 4200/1.93 8200/1.44 27900/1.90 15000/1.69 15000/1.6 27000/2.0 4930/3.34 3164/1.58 4900/2.15 HOMO/eV 5.00 5.04 5.31 5.84 5.05 5.30 5.23 5.00 5.10 5.15 5.20 5.21 5.14 5.06 5.04 5.11 5.08 4.68 4.88 4.96 5.30 5.20 5.15 5.20 5.19 5.00 5.10 5.10 4.77 4.92 4.95 5.28 5.33 4.92 5.00 4.93 5.80 5.60 5.66 5.64 5.20 5.02 5.04 5.18 5.12 5.14 5.20 4.80 4.50 4.50 4.40 4.50 5.40 5.50 5.99 5.94 5.21 5.12 m/cm2 V1 s1 3 10 1.4 101 2 102 1.4 105 6 102 6.3 101 1.5 101 2.5 101 3 102 4 102 103 7.2 102 3.3 101 1.5 103 3 101 2.2 103 9.1 103 2.8 102 1.5 102 2.6 102 1.3 101 3.5 103 5 102 8 102 1.5 1012.5 101 1.3 104 2.1 103 2.7 102 1.3 101 1.5 102 103 106 3.3 101 1.3 1025 102 5 1022.3 101 1.2 1013 101 5.1 103 6.6 103 2.8 103 1 1022 102 5.4 104 1.6 104 1.95 101 7 102 (h+) 4.6 102(e) 1.6 104 6 105 6 103 2.2 103 3.1 104 1.5 101 7.8 103 2.26 102 2 102 1.5 103 5.7 103 8.9 103 4.0 103 2.2 103 2.4 103 9.2 104 1.1 105 7.6 105 2 102 4 102 105 2 105 2.0 102 1 105 1.9 104
2
Compound Pp3 Pp4 Pp5 Pp6 Pp7 Pp8 Pp9 RQC10H21 Pp10 Pp11 Pp12 Pp13 Pp14A Pp14B Pp15 Pp16 Pp17A Pp17B Pp17C Pp17D Pp18 Pp19 Pp20 Pp21 Pp22 Pp23 Pp23A Pp23B Pp23C Pp23D Pp23E Pp24 Pp25 Pp26 Pp27A Pp27B Pp27C Pp28A Pp28B Pp29 Pp30 Pp31 Pp32 Pp33A Pp33B Pp34 Pp35A Pp35B Pp35C Pp35D Pp36 Pp37A Pp37B Pp38 Pp39A Pp39B Pp39C Pp40 Pp41 Pp42A Pp42B Pp43A Pp43B Pp44 Pp45 Pp46 Pp47 Pp48B Pp49 Pp50
a
ON/OFF ratio 2 10 >107 103 102 >105 >107 105 >107 106 106 103 106 >105 104 107 104 4 104 2 104 104 4 120 140 105 5 104 105106 2.4 102 7.1 103 1.5 105 1.9 105 9.1 104 103 o102 105107 105107 105107 4.9 103 1.3 106 2.8 104 >105 105 105 1.7 106 2.4 104 1.1 104 2.1 103 3 104 4 106 5 104 104 3.67 104 105 106 3 105 5.2 104 1.5 106 1.5 106 >106 5.7 104 104 1.3 103 1.2 103 1.2 102 >106 >106 5 102 5 103 105 103 5 104
2
Operating condition [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.]
Ref. 362 363a 364 364 365 12a, 366b 12a, 367 368 370 370 371b 371b 371a 371b 372 373 373 373 373 327 327 327 374 374 375 376 376 376 376 376 377 377 378 380 380 380 381 381 381 383 384 384 381 381 381 374 374 386 386 387 388 388 389 393 393 393 406 407a 407a 407a 407a 407a 406 406 386 386 412 413 414
[a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.]
[a.o.] [a.o.]
[a.o.] [a.o.] [a.o.] [a.o.] [a.o.]
[a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.] [a.o.]
All listed polymeric semiconductors were solution processed, [a.o.]-air operating.
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Scheme 31 Structures of thiophene polymers and copolymers discussed in the paper.
series (Pp13, Pp14, Pp15) show lower lying HOMO level than regioregular poly(3-alkylthiophene)s (see Table 4) which reects their improved oxidative stability. The oddeven phenomenon inuences their supramolecular organization. In the case of even number of fused rings (Pp14) the orientation of alkyl substituents facilitates the formation of densely packed structure. For odd number polymers (Pp13 and Pp15) the packing is less dense. This has a profound eect on the semiconducting properties of these polymers and, as expected, Pp14 shows two orders of magnitude higher OFET mobility than Pp13 and Pp15. Analogues of these thienothiophene-based copolymers which contain pyrrole units, namely copolymers of dithieno[3,2-b:2 0 ,3 0 -d]pyrroles Pp18 and alkylthiophene or dilalkylbithiophenes (Pp19 and Pp20 in Scheme 32) have also been synthesized by Stille coupling and tested as active materials in OFETs.327 Thin lms of these polymers show the structure of randomly oriented lamellae whose organization and orientation signicantly improve upon annealing. The presence of pyrrole moiety in the polymer chain causes an increase in the position of the HOMO level as compared to the thienoacene analogues (see Table 4). This has a negative impact on the ON/OFF ratio in the fabricated OFETs since these polymers are easy to be chemically doped and dicult to undope. As a result charge carriers originating from
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incomplete undoping or accidental doping exist in the polymer, increasing the OFF state current. Stille coupling procedure has also been applied to the synthesis of copolymers of thiophene (or bithiophene) with dithienosilolesother promising candidates for application in p-channel OFETs (Pp21, Pp22).374 These polymers show lower lying HOMO level as compared to regioregular poly(3-hexylthiophene) which improves their air stability in the OFET operating conditions. Solution processable polythiophene derivatives containing fused aromatic and heterocyclic units such as poly(4,8-dialkyl2,6-bis(3-alkylthiophen-2-yl)benzo[1,2-b:4,5-b 0 ]dithiophene)s (Pp23) also seem good candidates for application as active layers in p-channel OFETs. The monomers can, in this case, be prepared by Suzuki coupling of 2,6-dibromo-4,8-dialkylbenzo[1,2-b:4,5-b 0 ]dithiophene with 3-alkylthiophene-2-boronic acid ester. They are then oxidatively polymerized to the corresponding polymers using FeCl3 as the oxidizing/polymerizing agent (see Scheme 33).375 Other polymers based on fused aromatic-heterocyclic units, namely homopolymer of benzodithiophene (Pp23A) and alternating copolymers of benzodithiophene and bithiophenes (Pp23B, Pp23C, Pp23D, Pp23E) have been recently reported.376 They can be obtained by oxidative polymerization of the corresponding macromonomers. Very high OFET mobility
