TW201333156A - Method for producing an organic semiconductor device - Google Patents

Abstract

A method for producing an organic semiconductor device (110) having at least one organic semiconducting material (122) and at least two electrodes (114) adapted to support an electric charge carrier transport through the organic semiconducting material (122) is disclosed. The organic semiconducting material (122) intrinsically has ambipolar semiconducting properties. The method comprises at least one step of generating at least one intermediate layer (120) which at least partially is interposed between the organic semiconducting material (122) and at least one of the electrodes (114) of the organic semiconductor device (110). The intermediate layer (120) comprises at least one thiol compound having the general formula HS-R, wherein R is an organic residue. The thiol compound has an electric dipole moment pointing away from the SH-group of the thiol compound. The electric dipole moment has at least the same magnitude as the electric dipole moment in 4-Phenylthiophenol. By the intermediate layer (120) an ambipolar charge carrier transport between the electrodes (114) is suppressed in favor of a unipolar charge carrier transport.

Description

Method for preparing an organic semiconductor device

The present invention relates to a method for preparing an organic semiconductor device. In other aspects, the present invention relates to an organic semiconductor device, and an use of an intermediate layer comprising at least one thiol compound for suppressing bipolar charge carrier transport in an organic semiconductor device to facilitate single Polar charge carrier transport. The method, organic semiconductor device and use of the present invention are generally preferably applicable to the field of organic electronic devices, or better applied to the field of organic field effect transistors (OFETs).

In recent years, organic semiconductors such as polymerized semiconductors, monomeric semiconductors, or oligomeric semiconductors have attracted attention as promising alternative materials for conventional semiconductors such as germanium. Therefore, in many fields of electronic equipment, by using an organic semiconductor, a conventional inorganic semiconductor material can be replaced, or even a novel device can be produced. Thus, mention may be made of organic diodes and organic light emitting diodes (OLEDs), organic photovoltaic devices (OPDs) and organic transistors, in particular organic field effect transistors (OFETs). In the following, the invention will be primarily described with respect to potential uses in an organic field effect transistor without limiting the scope of the invention. However, it can be used for other applications.

One of the main advantages of organic semiconductors is that they can be processed into films by using low cost techniques. Thus, in particular, polymeric materials can be processed into transistors at low manufacturing costs, specifically for low-end electronic applications. The key requirements of organic semiconductors, specifically polymeric semiconductors, are excellent charge transport characteristics, chemical stability, good solubility in organic solvents, and low cost. Warm processing. In order to utilize higher organic materials and lower power consumption in complementary circuit technologies such as complementary metal oxide semiconductors (CMOS), different p-channel semiconductors are required in a CMOS device (hole-transmission semiconductors, hereinafter also Complementary operation of a so-called p-type semiconductor and an n-channel semiconductor (electron transport semiconductor, hereinafter also referred to as an n-type semiconductor). In addition to application to organic thin film transistors (OTFTs), combinations of these two types of semiconductor materials may also be necessary in OLED technology or OPV technology, particularly for efficient exciton formation or splitting.

A large number of organic materials for organic electronic devices are known and are still being developed. In most cases, a key feature of organic materials is the enlarged π-electron system, which delocalizes the orbital wave function and thereby provides for the transmission of positive and/or negative charge carriers. The movable positive charge in an organic semiconductor is often referred to as a "hole" compared to an inorganic semiconductor, and the movable negative charge is referred to as an "electron." This nomenclature will be used hereinafter, but it is known that charge carrier transport in organic materials is not exactly equivalent to charge carrier transport in conventional inorganic semiconductors. Similarly, the conductive strip of a conventional inorganic semiconductor is generally compared with the lowest unoccupied molecular orbital (LUMO) of an organic material, and the valence band of the inorganic semiconductor material is generally compared with the highest occupied molecular orbital (HOMO) of the organic semiconductor, but I understand that there are some shortcomings of these comparisons.

Among a large number of organic materials known to have semiconductor properties, naphthalene-quinone imine semiconductor polymers, in particular their potential use in organic transistor devices, have received much attention in the past. See WO 2009/098253 A1, Z. Chen et al., Napththalenedicarboximide-vs Perylenedicarboximide-Based Copolymers.Synthesis and Semiconducting Properties in Bottom-Gate N-Channel Organic Transistors, J. Am. Chem. Soc. 2009, 131, 8-9; and H. Yan et al., A high-mobility electron-transporting polymer for printed transistors, Nature, Volume 457, February 5, 2009, pp. 679-686.

In particular, it is known that in the TGBC (top gate contact type) thin film transistor structure with variations in dielectric, substrate and semiconductor deposition methods, poly{[N,N'-bis(2-octyl-12) Alkyl)-naphthalene-1,4,5,8-bis(dimethylimine)-2,6-diyl]-alternative-5,5'-(2,2'-bithiophene)} (P (NDI2OD-T2)) exhibits high n-channel mobility, ie high negative charge carriers or electron mobility, in the range of 0.1 cm ² V ^-1 s ^-1 to 0.65 cm ² V ^-1 s ^-1 . It was also measured under ambient conditions and determined to be stable. As an example of a low bandgap semiconductor, in particular a donor-acceptor copolymer, which exhibits some degree of bipolarity, whereby holes and electrons can pass through the material, in particular in the transistor and more specifically Inject and transfer in the OTFT device configuration. This can be observed when the semiconducting polymer is biased at a negative voltage, where the measured p-channel mobility is observed, ie the positive charge carrier mobility is between 0.1 cm ² V ^-1 s ^-1 to Within the range of 0.2 cm ² V ^-1 s ^-1 . Under certain bias conditions, there are areas where holes and electrons are present in the channel. However, this bipolar area creates several technical challenges. Therefore, a high or inconsistent threshold voltage is first required to obtain a unipolar p-type or unipolar n-type state. In addition, the combined effect of trapping charge carriers is secondarily generated because one or both types of charge carriers are subject to different captures, in particular due to their different chemical properties, such as different chemical moieties. Therefore, in most cases, it is obvious that bipolar is not desired, such as for applications such as display backplanes that utilize OTFTs.

In addition to the technical challenges associated with the design of materials and charge transport, known electrode designs are also a key issue in improving the performance of organic electronic devices. Therefore, in an airport effect transistor, contact resistance becomes a more significant problem when moving to a smaller channel length region to provide higher performance. Therefore, in most cases, the contact resistance problem is due to the energy level mismatch between the work function of the metal electrode and the HOMO of the organic semiconductor material (for hole injection) and/or due to the work of the metal electrode. The function appears with an energy level mismatch between the LUMO (for electron injection) of the organic semiconductor material. In devices with larger channel lengths, this effect can be ignored in most cases because the charge transfer resistance along the channel is a more pronounced effect. However, for small channel length devices, their application will become more prominent in the near future, and solutions to this problem must be found, such as by minimizing the energy level.