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Scheme 32 The structures of the polymers discussed in the paper ctd.
was measured for Pp23D (0.13 cm2 V1 s1). Other polymers of this series showed one-order of magnitude lower mobilities. A series of macromolecular compounds in which oligothiazoles and oligothiophenes units alternate, namely poly(dialkylbithiophene-alt-dialkylbithiazole)s (Pp24, Pp25)377 and poly(dialkyltetrathiophene-alt-dialkylbithiazole)s (Pp26)378 have been synthesized by Yamamoto and Stille coupling, respectively. They are typical donoracceptor type copolymers with electron accepting bithiazole units and electron donating oligothiophene ones. Copolymers containing fused thiazole rings have also been reported, for example poly(2,5-bis[3alkyl-5-(3-alkylthiophen-2-yl)thiophen-2-yl]thiazolo[5,4-d]thiazole)s (Pp27A, Pp27B, Pp27C).379,380 Pp26 is an interesting case. Its macromolecules spontaneously self-organize in the liquid crystalline mesophase, facilitating, through annealing, the formation of highly ordered supramolecular organization in which the direction of p-stacking is parallel to the substrate surface. Since such orientation is favorable for charge carriers transport, the resulting OFET mobilities reach 0.3 cm2 V1 s1. Similarly high mobility is reported for Pp27, although its thin layers are less ordered (Table 4). Detailed morphological
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studies have shown small lamellar-like ordered domains which are packed into amorphous structures. The domains percolate, however, facilitating the charge carriers transport. This example shows that appropriate morphology may lead to high OFET mobilities despite the fact that large volume fraction of the semiconductor layer is of disordered nature. Polymers consisting of fused aromatic thienopyrazine and quaterthiophene alternating units can be considered as another example of donoracceptor type macromolecular compounds. They are prepared by Stille coupling of 8,10-bis[5-bromo-3-alkylthiophen-2-yl)acenaphtho[1,2-e]thieno[3,4-b]pyrazine (Pp28A and Pp28B) (Scheme 34) or 10,12-bis[5bromo-3-alkylthiophen-2yl]dibenzo[f,h]-thieno[3,4-b)quinoxaline with distannylated 3,3 0 -dialkylbithiophene (Pp29).381 Showing low band gap (1.161.43 eV) these polymers are not only suitable for the OFETs applications but also for photovoltaic applications. Copolymers of uorene and thiophene or oligothiophenes constitute an important group of semiconductors for p-channel OFETs applications. Alternating copolymers of 9,9-di-n-octyluorene and bithiophene (Pp30) were prepared
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Scheme 33 Synthesis of Pp23.
Scheme 34 Thienopyrazine, uorene and related copolymers with thiophene used in p-channel FETs.
from 9,9-di-n-octyluorene-2,7-di(ethyleneboronate) and 5,5 0 dibromo-2,2 0 -bithiophene by Suzuki coupling.382 Pp30 shows nematic liquid crystal behavior. This property can be exploited for the orientation of the polymer chain with the help of a special alignment layer. The resulting OFETs exhibit good operating stability.383
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Copolymers containing fused thienothiophene segments in their oligothiophene unit, namely poly{2-[5-(9,9-dibutyl-9Huoren-2-yl)-3-hexylthiophen-2-yl]-5-(3-hexylthiophen-2-yl)thieno[3,2-b]thiophene} (Pp31) and poly{2-[5-(9,9-dibutyl-9Huoren-2-yl)-3-hexylthiophen-2-yl]-5-(4-hexylthiophen-2-yl)thieno[3,2-b]thiophene} (Pp32) were also synthesized by the
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same method.384 Note that the oligothiophene segment in (Pp31) is identical to the repeat unit of (Pp8). Pp8 is liquid crystalline but its copolymer with uorene Pp31 does not show liquid crystal properties and yields amorphous layers upon casting. For these reasons it shows rather moderate OFET mobility (see Table 4). Another group of donoracceptor copolymers consists of alternating units of terthiophene functionalized with aromatic fused pyrazine and 9,9-dialkyluorene. These copolymers were obtained by Suzuki coupling (Pp33 and Pp34).381,385 Similarly as Pp28 and Pp29 these copolymers are low band gap semiconductors and for this reason they are also suitable for photovoltaic application. Very high OFET mobility of Pp33A containing dodecyl substituents should be underlined (Table 4). Pp33B with 2-ethylhexyl substituent shows ambipolar behavior. Benzosilole analogues of uorene have also been tested together with thiophene or bithiophene as comonomers. The resulting copolymers (Pp35A, Pp35B), obtained by Suzuki coupling, showed molecular weights exceeding 30000 g mol1, however with a rather high polydispersity coecient. Pp35A and Pp35B show signicantly lower lying HOMO level than copolymers of dithienosiloles and thiophene (Pp21) or bithiophene (Pp22). For this reason OFETs operating in air can be fabricated from these polymers which however suer from a rather low charge carriers mobilities (see Table 4).374 Alternating copolymers of 2,7-carbazoles and bithiophenes are usually prepared by Stille coupling of dibromoderivative of carbazole and distannylated bithiophene (Pp35C) (Pp35D).386 As deposited thin lms are amorphous, however annealing of Pp35C layers improves their supramolecular organization as evidenced by X-ray studies. Pp35D layers remain amorphous after thermal treatment. For these reasons the OFET mobility of Pp35C is very sensitive to the chosen processing method reaching 2 103 cm2 V1 s1 for optimal processing conditions (see Table 4). Copolymers containing alternating dialkylquaterthiophene and vinylene units (Pp36) have been prepared by Lim et al.387 The macromonomer was rst prepared by Stille coupling, then brominated and nally condensed to the corresponding copolymer via nickel mediated coupling according to Yamamoto reaction conditions. Its HOMO level is slightly lower than that of regioregular P3HT which leads to an improvement of its air stability in OFET operating conditions. Thin layers of Pp36 show highly ordered supramolecular organization which results in a high charge carriers mobility (Table 4).