Several methods for solving this problem are known from the literature. Thus, it will be apparent that one method may be to use a contact material having a suitable energy level, such as using a low work function metal for electron injection or a high work function metal for hole injection, and/or designing with appropriate HOMO and/or LUMO energy. Organic material of the order. However, other methods are known. Therefore, an intermediate layer can be used between the electrode and the organic semiconductor. In particular, it is known from the literature to use a self-assembled monolayer (SAM) between an electrode and an organic semiconductor. It is known that the SAM on the metal electrode can affect the work function of the electrode. Therefore, it is disclosed in M. Kitamura et al., Threshold voltage control of bottom-contact n-channel organic thin-film transistors using modified drain/source electrodes, Applied Physics Letters 94, 083310 (2009) having a modification from thiophenol derivatives. The bottom of the 汲 electrode/source electrode contacts the n-channel C ₆₀ thin film transistor. The self-assembled monolayer is disposed between the conventional electrode and the organic semiconductor material to introduce a dipole. It is known that a dipole moment changes the interface to produce a lower charge (hole or electron to be transmitted) into the barrier. In addition, thiol compounds have been evaluated for work functions of conditioning materials such as silver and gold. Therefore, reference may be made to D. Boudinet et al., Modification of gold source and drain electrodes by self-assembled monolayer in staggered n-and p-channel organic thin film transistors, Organic Electronics 11 (2010) 227-237; X. Cheng et al. Controlling Electron and Hole Charge Injection in Ambipolar Organic Field-Effect transistors by Self-Assembled Monolayers, Adv. Funct. Mater. 2009, 19, 2407-2415; and J.-P. Hong et al., Tuning of Ag work functions by Self-assembled monolayers of aromatic thiols for an efficient hole injection for solution processing triisopropylsilylethynyl pentacene organic thin film transistors, Applied Physics Letters 92, 143311 (2008). In particular, it is known that the use of self-assembled monolayers produces clear bipolar features with balanced electron and hole mobility (see X. Cheng et al.).

However, as outlined above, in many technical applications, the bipolarity of organic transistor devices is not a pleasure and creates technical challenges. In particular, it is quite difficult to control a transistor device with bipolar charge carrier transport. In addition, many applications require the use of pure n-channel or pure p-channel transistor devices. In particular, the design is mainly due to the chemical stability of the negative charge in the organic material, and the design of the n-type organic semiconductor material and thus the design of the n-channel organic-effect transistor is still an unsolved problem.

Accordingly, it is an object of the present invention to provide an organic semiconductor device and a method of fabricating the same that overcomes the challenges and problems of the methods and devices known from the prior art. In particular, it is an object of the present invention to provide a unipolar device having good charge carrier transport and charge carrier injection characteristics.

It is also an object of the present invention to provide a method of inhibiting bipolar charge carrier transport in a device comprising a bipolar organic semiconductor material.

This target technical problem is solved by the subject matter of the independent item of patent application. The preferred embodiments of the invention, which may be implemented independently or in any combination with other embodiments, are disclosed in the dependent claims.

In a first aspect of the invention, a method for preparing an organic semiconductor device is disclosed. The organic semiconductor device has at least one organic semiconductor material and at least two electrodes adapted to support charge carrier transport via the organic semiconductor material. As used herein, the term organic semiconductor device refers to an electronic device having at least one organic semiconductor material. The organic semiconductor device may be a pure organic semiconductor device composed only of an organic material. However, other embodiments are possible, such as organic semiconductor devices having at least one organic semiconductor material and at least one inorganic semiconductor material. The term semiconductor material refers to any material suitable for supporting charge carrier transport, that is, suitable for providing electrical current. Preferably, at least one type of charge carriers of the bulk state semiconductor material, that is, negative charge carriers and/or positive charge carriers, preferably have a field effect mobility of at least 10 ^-5 cm ² V ^{- 1} s ^-1 , more preferably at least 10 ^-4 cm ² V ^-1 s ^-1 and even more preferably at least 10 ^-3 cm ² V ^-1 s ^-1 .

Moreover, as used herein, the term electrode is used to be suitable for electrical contact and is suitable for injecting negative and/or positive charge carriers into an organic semiconductor material and/or for extracting negative and/or positive charge currents from an organic semiconductor material. Sub-component. Preferably, the at least one electrode may comprise at least one electrically conductive material, such as a conductivity measured in the bulk state of at least 1 x 10 ⁵ S/m, more preferably at least 1 x 10 ⁶ S/m and even more preferably at least 5 x. Conductive material of 10 ⁶ S/m or even at least 20×10 ⁶ S/m. Thus, the at least one electrode preferably comprises at least one metallic material such as aluminum, silver, gold or a combination thereof.

In general, an organic semiconductor device can be or can include any type of electronic device. Thus, the organic semiconductor device can be or can comprise at least one diode and/or at least one transistor. As outlined above, the organic semiconductor device preferably has an airport effect transistor or comprises at least one organic field effect transistor. As used herein, the term organic field effect transistor (OFET) refers to a field effect transistor that uses at least one organic semiconductor material as a channel material. Therefore, the organic field effect transistor may comprise at least one source electrode and at least one germanium electrode, and further comprising at least one channel, wherein the organic field effect transistor is designed such that positive charge carriers and/or negative charge carriers are self-contained The source electrode is transmitted via the channel to the germanium electrode, or vice versa. In addition, an airport effect transistor typically includes at least one gate electrode, that is, an electrode designed to produce an electric field suitable for influencing the charge carrier density in the channel. The channel and the gate electrode are typically separated by at least one insulating material, such as by at least one insulating layer open. By applying an electric field, the density of positive or negative charge carriers in the channel can be adjusted to provide the possibility of controlling positive or negative charge carriers in the channel, in particular providing control of the transfer of positive or negative charge carriers from the source electrode to the ruthenium electrode. Possibility, or vice versa. Preferred embodiments of the organic semiconductor device are disclosed below, and a preferred embodiment of an airport effect transistor is better disclosed.

Organic semiconductor materials inherently have bipolar semiconductor properties. As used herein, the term bipolar semiconductor property means that the electron and hole mobility of the material differ by less than two orders of magnitude, more preferably by less than an order of magnitude. Such electron and hole mobility refer to the overall mobility of the organic semiconductor material and/or the mobility measured under normal operating conditions. The term normal operating conditions may refer to a measurement configuration that measures mobility using two bare metal electrodes (such as Au, Ag, Al, or combinations thereof) in contact with an organic semiconductor material. Thus, the organic semiconductor in a specific organic thin film transistor (OTFT) configuration can be measured by using an OFET configuration, which is made of Au and/or Ag deposited by any known means. The source electrode and the germanium electrode are in contact. Thus, the metal electrode can be deposited by sputtering, electron beam deposition, thermal deposition, printing, or other means. The term "naked" refers to the absence of an intentional additional layer between the metal electrode and the organic semiconductor material, such as without the intentional insertion of additional surface groups, such as by being inserted into a bare metal. The definition of the characteristics of the bipolar semiconductor mentioned above preferably refers to such a measurement configuration.

The method further includes the step of producing at least one intermediate layer at least partially interposed between the organic semiconductor material and the at least one electrode. Various embodiments for producing an intermediate layer exist depending on the configuration of the organic semiconductor device. Therefore, for the generation of the intermediate layer, at least one of the top deposition may be The intermediate layer is deposited on the electrode or at least one electrode prior to the semiconductor material. Alternatively or additionally, at least one intermediate layer may be produced by depositing the at least one intermediate layer on at least one organic semiconductor material prior to depositing the electrode and/or at least one of the electrodes. A combination of these possibilities and/or other possibilities is possible. Preferably, the at least one intermediate layer is deposited on top of the electrode and/or the at least one electrode prior to depositing one or more layers of the at least one organic semiconductor material.

As used herein, the term "insert at least partially" means that at least one intermediate layer can extend beyond the side edges of the electrode-organic semiconductor material interface. Thus, the at least one intermediate layer can extend beyond the interface in at least one dimension. Further, as used herein, the term layer refers to a thin film of material, preferably having a film thickness of less than 50 nm, preferably less than 10 nm and even more preferably less than 1 nm. The term layer preferably refers to a closed layer. However, the term also encompasses the possibility of incomplete coverage, such as island growth and/or layers with openings or voids. The coverage of the surface covered by the layer is preferably greater than 20%, more preferably greater than 50%, or even more preferably greater than 80%. The term intermediate layer refers to a layer interposed between at least two other materials, such as between two layers. Thus, the intermediate layer can be at least partially interposed between at least one metal layer of the at least one electrode and at least one layer of the organic semiconductor material. In this or other embodiments of the invention, the organic semiconductor device preferably comprises a layer configuration, preferably a layer configuration in which the thickness of each layer does not extend beyond 1 μm, more preferably exceeds 500 nm.

At least one intermediate layer can be interposed between the organic semiconductor material and one or more electrodes. Thus, the electrode can comprise at least one source electrode and at least one ruthenium electrode. At least one intermediate layer can be inserted in at least one of the source electrodes and at least one of Between the semiconductor materials and/or between the at least one germanium electrode and the at least one organic semiconductor material. The intermediate layer is preferably interposed between the two electrodes and the organic semiconductor material. Preferably, the at least one source electrode and the at least one germanium electrode are disposed in the same plane of the layer configuration of the organic semiconductor device, such as by depositing at least one organic semiconductor prior to depositing the at least one intermediate layer on top of the one or both electrodes A source electrode and a germanium electrode are deposited on the substrate before the material is deposited on top of the configuration.

For producing at least one intermediate layer, various techniques known to those skilled in the art can be used. Thus, at least one intermediate layer can be produced by processing from a solution comprising at least one solvent and at least one interlayer material in an intermediate layer in a dissolved and/or dispersed state. Processing from solution can include spin coating, printing, Langmuir-Blodgett technique, blade scraping, combinations of such techniques, or other techniques. Further, other techniques, such as chemical vapor deposition and/or physical vapor deposition, may be used instead of or in addition to solution processing.

In the process of the invention, the intermediate layer comprises at least one thiol compound of the formula HS-R, wherein R is an organic residue. As used herein, the term "organic residue" refers to a bond or one or more organic moieties bonded to an HS group by covalent bonding, complex bonding, or ionic bonding. Preferred embodiments of the organic residue R are listed below.

The thiol compound has a dipole moment. As used herein, the term dipole moment refers to the electric dipole moment, which is a measure of the separation of positive and negative charges in a molecule of a thiol compound. The electric dipole moment is a vector of self-negative charges pointing to positive charges. In complex charge systems, electronic systems such as HS-R molecules must be considered Calculate and/or measure the charge distribution.

Preferably, the dipole moment of the thiol compound is the dipole moment from the SH moiety to the residue R, meaning the dipole moment of the thiol compound and the S of the SH group and the R of the S attached to the SH group. The bond between the atoms of the residue forms an angle of less than 90°, preferably less than 45°. The bond between the S of the S-H group and the atom of the R residue attached to S of the S-H group may be a covalent bond, an ionic bond or a complex bond. The bond is preferably a covalent bond.

The dipole moment of the thiol compound may have the same direction and at least the same magnitude as the dipole moment of the 4-phenylthiophenol, that is, the dipole moment from the SH portion to the residue R and the 4-phenylthiophenol The dipole moments have at least the same magnitude.

As used herein, the expression "direction" in the case of the dipole moment of a thiol compound refers to the problem with respect to the SH group directed to the thiol compound or the dipole moment vector pointing away from the SH group of the thiol compound. Therefore, the dipole moment having the dipole moment vector of the SH group directed to the thiol compound can be classified as having a dipole moment of the first direction, and the dipole moment having the SH group directed away from the thiol compound can be The dipole moment of the vector is classified as having a dipole moment of the second direction. Currently, the thiol compound used in the intermediate layer may have the same direction as the dipole moment of 4-phenylthiophenol. Thus, in the present invention, at least one thiol compound to be used in at least one intermediate layer has a dipole moment vector pointing away from the SH group of the thiol compound, for example as in 4-phenylthiophenol.

Accordingly, preferably, the thiol compound used in the intermediate layer of the present invention has an electric dipole moment of at least 1.22, more preferably at least 1.3, even more preferably at least 1.4 and most preferably at least 1.5. In this paper, all dipole moments are given using the unit "Debye", which corresponds to approximately 3.33564 x 10 ^-30 coulomb x metre.

The electric dipole moment of the thiol compound can be calculated and/or can be measured, for example, by using a commercial dipole meter. At present, it is not intended to limit the scope of the patent application. All dipole moments given herein are made by using molecular modeling that is widely used and familiar to those skilled in the art and commercially available as Wavefunction, Inc., Irvine, USA. And calculate the chemical software "Spartan '06" to calculate. The dipole moment of the equilibrium geometry in the ground state is calculated using the density functional B3LYP method. However, other types of calculations and/or measurements can be used because, as outlined above, the direction and magnitude of the dipole moment of the thiol compound can be simply compared to the direction and magnitude of 4-phenylthiophenol. The reason. The thiol compound may only have to have the same orientation and at least the same magnitude as the dipole moment of 4-phenylthiophenol, regardless of the manner in which the measurement and/or the calculation of the dipole moment is used.

The intermediate layer inhibits bipolar charge carrier transport between the electrodes to facilitate unipolar charge carrier transport. In other words, by using at least one intermediate layer having at least one thiol compound having the above-identified characteristics, the bipolar semiconductor characteristics of at least one organic semiconductor material are reduced, and unipolar charge carrier transport is increased. As used herein, the term unipolar charge carrier transport refers to the transport of electrons from a hole that differs by at least two orders of magnitude or more than two orders of magnitude, preferably three orders of magnitude or more of charge carriers. Thus, by using at least one intermediate layer, the bipolar semiconductor properties of the at least one organic semiconductor material can become unipolar semiconductor properties. Such unipolar semiconductor characteristics may include n-type unipolar semiconductor characteristics or p-type unipolar semiconductor characteristics, wherein n-type unipolar semiconductor characteristics are preferred. Therefore, by using at least one having at least one thiol compound The intermediate layer, the characteristics of the bipolar semiconductor can become the characteristics of the n-type unipolar semiconductor, that is, the n-type semiconductor characteristics of electron mobility higher than the hole mobility of at least two orders of magnitude, or become p-type unipolar semiconductor characteristics, that is, electricity The hole mobility is higher than the semiconductor characteristics of the electron mobility by at least two orders of magnitude.