Donoracceptor type copolymers consisting of alternating naphthylene cyclopentadienone acceptors and dialkylquaterthiophene donors (Pp37) were synthesized by Yang et al.388 using Stille coupling of dibromo derivative of 2,5-dithienyl-3,4(1,8-naphthylene)cyclopentadienone and distannylated 4,4 0 -dialkyl-2,20 -bithiophene. Pp37A and Pp37B show similar position of the HOMO level to that of regioregular P3HT and reasonable charge carriers mobility (Table 4). This contradicts frequently expressed belief that carbonyl groups in the conjugated backbone act as charge traps and their presence should be avoided. An interesting group of semiconducting polymers containing thienylene, vinylene and uorene groups in their main chain have also been reported. Poly[(1,2-bis-(2 0 -thienyl)vinyl-5 0 ,50 0 diyl)-alt-(9,9-dioctyluorene-2,7-diyl)] (Pp38), synthesized by Chung et al.,389 is a representative example of this group of compounds. Thin layers of Pp38 are amorphous; however the measured OFET mobilities are surprisingly high taking into account the disordered layer structure. Metallated donoracceptor conjugated polymers have extensively been used for the fabrication of active layers in bulk heterojunctiontype photovoltaic cells.390 Justication of their use in organic electronic devices requires some explanation. Incorporation of an electron donating transition metal such as Pt into the conjugated polymer main chain enhances intrachain charge transport as a consequence of better p-electron delocalization along the polymer chain especially if the metal atom is directly connected to two alkyne groups.391 This is due to the fact that the d-orbitals (dxy and dxz) of Pt overlap with the py* and pz* orbitals of the alkyne unit.392 Attempts to use this type of polyconjugated systems for p-channel OFETs turned out to be successful. The metallated polymers (Pp39) have been prepared by coupling of alkyne terminated macromonomer with trans-dichlorobis(trialkylphosphine) platinum(II) using classical dehydrohalogenation393 (see Scheme 35). The HOMO level of Pp39 polymers is lower than that of regioregular P3HT which makes them promising candidates for fabrication of air operating transistors. Although thin layers of these semiconductors are amorphous, the measured mobilities approach 102 cm2 V1 s1. This representative but not exhaustive review clearly indicates that essentially all methods used for the preparation of thiophene-based homo- co- and terpolymers, applied for p-channel OFETs fabrication, frequently lead to products showing high polydispersity index24a although cases of the synthesis of polymers with reduced polydispersity are known.394
Scheme 35 Preparation of metallated polymer Pp39.
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The reported molecular masses and polydispersity indices are collected in Table 4. Such polydispersity is disadvantageous from the point of view of transistors or other devices fabrication and the polymers used for electronic applications should be fractionated to get fractions of reduced polydispersity index. The most popular fractionation method consists of sequential extractions of fractions with increasing molecular mass in a Soxhlet apparatus, applying a set of the experimentally determined extracting solvents.395 Using fractions of reduced polydispersity it was possible to demonstrate that the FET charge carriers mobility in regioregular poly(3-hexylthiophene) (RR-P3HT) increases over 5 orders of magnitude reaching 101 cm2 V1 s1 when the molar mass increases from ca. 1000 g mol1 to 27 000 g mol1.229,396 A similar phenomenon has also been observed for poly(3,30 0 -octyl2,20 :50 ,20 0 -terthiophenes) (PDOTT).23 It should also be added that the molecular mass data of poly(thiophene) derivatives found in the literature or provided by the polymer producers should be treated with extreme caution. It has been shown that the molecular mass determination by size exclusion chromatography leads to its underestimation for molar masses up to ca. 2000 g mol1372 and to an overestimation for masses above 2000 g mol1.397 Moreover this overestimation increases with increasing Mn. Charge carriers mobility is not the only parameter which is sensitive to Mn, other properties of poly(thiophene)s such as the position of the HOMO and LUMO levels, the width of the band gap etc. are also inuenced by the molecular mass and this dependence persists to high Mn values These two facts should always be taken into consideration in any comparative studies of polythiophene-based electronic devices.
Fig. 8 Typical structure of P3HT with a E 16 A and c E 7.6 A.