As outlined above, in a preferred embodiment, at least one bipolar charge carrier transport of semiconductor material can be inhibited to facilitate negative charge carrier transport. Thus, preferably, bipolar charge carrier transport is preferably converted to a unipolar charge stream by introducing at least one intermediate layer having at least one thiol compound compared to a semiconductor device having no at least one intermediate layer. Sub-transmission, preferably converted to n-type unipolar charge carrier transport.

In another preferred embodiment, the thiol compound is selected such that the push electron property of R is at least equal to the electron-withdrawing property of the biphenyl group in the 4-phenylthiophenol.

In a preferred embodiment, the process of the invention comprises at least one thiol compound of the formula HS-R wherein R is selected from the group consisting of alkyl groups wherein the alkyl group is linear, cyclic or branched. And may contain 1 to 20 carbon atoms, more preferably 10 to 20 carbon atoms, preferably decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, Octadecyl, eicosyl and cyclohexyl; benzyl, phenyl; alkylphenyl, wherein the alkyl group of the phenyl group may contain from 1 to 20 carbon atoms, which is a linear, cyclic or branched chain and Preferably located at the 2- or 4-position of the phenyl group with respect to the thiol group, such as 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, 2,3-dimethylphenyl, 2 , 4-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,3,4-trimethyl Phenyl, 2,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 2,3,5,6-tetramethylphenyl, 2,3,4,6-tetra Methylphenyl or 2,3,4,5-tetramethylphenyl, 2,3,4,5,6-pentamethylphenyl, n-butylphenyl, preferably 2-n-butylbenzene Base, 4-n-butylphenyl, tert-butylphenyl, pentylphenyl, hexylphenyl, cyclohexylphenyl, heptylphenyl, octylphenyl, ethylhexylphenyl, and more preferably Is 4-methylphenyl or 4-butylphenyl; alkoxyphenyl, preferably methoxyphenyl, more preferably 2-methoxyphenyl, 3-methoxyphenyl or 4 -methoxyphenyl; dimethoxyphenyl, preferably 2,3-dimethoxyphenyl, 2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl, 3,4-dimethoxyphenyl or 3,5-dimethoxyphenyl; trimethoxyphenyl, preferably 2,3,4-trimethoxyphenyl, 2,4,5-trimethyl Oxyphenyl or 2,4,6-trimethoxyphenyl; 2,3,5,6-tetramethoxyphenyl, 2,3,4,6-tetramethoxyphenyl or 2,3 , 4,5-tetramethoxyphenyl, 2,3,4,5,6-pentamethoxyphenyl; alkylthiophenyl, preferably methylthiophenyl, more preferably 2- Methylthiophenyl, 3-methylthiophenyl or 4-methylsulfide Phenyl, benzylphenyl, arylphenyl, preferably 4-phenylphenyl, 2-thionaphthyl, 4-(dimethylamino)phenyl; heteroaryl, preferably 2-thiophene base.

In another preferred embodiment, a combination of two or more of the above thiol compounds may be included.

In another preferred embodiment, the thiol compound may be selected from one or more of the following: 1-anthracenthiol; 4-methylthiophenol; 4-(methylthio)thiophenol; 3,4-dimethyl oxygen Thiol phenol; 4-butyl thiophenol; 4-phenyl thiophenol; 2-nathenyl thiol (2-Thionaphthol); 4-(dimethylamino) thiophenol; benzyl thiol (Benzyl mercaptan); 3,4,5,6-pentamethylbenzene-1-thiol.

In a preferred embodiment of the invention, the thiol compound forms at least one self-assembled monolayer. As used herein, the term self-assembled monolayer (SAM) refers to a tissue layer of amphiphilic molecules in which one end of the molecule exhibits a particular affinity for the substrate. The thickness of the self-assembled monolayer is typically in the range of 0.1 nm to 2 nm. The molecular end of the substrate, such as the affinity for exhibiting at least one electrode and/or at least one organic semiconductor material (depending on the manufacturing technique), is commonly referred to as the head group of the molecule. The SAM can be produced by chemically adsorbing a hydrophilic or hydrophobic head end gas phase or liquid phase onto a substrate, followed by slow two-dimensional tissue such as the tail end of the hydrophobic tail.

In another preferred embodiment of the invention, the method further includes the step of providing at least one gate electrode, wherein the gate electrode is adapted to affect charge carrier transport between the electrodes by an electric field. Thus, the electrodes mentioned above may comprise a source electrode and a germanium electrode, wherein the gate electrode may be adapted to generate an electric field in the organic semiconductor material, thereby affecting the charge carrier density and/or between the source electrode and the germanium electrode. Charge carrier transport, or vice versa. Thus, at least one gate electrode can be separated from at least one organic semiconductor material by at least one insulator material to prevent charge carriers from being injected into the organic semiconductor material from the gate electrode and/or to prevent charge carriers from being extracted from the organic semiconductor material. In the gate electrode.

The gate electrode is preferably selected from the group consisting of: a bottom gate electrode at least partially located between the substrate of the organic semiconductor device and the organic semiconductor material, And a top gate electrode at least partially located on a face of the organic semiconductor material opposite the substrate of the organic semiconductor device. Thus, the gate electrode can be deposited prior to deposition of the organic semiconductor material, or the gate electrode can be deposited on top of the organic semiconductor material. In either case, at least one insulating layer can be interposed between the gate electrode and the organic semiconductor material. Thus, in another preferred embodiment of the invention, the method may further comprise the step of producing at least one insulating layer, wherein the insulating layer is at least partially located between the gate electrode and the organic semiconductor material. The at least one insulating layer may comprise the use of any organic and/or inorganic material, such as poly(methyl methacrylate) (PMMA) and/or polystyrene (PS).

In another preferred embodiment of the present invention, at least one electrode, that is, at least one source electrode and/or at least one germanium electrode and/or preferably at least one gate electrode, comprises a metal, preferably selected from the group consisting of Metal: silver, gold and aluminum, and better silver and / or gold.

In another preferred embodiment, the organic semiconductor material is a low band gap organic semiconductor material. Therefore, in a preferred embodiment, the energy gap between the HOMO energy level and the LUMO energy level of the organic semiconductor material is in the range of 1.0 eV to 2.5 eV, as measured by absorption UV-VIS spectroscopy, more preferably 1.5 eV to 2.0 eV. Alternatively or additionally, such as measured by cyclic voltammetry, such as disclosed in WO 2009/098253 A1, the HOMO energy level of the organic semiconductor material preferably ranges from 5.5 eV to 6.5 eV below the vacuum level. Within the scope. The LUMO energy level can preferably be in the range of 3.5 eV to 4.5 eV below the vacuum level by measurement using cyclic voltammetry. Regarding the electrode, preferably with respect to the source electrode and/or the germanium electrode, this electricity The work function of the electrode material used in the electrode is preferably in the range of 3.8 eV to 5.6 eV, more preferably in the range of 4.0 eV to 5.4 eV. Therefore, silver and/or gold is preferably used as the electrode material.

In another preferred embodiment of the invention, the organic semiconductor material comprises at least one semiconducting polymer.