Another key factor, which must be taken into account when selecting polythiophene-based semiconductors for transistor applications, is their supramolecular organization. Regioregular poly(3-hexylthiophene) (P3HT) (Pp1) can be treated here as an instructive example. Its macromolecules not only exhibit a very regular linear conformation favoring extended conjugation length but also, owing to the regular distribution of the hexyl side groups along the polymer chain, they show a remarkable ability to form a self assembled supramolecular organization, resulting in a very regular stacking of polythiophene chains at least in two perpendicular directions in space. Since early 90s, the crystalline structure of P3HT has been studied in detail and the authors proposed an orthorhombic unit cell for the average structure in which the inter-chain distance along the hexyl side-groups is equal to 16 A, while the repeating distance between the two neighboring chains in the perpendicular direction (the so-called p stacking distance) was evaluated to be around 3.8 A (Fig. 8).398 This structural arrangement is remarkably robust. It can be found in P3HT (Pp1) layers deposited by dierent processing techniques, it is also little dependent on the type of the substrate used. In real OFET devices on Si/SiO2 substrates the macromolecules are arranged in such a way that the p-stacking period is maintained, for their major part, parallel to the substrate (c/2 distance in Fig. 8). This favors the charge carriers transport in between the source and the drain electrodes for typical layer-type transistor conguration. The same structural arrangement is obtained for other substrates (glass, ITO), including exible polymeric ones. This is not surprising taking into account that almost all conjugated molecules or macromolecules bearing alkyl side groups have the tendency to adopt the position in which the alkyl chains stand right up on the SiO2 surface. It must be noted that this is in striking contrast with the arrangement of P3HT macromolecules on the HOPG substrate. In this case the thiophene rings prefer to fully interact with six-carbon rings of graphite forcing the macromolecule to stack at on the substrate surface with alkyl side groups registered with the underneath graphite lattice22,399 (with a axis shown in Fig. 8 parallel to the surface). This means that the nature of the substrate has crucial importance for the orientation of the P3HT crystallographic unit cell with respect to its surface. Good performance of P3HT (Pp1)-based OFETs prompted several research groups to carry out research aimed at improving the transistor performance and stability by tuning the semiconductor properties through appropriate functionalization. In the majority of newly developed semiconductors the structure is isomorphic with that of P3HT (Pp1). In layers deposited on the substrates used for the fabrication of OFETs the long period (a distance in Fig. 8) is perpendicular to the substrate surface, along which two polymer chains are separated by a bi-layer of alkyl side groups. In this arrangement, the p-stacking period is parallel to the substrate surface (c/2 distance in Fig. 8). In the semiconductors described in this review the found long periods vary from 15.4 A for the shortest to 27.7 A, depending on the size of the alkyl side chains, the degree of their interdigitation and the tilt angle. The p-stacking distances vary from 3.6 to 4.2 A. Most often the mobilities measured for the OFETs are much better when
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the active layer is highly structured and the found p-stacking distance is not too long i.e. inferior or equal to 3.8 A. It should be noted that based on the available crystallographic data no precise information could be gained concerning the exact ordering in the direction along the polymer chains and the exact way the chains are stacked. This stacking is necessary to obtain good mobility but it can also be postulated that the mode of chains stacking may also inuence the mobility. Thus the control of this stacking pattern would be benecial for the transistor optimization. Another point to be taken into account is the morphology of the deposited layers at a larger scale that the crystallographic unit cell. When the active layer deposition process results in a very irregular morphology with small crystallites more or less randomly oriented the electrical parameters in terms of charge carrier mobility and ON/OFF ratio are usually worse. It should also be pointed out that the macromolecular nature of semiconductors discussed here usually impedes the formation of extended ordered domains as those obtained in layers of low molecular weight semiconductors. As compared to low molecular weight compounds, polymers assure however longer pathway of the intramolecular transport and better degree of interchain connectivity facilitating intermolecular charge carriers transport. For this reason reasonable mobility values are sometimes measured for amorphous active layers like in the case of copolymers of uorenes and thienothiophenes384 or terpolymers containing thienylene, vinylene and uorene units.389 Structural studies are in such cases of limited use since they usually cannot provide an answer to the question why some amorphous materials exhibit high mobility whereas others are poor semiconductors. Many of polymers and co-polymers of polythiophene family combine solution processability with remarkably good charge carriers mobility as seen from the data collected in Table 4. It is however clear that their HOMO level should not be raised above 4.9 eV with respect to the vacuum level; otherwise the ON/OFF ratios are very low. For high ON/OFF ratio low conductivity in the OFF state must be assured. This is possible only in cases when negligible amounts of charge carriers are present in the polymer in the OFF state i.e. the polymer is strictly undoped. Undoping of polymers with high lying HOMO level is dicult, as their accidental p-doping is easy, since they are more stable in the p-doped state than in the undoped one. This is always the case of copolymers containing pyrrole moiety such as copolymers of dithieno[3,2-b:2 0 ,3 0 d]pyrroles and alkylthiophenes (Pp18 and Pp19).
Scheme 36 Synthesis of poly(triarylamine)s.
Poly(triarylamine)s and their derivatives. Poly(trilarylamine)s as semiconductors for p-channel OFETs have been extensively studied in the past decade, it should however be noted that the research interest in these polymers as electroactive materials comes down to late 80 of the past century.400 This interest is not only limited to organic electronics where poly(triarylamine)s can be used as hole transporting materials in electroluminescent devices401 or semiconductors in p-channel OFETs402 but also as electroactive separator materials in rechargeable lithium batteries403 or components of the cathode.404
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For electrochemical applications poly(triarylamine)s are usually prepared by chemical or anodic oxidation of nonfunctionalized monomers. For the use in organic electronics they must be prepared in a solution processable form by methods which are more regiospecic since the control of the polymer chain structure is, in this case, of crucial importance. Solution processable polymers, suitable for the use in OFETs can be prepared by metal catalyzed Yamamoto-type coupling of dihalotriarylamine monomers,405 as shown in Scheme 36. Poly(trihaloamine)s can also be prepared in a two-step procedure in which the intermediate product undergoes Suzuki AB-type condensation406 as shown below for dimethyl substituted poly(triarylamine) (Pp40) (Scheme 36). Microwave assisted, palladium catalyzed condensation of aniline derivatives with dibromobiphenyl or dibromoderivative of other aromatic compounds407 also turned out to be a convenient method to prepare these polymers (Scheme 36). This step growth polymerization requires strictly stoichoimetric amounts of reagents. In addition high conversion degrees (usually >0.95) are necessary to obtain high molecular weight products. Poly(arylamine)-based semiconductors are easy to solution process. Moreover, a signicant progress in controlling their molecular weight and improving their air stability in FET operating conditions, have been achieved in the past few years.408 Thin layers of these polymers are usually amorphous but their OFET mobility reaches reasonable values.409 Copolymers of triarylamine with uorene and other monomers used for the preparation of semiconducting polymers have been studied for more than decade.410 They are usually prepared by Suzuki coupling but other methods are also used. For example microwave assisted, palladium catalyzed condensation of aniline derivatives, described above, can also be used for the preparation of alternating copolymers of
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Scheme 37 Poly(triarylamines) and polycarbazoles.
triarylamine with uorenes (Pp42A and Pp42B) or carbazoles (Pp43A and Pp43B) (Scheme 37).407a Both types of copolymers studied showed lower OFET mobility than the corresponding poly(triarylamine) homopolymer (see Table 4). Dierent results have been reported in a recent paper of Zhang et al.406 These authors have shown that copolymers of triarylamines with uorenes (Pp44) and indenouorenes (Pp45) obtained from diboronate esters of uorene (or indenouorene) and dihalotriarylamine by Suzuki coupling show excellent air operating stability in OFETs and improved charge carriers mobility as compared to the corresponding poly(triarylamine) homopolymer. These polymeric semiconductors can therefore be considered as very promising materials for p-channel OFETs taking into account their relatively facile preparation, excellent processability and air operating stability. Poly(carbazole)s and poly(indenocarbazole)s. Polycarbazoles and their derivatives constitute another group of solution processable polymers which can be applied as p-type
semiconductors in OFETs. An excellent review on their synthesis is recommended.411 Poly(2,7-carbazole)s with dierent substituents can be obtained from dibromocarbazoles by Yamamoto coupling (Pp46), (Pp47). Transistors fabricated from Pp46 and Pp47 can operate in air since these polymers have low lying HOMO level, however they suer from a very low charge carriers mobility and low ON/OFF ratio (see Table 4). Li et al.412 reported on the synthesis of poly(indolo[3,2-b]carbazole)s (Pp48A, Pp48B) together with their physicochemical and electrical characterization. Pp48A was obtained by dehalogenative coupling of dichloroindolo[3,2-b]carbazoles using Zn/NiCl2/PPh3 catalytic system. Pp48B can be obtained by the same method or alternatively from indolo[3,2-b]carbazoles by oxidative coupling which, in this case, is regioselective because its para positions (with respect to the amino groups) are highly activated. As shown by X-ray diraction studies both polymers exhibit highly ordered supramolecular organization. Pp48B prepared by FeCl3 mediated oxidative coupling is a