In a preferred embodiment, the at least one organic semiconductor material may comprise one or more naphthalene-based semiconducting polymers and related compositions, composites and/or devices. Such naphthalene-based semiconducting polymers can exhibit semiconductor characteristics such as high carrier mobility and/or good current modulation characteristics in field effect devices, light absorption/charge separation in photovoltaic devices, and/or illumination devices. Charge transfer / recombination / light emission. Additionally, such naphthalene-based semiconducting polymers may have certain processing advantages such as solution processability under ambient conditions and/or good stability (e.g., air stability). The naphthalene-based semiconducting polymer taught by the present invention can be used to prepare p-type or n-type semiconductor materials, which in turn can be used to fabricate various organic electronic articles, structures, and devices, including field effect transistors, unipolar circuits, complementary circuits, photovoltaics. Device and illuminating device.

Preferably, at least one organic semiconductor material, in particular at least one semiconducting polymer and even more preferably at least one naphthalene-based semiconducting polymer, may comprise at least one copolymer. More specifically, the polymer may be an AB copolymer comprising a first repeating unit comprising an aromatic quinone imine (monomer A, M ₁ ) and a second repeating unit comprising one or more cyclic moieties (single Body B, M ₂ ). In various embodiments, monomer A and monomer B may comprise an aromatic or otherwise highly conjugated cyclic (carbocyclic or heterocyclic) moiety, wherein the cyclic moiety may optionally undergo one or more electron pulls. Substituted or electron-donating or functionalized. The pairing of monomers A and B, the functionalization of the quinone imine position of monomer A, and any additional functionalization on either monomer can be affected by one or more of the following factors: 1) under air and stable charge transport operations The ability to pull electrons in semiconductor processing; 2) the adjustment of the main carrier type of the electronic structure of monomers A and B; 3) the chemistry of the polymerization of the region-regulated polymer; 4) the flat core of the polymer chain Degree and linearity; 5) the ability of the π-conjugated core to additionally functionalize; 6) increase the potential of polymer solubility for solution processing; 7) achieve strong π-π interaction / intermolecular electron coupling; Bandgap modulation via electron donor-acceptor coupling of electron-deficient (receptor) and electron-rich (donor) AB or BA repeat units. The resulting polymers and related methods can be used to enhance the efficacy of related devices, such as organic field effect transistors, luminescent transistors, solar cells, or the like.

More specifically, the monomer A of the polymer of the present invention generally comprises a naphthyl imine or a monoquinone imide which is optionally substituted (core substituted and/or quinone substituted), and monomer B generally comprises One or more optionally substituted aromatic (or otherwise π-conjugated) monocyclic moieties. In certain embodiments, monomer B can include one or more linking moieties and/or one or more polycyclic moieties in addition to one or more monocyclic moieties. In various embodiments, monomer B as a whole may comprise a highly conjugated system. The teachings of the present invention are also directed to homopolymers of monomer A.

In the present application, where the composition is described as having, including or comprising a particular component, or where the method is described as having, including or comprising a particular method step, the composition encompassing the teachings of the present invention is also substantially Or consisting of the components, and the method of the present teachings consists essentially of or consists of the method steps.

In the present application, where an element or component is considered to be included in and/or selected from the list of the element or component, it is understood that the element or component can be any one of the element or component and A group consisting of two or more of said elements or components is selected. In addition, it is to be understood that the elements and/or features of the compositions, devices or methods described herein may be combined in various ways, without departing from the spirit and scope of the invention.

Unless otherwise expressly stated, the terms "include", "includes", "including", "have", "has" or "having" are used. It should be understood as open and non-limiting.

The use of the singular includes the plural (and vice versa) unless otherwise specified. In addition, the term "about" is used in the context of a numerical value unless the context clearly dictates otherwise. The term "about" as used herein, unless otherwise indicated or inferred, refers to a deviation of ±10% of the rating.

It should be understood that the order of the steps or the order in which certain acts are performed is not critical, as long as the teachings of the present invention are still operational. In addition, two or more steps or actions can be performed simultaneously.

As used herein, "polymer" or "polymeric compound" refers to a molecule (eg, a macromolecule) comprising a plurality of repeating units joined by covalent chemical bonds. The polymer can be represented by the following formula: Wherein M is a repeating unit or a monomer, and n is the number of M in the polymer. For example, if n is 3, it should be understood that the polymer shown above is: MMM.

The polymer or polymeric compound may have only one type of repeating unit and two or more types of different repeating units. In the former case, the polymer may be referred to as a homopolymer. In the latter case, the terms "copolymer" or "copolymeric compound" are used interchangeably, especially when the polymer includes chemically distinct repeating units. The polymer or polymeric compound can be linear or branched. Branched polymers can include dendritic polymers such as dendrimers, hyperbranched polymers, brush polymers (also known as bottle brushes), and the like. Unless otherwise indicated, the combination of repeating units in the copolymer can be head to tail, head to head or tail to tail. Additionally, unless otherwise indicated, the copolymer may be a random copolymer, an alternating copolymer or a block copolymer.

As used herein, "cyclic moiety" may include one or more (eg, 1 to 6) carbocyclic or heterocyclic rings. The cyclic moiety can be a cycloalkyl, heterocycloalkyl, aryl or heteroaryl group (which may include only saturated bonds, or may include one or more unsaturated bonds that are not related to aromaticity), each including, for example, 3 Up to 24 ring atoms and may be optionally substituted as described herein. In the embodiment where the cyclic moiety is a "monocyclic moiety", the "monocyclic moiety" may include a 3 to 14 membered aromatic or non-aromatic carbocyclic or heterocyclic ring. Monocyclic moieties can include, for example, phenyl or 5- or 6-membered heteroaryl, each of which can be optionally substituted as described herein. In the embodiment where the annular portion is a "polycyclic portion", the "polycyclic portion" may include two or more fused (ie, sharing a common bond) and/or via a spiro atom or one or more bridges. A ring in which atoms are connected to each other. The polycyclic moiety may comprise 8 to 24 membered aromatic or non-aromatic carbocyclic or heterocyclic rings, such as C _8-24 aryl, or 8 to 24 membered heteroaryl, such as thienothiophenyl or 3 to 7 thick The groups consisting of the thiophene rings can each be optionally substituted as described herein.

As used herein, "fused ring" or "fused ring moiety" refers to a polycyclic ring system having at least two rings, wherein at least one ring is an aromatic ring and the aromatic ring (carbocyclic or heterocyclic) has at least one other ring The at least one other ring may be an aromatic or non-aromatic carbocyclic or heterocyclic ring. Such polycyclic systems can be highly π-conjugated systems and can include polycyclic aromatic hydrocarbons such as rylene (or an analog thereof containing one or more heteroatoms): Where a ^o can be an integer in the range 0 to 3; coronene of the formula (or an analog thereof containing one or more heteroatoms): Wherein b ^o can be an integer in the range of 0 to 3; and linear acene of the formula (or an analog thereof containing one or more heteroatoms): Where c ^o can be an integer ranging from 0 to 4. The fused ring portion can be optionally substituted as described herein.

As used herein, "halo" or "halogen" means fluoro, chloro, bromo and iodo.

As used herein, "oxo" refers to double bond oxygen (ie, =0).