Scheme 38 Synthesis of hyperbranched polymer Pp49.
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Scheme 39 Synthesis of Pp50.
very good candidate for OFET application showing surprisingly high charge carriers mobility for a polymer of a rather low molecular weight and high polydispersity index (see Table 4). Semiconducting carbazole-based hyperbranched polymer was prepared from bifunctional diboronate esters of N-alkylcarbazole and tetrabromo-substituted carbazole trimer in a one pot Suzuki coupling reaction (Pp49) (see Scheme 38).413 The HOMO level of Pp49 is lower than that of regioregular poly(3-hexylthiophene) so potentially it can be considered as a good candidate for air operating OFETs, however the mobility and the ON/OFF ratio, measured for thin layers, are very low. This is probably associated with highly disordered supramolecular organization, expected for hyperbranched polymers. Moreover the obtained molecular weights are rather low (see Table 4). Suzuki coupling reaction was also used for the preparation of donor acceptor-type alternating copolymers of indolo[3,2-b]carbazole and four dierent acceptors of pyrazine and thiadiazole families.414 Although these polymers were prepared with the goal to be used as components of photovoltaic cells, they were also tested as semiconductors for p-channel OFETs. The main problem associated with the use of these compounds in transistors is their too high lying HOMO level (from 4.62 eV to 4.90 eV with respect to the vacuum level). As a result low ON/OFF ratio are obtained. The most promising seems to be the copolymer with 2,3-[4-(2-ethylhexyloxy)phenyl]quinoxaline (Pp50), whose HOMO position is lower, but even in this case the measured mobilities are rather low (Scheme 39) (see Table 4). To summarize, although the highest charge carriers mobilities are still obtained for polymers containing thiophene moiety in their main chain (see Table 4), there exist several other groups of semiconducting polymers which can compete with polythiophene derivatives in terms of their excellent solution processability and improved stability in air operating conditions. This includes polymers which show surprisingly high charge carriers mobilities, despite the fact that their thin layers are of amorphous nature. 5.3 Blends as semiconducting materials
Blends of two polymers or a polymer and a low molecular weight compound are frequently used in technology since they frequently oer better physical and physicochemical properties than those of individual components of the blend.
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This approach was also exploited in the domain of designing and fabrication of OFETs. Three main type of blends containing organic semiconductors can be distinguished: (i) blends of low molecular weight semiconductors (LMWSC) with insulating polymers; (ii) blends of semiconducting polymers with insulating ones and (iii) blends of low molecular weight semiconductors (LMWSC) with semiconducting polymers. There are several reasons which make the preparation of blends of low molecular weight semiconductors (LMWSC) and industrial polymers technologically interesting. Solution processing of LMWSC is dicult and frequently yields nonuniform lms of uneven thickness. From this point of view processing from a solution which contains a LMWSC and a polymer is much easier since the rheological properties of such solution are governed by its macromolecular component and are easier to control. Moreover polymers have lm forming properties. Finally blending frequently improves air operating stability of the semiconducting component. Blends of this type usually involve polystyrene and related commercial polymers like poly(methylstyrene), poly(methylmetacrylate), poly(vinylphenol). Varying the molecular weight of the polymeric binder its tacticity as well as addition of crystallization inhibiting agents enables strict control of the blend morphology.415 There are two strategies in the preparation of LMWSCinsulating polymer blends. The rst strategy is based on percolation phenomena where a percolating network of LMWSC is formed within the polymer matrix which assures charge carriers transport between the source and drain electrode. The second approach exploits the stratication concept. Blending of 6,13-bis(triisopropylsilylethynyl)pentacene (P5) with semi-crystalline isotactic polystyrene (i-PS) is an instructive example of this approach. When the binding polymer crystallizes from solution more slowly than the LMWSC component, stratication of the semiconductor is observed to both interfaces. The polystyrene layer constitutes in this case a natural barrier against ambient air and reasonable values of stable saturated hole mobility are obtained for low weight contents of the semiconductor components of ca. 10 wt%.416 Similar behavior was found for blends of 6,13-bis(triisopropylsilylethynyl)pentacene (P5) with high molecular weight poly(a-methylmetacrylate).417 Blends of commodity polymers with high molecular weight semiconductors (HMWSC) such as regioregular poly(3-hexylthiophene) or poly(triarylamine)s were also studied. In blends
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with semi-crystalline polymers, crystallization-induced phase segregation of both components occurs which leads to stratication phenomena in which the semiconducting polymer is expelled to the surfaces of the lm formed, similarly as in the case of LMWSCpolymer blends discussed above.418 As a result high charge carriers mobility and high transistor stability is assured for blends with isotactic polystyrene (i-PS) or linear high density polyethylene (HDPE) containing very small contents of the semiconductor component (around 2 wt% and 5 wt% for HDPE-based and i-PS-based blends, respectively). In the case of blends with amorphous polymers such as atactic polystyrene (a-PS) or branched low density polyethylene (LDPE) this phase separation is not so pronounced and the relationship between the content of poly(3-hexylthiophene) and charge carriers mobility is of classical percolation character. One must however be aware of the fact that the percolation threshold is strongly dependent on the aspect ratio, being extremely small for elongated objects such as bers of nanowires. It is known that nanobers of regioregular poly(3-hexylthiophene) can be obtained by appropriately adjusting solution processing conditions.419 The formation of such nanobers facilitates the percolation in blends with amorphous polymers such as atactic polystyrene (a-PS) and others. Thus high charge carriers mobilities can also be obtained for blends of amorphous polymers containing low amounts of a semiconducting polymer, provided that the latter exhibits high aspect ratio.420 Blends with poly(triarylamine)s were also studied. In this case the semiconducting polymer is amorphous. Its blending with amorphous polymers (atactic poly(methylmetacrylate), atactic polystyrene and others) does not involve crystallization induced phase separation and no stratication processes are observed. The dependence of the charge carriers mobility on the content of the semiconductor polymer shows in this case classical percolation behavior. Lower percolation threshold is found for blends with semicrystalline isotactic polystyrene (i-PS), indicating the role of the matrix crystallization in the formation of continuous phase of the amorphous polymeric semiconductor.421 The third group of blends used as active layers in p-channel OFETs consists of high molecular weight semiconductors (HMWSC) with low molecular ones (LMWSC) ones, for example poly(triarylamine) and 6,13-bis(triisopropylsilylethynyl)pentacene (P5)422 or 5,11-bis(triethylsilylethynyl)anthradithiophene (P8).423 Blending signicantly improves processing of the low molecular weight component and as a result high quality lms of reproducible properties are obtained. The measured high mobility in operating conditions is probably caused by improved conductive pathway since both blend components are semiconductors.
with extended air operating stability were developed. At this point a new question arises: is it better from the technological point of view to process neat organic semiconductors or rather their blends with insulating commodity polymers? The blending approach, both using the stratication and percolation concepts, is attractive because solutions of such blends show superior and more controllable rheological properties than solutions of neat semiconductors. The next problem is the control of the supramolecular organization in the deposited layers which frequently determines the electrical charge transport properties in the fabricated devices. There exist examples of amorphous (glassytype) semiconductor layers exhibiting reasonable charge carriers mobilities, still the best transistor parameters are obtained in these cases where the active layers are highly ordered or exhibit morphologies favoring the charge carriers transport. This underlines the importance of the use of supramolecular chemistry concepts in the development of new molecular semiconductors. Application of these concepts is especially important in the case of quickly progressing hybrid (organicinorganic) electronics. Organicinorganic hybrids have been used in recent years for the fabrication of photovoltaic cells, light emitting diodes, photodiodes, transistors and other devices. Processing of hybrid materials is especially dicult because of the distinctly dierent chemical nature of their organic and inorganic components. Functionalization, leading to molecular recognition or other phenomena promoting hierarchical self-assembly, is frequently needed for solution processing of hybrid systems. Commodity polymers cannot assure, in these cases, the molecular level processing and careful design of all components of the hybrid material is needed.
Acknowledgements
Financial support from Polish Ministry of Science and Higher Education through research project no. NN205105735 in years 2008-2011 is acknowledged. We thank Dr B.Grevin and F. Gustavo for providing FET device pictures.
References
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6. Conclusions
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Conducting polymers for carbon electronics themed issue