As used herein, "alkyl" refers to a straight or branched chain saturated hydrocarbon group. Examples of the alkyl group include a methyl group (Me), an ethyl group (Et), a propyl group (e.g., n-propyl group and isopropyl group), and a butyl group (e.g., n-butyl group, isobutyl group, second butyl group, and third butyl group). Base), pentyl (eg n-pentyl, isopentyl, neopentyl), hexyl and the like. In various embodiments, the alkyl group can have from 1 to 40 carbon atoms (ie, C _1-40 alkyl groups), such as from 1 to 20 carbon atoms (ie, C _1-20 alkyl groups). In some embodiments, an alkyl group can have from 1 to 6 carbon atoms and can be referred to as a "lower alkyl group." Examples of lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and isopropyl) and butyl (e.g., n-butyl, isobutyl, t-butyl, t-butyl). In some embodiments, an alkyl group can be substituted as described herein. Alkyl groups are generally not substituted by another alkyl, alkenyl or alkynyl group.

As used herein, "haloalkyl" refers to an alkyl group having one or more halo substituents. In various embodiments, haloalkyl groups can have from 1 to 40 carbon atoms (i.e., C _1-40 haloalkyl), such as from 1 to 20 carbon atoms (i.e., C _1-20 haloalkyl). Examples of haloalkyl groups include CF ₃ , C ₂ F ₅ , CHF ₂ , CH ₂ F, CCl ₃ , CHCl ₂ , CH ₂ Cl, C ₂ Cl ₅ and the like. A perhaloalkyl group, that is, an alkyl group in which all hydrogen atoms are replaced by a halogen atom (e.g., CF ₃ and C ₂ F ₅ ), is included in the definition of "haloalkyl". For example, a C _1-40 haloalkyl group can have the formula -C _z H _2z+1-t X ⁰ _t , wherein X ⁰ is F, Cl, Br, or I at each occurrence, and z is in the range of 1 to 40. An integer within, and t is an integer in the range of 1 to 81, with a constraint that t is less than or equal to 2z+1. Haloalkyl groups other than perhaloalkyl groups can be substituted as described herein.

As used herein, "alkoxy" refers to -O-alkyl. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy (eg, n-propoxy and isopropoxy), tert-butoxy, pentyloxy, hexyloxy, and Similar group. The alkyl group in the -O-alkyl group can be substituted as described herein.

As used herein, "alkylthio" refers to -S-alkyl (which in some instances may be represented as -S(O) _w -alkyl, wherein w is 0). Examples of alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio (eg, n-propylthio and isopropylthio), tert-butylthio, pentylthio, hexylthio, and Similar group. The alkyl group in the -S-alkyl group can be substituted as described herein.

As used herein, "arylalkyl" refers to an alkyl-aryl group wherein the arylalkyl group is covalently attached via an alkyl group to a defined chemical structure. An arylalkyl group is within the definition of -YC _6-14 aryl, wherein Y is as defined herein. An example of an arylalkyl group is benzyl (-CH ₂ -C ₆ H ₅ ). The arylalkyl group can be optionally substituted, that is, the aryl group and/or alkyl group can be substituted as disclosed herein.

As used herein, "alkenyl" refers to a straight or branched alkyl group having one or more carbon-carbon double bonds. Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a butadienyl group, a pentadienyl group, a hexadienyl group, and the like. One or more carbon-carbon double bonds may be internal (such as 2-butene) or terminal (such as 1-butene). In various embodiments, an alkenyl group can have from 2 to 40 carbon atoms (i.e., a C _2-40 alkenyl group), such as from 2 to 20 carbon atoms (i.e., a C _2-20 alkenyl group). In some embodiments, an alkenyl group can be substituted as described herein. Alkyl groups are generally not substituted by another alkenyl, alkyl or alkynyl group.

As used herein, "alkynyl" refers to a straight or branched alkyl group having one or more carbon-carbon conjugates. Examples of alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl and the like. The one or more carbon-carbon bonds may be internal (such as 2-butyne) or terminal (such as 1-butyne). In various embodiments, an alkynyl group can have from 2 to 40 carbon atoms (ie, a C _2-40 alkynyl group), such as from 2 to 20 carbon atoms (ie, a C _2-20 alkynyl group). In some embodiments, an alkynyl group can be substituted as described herein. Alkyl groups are generally not substituted by another alkynyl group, alkyl group or alkenyl group.

As used herein, "cycloalkyl" refers to a non-aromatic carbocyclic group, including cyclized alkyl, alkenyl, and alkynyl groups. In various embodiments, a cycloalkyl group can have from 3 to 24 carbon atoms, such as from 3 to 20 carbon atoms (eg, a C _3-14 cycloalkyl group). A cycloalkyl group can be a monocyclic (e.g., cyclohexyl) or polycyclic (e.g., containing a fused, bridged, and/or spiro ring system) wherein the carbon atoms are internal or external to the ring system. Any suitable ring position of the cycloalkyl group can be covalently attached to the defined chemical structure. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornane. Base, norpinyl, norcaryl, adamantyl and spiro[4.5]nonanyl as well as homologs, isomers and the like. In some embodiments, a cycloalkyl group can be substituted as described herein.

As used herein, "heteroatom" refers to an atom of any element other than carbon or hydrogen and includes, for example, nitrogen, oxygen, helium, sulfur, phosphorus, and selenium.

As used herein, "cycloheteroalkyl" refers to a ring heteroatom containing at least one member selected from the group consisting of O, S, Se, N, P, and Si (eg, O, S, and N) and optionally one or more double bonds. Or a non-aromatic cycloalkyl group. The cycloheteroalkyl group may have 3 to 24 ring atoms, for example 3 to 20 ring atoms (for example, 3 to 14 membered cycloheteroalkyl groups). One or more N, P, S or Se atoms (eg, N or S) in the cycloheteroalkyl ring may be oxidized (eg, morpholine N-oxide, thiomorpholine S-oxide, thiomorpholine S) , S-dioxide). In some embodiments, the nitrogen or phosphorus atom of the cycloheteroalkyl group can bear a substituent, such as a hydrogen atom, an alkyl group, or other substituents as described herein. The cycloheteroalkyl group may also contain one or more pendant oxy groups, such as pendant oxypiperidinyl, pendant oxazolidinyl, di-oxy-(1H,3H)-pyrimidinyl, pendant oxy-2. (1H)-pyridyl and the like. Examples of cycloheteroalkyl groups include, in particular, morpholinyl, thiomorpholinyl, piperidyl, imidazolidinyl, imidazolinyl, oxazolidinyl, pyrazolyl, pyrazolinyl, pyrrolidinyl, pyrrole A phenyl group, a tetrahydrofuranyl group, a tetrahydrothiophenyl group, a piperidinyl group, a piperazinyl group, and the like. In some embodiments, a cycloheteroalkyl group can be substituted as described herein.