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Chem. Soc. Rev., 2010, 39, 25772632 | 2577

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Scheme 2 Synthesis of HOMO/LUMO positions.

Scheme 3 Synthetic pathway to alternating copolymers of oxadiazole and oligothiophene.

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Chem. Soc. Rev., 2010, 39, 25772632 | 2581

ELUMO = (Ered EHOMO = (Eox

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3. Principles of eld eect transistor operation

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Fig. 5 Possible congurations of organic eld eect transistors.

4. Organic semiconductors for n-channel eld eect transistors

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Chem. Soc. Rev., 2010, 39, 25772632 | 2585

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Synthesis of core-unsubstituted naphthalene and perylene bisimides.

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Scheme 7 Functionalization of the core in perylene bisimides.

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Functionalization of the core in naphthalene bisimides.

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Chem. Soc. Rev., 2010, 39, 25772632 | 2593

Scheme 9 Miscellaneous aromatic bisimides studied as active components of n-channel OFETs.

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Scheme 11 Thiophene co-oligomers and quinoidal oligomers.

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Scheme 12 Polymers used in n-channel transistors.

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Scheme 13 Fullerene derivatives and metal complexes used in n-channel FETs.

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5. Organic semiconductors for p-channel eld eect tranistors

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ON/OFF ratio 5 10 3.3 104 104 107 >104 2 107

Ref. 227 232 80b 241 243 245

[a.o.] - air operating.

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Scheme 14 Transformation of soluble precursor into a,o-distyryloligothiophenes through thermal treatment.

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Scheme 15 Fused aromatic compounds used in p-channel FETs.

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Scheme 16 Final step of the synthesis of P17.

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