As used herein, "aryl" refers to an aromatic monocyclic hydrocarbon ring system or a polycyclic ring system in which two or more aromatic hydrocarbon rings are fused (ie, have a common bond) together or at least one aromatic single. The cyclic hydrocarbon ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings. An aryl group can have from 6 to 24 carbon atoms (e.g., a _C6-20 aryl group) in its ring system, which can include a plurality of fused rings. In some embodiments, the polycyclic aryl group can have from 8 to 24 carbon atoms. Any suitable ring position of the aryl group can be covalently attached to the defined chemical structure. Examples of the aryl group having only an aromatic carbocyclic ring include phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), fluorenyl (tricyclic), phenanthryl (tricyclic), fused pentaphenyl ( Five rings) and similar groups. Examples of polycyclic systems in which at least one aromatic carbocyclic ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings include, in particular, benzo derivatives of cyclopentane (i.e., indanyl, which is 5 , 6-bicyclic cycloalkyl/aromatic ring system), benzo derivative of cyclohexane (ie, tetrahydronaphthyl group, which is 6,6-bicyclic cycloalkyl/aromatic ring system), benzophenone of imidazoline a derivative (i.e., a benzimidazolyl group which is a 5,6-bicyclic cycloheteroalkyl/aromatic ring system) and a benzo derivative of a piperene (i.e., Alkenyl, which is a 6,6-bicyclic cycloheteroalkyl/aromatic ring system). Other examples of aryl groups include benzodioxanyl, benzodioxolyl, Alkyl, porphyrinyl and the like. In some embodiments, an aryl group can be substituted as described herein. In some embodiments, an aryl group can have one or more halogen substituents and can be referred to as a "haloaryl." A perhaloaryl group, that is, an aryl group in which all hydrogen atoms are replaced by a halogen atom (e.g., -C ₆ F ₅ ) is included in the definition of "haloaryl". In certain embodiments, an aryl group is substituted with another aryl group and may be referred to as a biaryl group. Each aryl group in the biaryl group can be substituted as disclosed herein.

As used herein, "heteroaryl" refers to an aromatic monocyclic ring system containing at least one ring heteroatom selected from the group consisting of oxygen (O), nitrogen (N), sulfur (S), cerium (Si), and selenium (Se). Or a polycyclic ring system in which at least one ring present in the ring system is an aromatic ring and contains at least one ring hetero atom. Polycyclic heteroaryl includes polycyclic heteroaryl groups having two or more heteroaryl rings fused together, and having at least one monocyclic heteroaryl ring and one or more aromatic carbocyclic rings, A polycyclic heteroaryl group fused to an aromatic carbocyclic ring and/or a non-aromatic cycloheteroalkyl ring. The heteroaryl group may have, for example, 5 to 24 ring atoms and 1 to 5 ring hetero atoms (i.e., 5 to 20 membered heteroaryl groups). The heteroaryl group can be attached to the defined chemical structure at any heteroatom or carbon atom that results in a stable structure. In general, heteroaryl rings do not contain OO, SS or SO bonds. However, one or more of the N or S atoms in the heteroaryl group can be oxidized (eg, pyridine N-oxide, thiophene S-oxide, thiophene S, S-dioxide). Examples of heteroaryl groups include, for example, a 5- or 6-membered single ring system and a 5 to 6 double ring system as follows: Wherein T is O, S, NH, N-alkyl, N-aryl, N-(arylalkyl) (e.g., N-benzyl), SiH ₂ , SiH (alkyl), Si (alkyl) ₂ SiH (arylalkyl), Si(arylalkyl) ₂ or Si(alkyl)(arylalkyl). Examples of such heteroaryl rings include pyrrolyl, furyl, thienyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl , thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, fluorenyl, isodecyl, benzofuranyl, benzothienyl, quinolyl, 2-methyl Quinolinyl, isoquinolyl, quinoxalinyl, quinazolinyl, benzotriazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzo Oxadiazolyl, benzoxazolyl, Lolinyl, 1H-carbazolyl, 2H-carbazolyl, pyridazinyl, isobenzofuranyl, Pyridyl, pyridazinyl, acridinyl, fluorenyl, oxazolopyridyl, thiazolopyridyl, imidazopyridyl, furopyridinyl, thienopyridyl, pyridopyrimidinyl, pyridopyrazinyl , pyridopyridazinyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl and the like. Other examples of heteroaryl groups include 4,5,6,7-tetrahydroindenyl, tetrahydroquinolyl, benzothienopyridyl, benzofuropyridinyl and the like. In some embodiments, a heteroaryl group can be substituted as described herein.

The polymer taught by the present invention may include a "divalent group" as defined herein as a linking group capable of forming a covalent bond with two other moieties. For example, the polymers taught by the present invention may include a divalent C _1-20 alkyl group (eg, a methylene group), a divalent C _2-20 alkenyl group (eg, vinylyl), and a divalent C _{2 - 2 . 20} alkynyl (eg ethynylyl); divalent C _6-14 aryl (eg phenylyl); divalent 3 to 14 membered cycloalkyl (eg pyrrolidyl) And/or a divalent 5 to 14 membered heteroaryl group (e.g., thienylyl). In general, it will be appreciated that a chemical group (e.g., -Ar-) is a divalent group by including two bonds before and after the group.

The electron-withdrawing or pull-electron properties of hundreds of the most commonly used substituents have been identified, quantified, and publicly reflected in all commonly used classes of substituents. The most common quantitative basis for pushing electrons and pulling electrons is the Hammett σ value. The Hammett σ value of hydrogen is zero, while the Hammett σ values of other substituents are directly or negatively increasing in association with their pull electron or push electron characteristics. It is believed that the substitution of Hammett's σ value is negative, and that the Hammett σ value is positive. The substituent has an electron pull. See Lange's Handbook of Chemistry, 12th Ed., McGraw Hill, 1979, Table 3-12, pages 3-134 to 3-138, which lists the Hammett σ values of a large number of commonly encountered substituents and by way of citation Incorporated herein.

It should be understood that the term "electron accepting group" and "electron acceptor" and "electron withdrawing group" are used synonymously herein. In particular, "electron group"("EWG") or "electron accepting group" or "electron acceptor" refers to a functional group that attracts electrons to themselves larger than a hydrogen atom when occupying the same position in the molecule. Examples of electron withdrawing groups include, but are not limited to, halogen or halo (eg, F, Cl, Br, I), -NO ₂ , -CN, -NC, -S(R ⁰ ) ₂ ⁺ , -N(R ⁰ ) ₃ ⁺ , -SO ₃ H, -SO ₂ R ⁰ , -SO ₃ R ⁰ , -SO ₂ NHR ⁰ , -SO ₂ N(R ⁰ ) ₂ , -COOH, -COR ⁰ , -COOR ⁰ , - CONHR ⁰ , -CON(R ⁰ ) ₂ , C _1-40 haloalkyl, C _6-14 aryl and 5 to 14 member electron-deficient heteroaryl; wherein R ⁰ is C _1-20 alkyl, C _{2- 20} alkenyl, C _2-20 alkynyl, C _1-20 haloalkyl, C _1-20 alkoxy, C _6-14 aryl, C _3-14 cycloalkyl, 3 to 14 membered cycloalkyl And 5 to 14 membered heteroaryl groups, each of which may be optionally substituted as described herein. For example, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _1-20 haloalkyl, C _1-20 alkoxy, C _6-14 aryl, C _{3 -14} cycloalkyl, 3 to 14 membered cycloheteroalkyl and 5 to 14 membered heteroaryl each optionally substituted with 1 to 5 small electron withdrawing groups such as F, Cl, Br, -NO ₂ , -CN, -NC, -S(R ⁰ ) ₂ ⁺ , -N(R ⁰ ) ₃ ⁺ , -SO ₃ H, -SO ₂ R ⁰ , -SO ₃ R ⁰ , -SO ₂ NHR ⁰ , -SO ₂ N(R ⁰ ) ₂ , -COOH, -COR ⁰ , -COOR ⁰ , -CONHR ⁰ and -CON(R ⁰ ) ₂ .

It should be understood that the terms "electron-inducing group" and "electron donor" are used synonymously. In particular, "electron-inducing group" or "electron donor" refers to a functional group that supplies electrons to adjacent atoms greater than a hydrogen atom when occupying the same position in the molecule. Examples of electron-withdrawing groups include -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ , -N(R ⁰ ) ₂ and 5 to 14 membered electron-rich heteroaryl groups, wherein R ⁰ is a C _1-20 alkyl group. , C _2-20 alkenyl, C _2-20 alkynyl, C _6-14 aryl or C _3-14 cycloalkyl.

Various unsubstituted heteroaryl groups can be described as electron rich (or π excess) or electron deficient (or π deficient) groups. This classification is based on the average electron density of each ring atom compared to the carbon atom on the benzene. Examples of electron rich systems include 5-membered heteroaryl groups having one hetero atom, such as furan, pyrrole, and thiophene; and benzo-fused counterparts thereof, such as benzofuran, benzopyrrole, and benzothiophene. Examples of electron-deficient systems include 6-membered heteroaryl groups having one or more heteroatoms such as pyridine, pyrazine, pyridazine, and pyrimidine; and benzo-fused counterparts thereof, such as quinoline, isoquinoline, quinoxaline Porphyrin, Porphyrin, pyridazine, Pyridine, quinazoline, phenanthridine, acridine and hydrazine. The mixed heteroaromatic ring belongs to any class of the type, number and position of one or more heteroatoms in the visible ring. See Katritzky, AR and Lagowski, JM, Heterocyclic Chemistry (John Wiley & Sons, New York, 1960).

Substituents for monomers A and B are disclosed in groups or ranges at various points in the specification. In particular, it is intended that the description include each individual sub-combination of the members of the group. For example, the term "C _1-6 alkyl" is specifically intended to specifically disclose C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₁ -C ₆ , C ₁ -C ₅ , C ₁ -C ₄ , C ₁ -C ₃ , C ₁ -C ₂ , C ₂ -C ₆ , C ₂ -C ₅ , C ₂ -C ₄ , C ₂ -C ₃ , C ₃ -C ₆ , C ₃ - C ₅ , C ₃ -C ₄ , C ₄ -C ₆ , C ₄ -C ₅ and C ₅ -C ₆ alkyl. In other instances, integers in the range of 0 to 40 are intended to specifically reveal 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 , 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 and 40 And integers in the range of 1 to 20 are intended to specifically reveal 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20. Other examples include the phrase "substituted by 1 to 5 substituents as appropriate". The specific meaning of the disclosure may include 0, 1, 2, 3, 4, 5, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 0 to 1, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, 2 to 3, 3 to 5, 3 to 4 and 4 to 5 substituents Chemical group.

The polymers described herein may contain asymmetric atoms (also known as palmar centers), and some compounds may contain two or more asymmetric atoms or centers, which may thus produce optical isomers (enantiomers) And diastereomers (geometric isomers). The teachings of the present invention include such optical isomers and diastereomers, including their respective resolved enantiomeric or diastereomeric pure isomers (e.g., (+) or (-) stereoisomers. And its racemic mixture, as well as other mixtures of enantiomers and diastereomers. In some embodiments, enantiomerically enriched or pure forms of optical isomers can be obtained by standard procedures known to those skilled in the art, including, for example, palm separation, diastereoisomerism. Salt formation, kinetic analysis and asymmetric synthesis. The teachings of the present invention also encompass cis and trans isomers of polymers containing alkenyl moieties such as olefins, azo and imine. It should also be understood that the polymers taught by the present invention encompass all possible regioisomers and mixtures thereof in pure form. In some embodiments, the preparation of the polymers of the present invention can include the use of standard separation procedures known to those skilled in the art, for example, by using a column layer. One or more of the separation, thin layer chromatography, simulated moving bed chromatography, and high performance liquid chromatography are used to separate the isomers. However, mixtures of regioisomers can be used analogously to the use of the individual regioisomers as taught herein and/or as known to those skilled in the art.

In particular, the description of a regioisomer includes any other regioisomer and any regioisomeric mixture unless specifically stated otherwise.

As used herein, "leaving group"("LG") refers to a charged or uncharged atom (or group of atoms) that can be replaced by a stabilizing substance due to, for example, substitution or elimination of a reaction. Examples of leaving groups include, but are not limited to, halogen (eg, Cl, Br, I), azide (N ₃ ), thiocyanate (SCN), nitro (NO ₂ ), cyanate groups ( CN), water (H ₂ O), ammonia (NH ₃ ) and sulfonate groups (for example OSO ₂ -R, wherein R can be a C _1-10 alkyl group or a C _6-14 aryl group, each depending on the case 1 to 4 groups independently selected from C _1-10 alkyl and electron withdrawing groups), such as tosylate (toluenesulfonate, OTs), mesylate Mesylate (methanesulfonate, OMs), brosylate (p-bromobenzenesulfonate, OBs), nitrobenzenesulfonate Nosylate (4-nitrobenzenesulfonate, ONs) and triflate (trifluoromethanesulfonate, OTf).

As discussed above, the term "p-type semiconductor material" or "p-type semiconductor" refers to a semiconductor material having a hole as a main carrier. In some embodiments, when a p-type semiconductor material is deposited on a substrate, a hole mobility of more than about 10 ^-5 cm ² /Vs can be provided. In the case of field effect devices, the p-type semiconductor can also exhibit a current on/off ratio greater than about 10.

As discussed further above, the term "n-type semiconductor material" or "n-type semiconductor" refers to a semiconductor material having electrons as the main carrier. In some embodiments, an electron mobility of more than about 10 ^-5 cm ² /Vs can be provided when the n-type semiconductor material is deposited on the substrate. In the case of a field effect device, the n-type semiconductor can also exhibit a current on/off ratio of greater than about 10.

As used herein, the term "mobility" refers to a measure of the rate at which charge carriers move through a material under the influence of an electric field, such as a hole (or a positive charge unit) in the case of a p-type semiconductor material. And in the case of an n-type semiconductor material, it is an electron.

As used herein, a compound can be considered "surrounded" when the compound is exposed to ambient conditions such as air, ambient temperature, and humidity for a period of time, when the carrier mobility or reduction potential of the compound is maintained at about its initial measurement. Or "stable under ambient conditions." For example, if the compound is exposed to ambient conditions including air, humidity, and temperature for 3 days, 5 days, or 10 days, its carrier mobility or reduction potential does not change by more than 20% of its initial value or does not exceed At 10%, the compound can be described as a peripherally stabilizing compound.

As used herein, "solution processable" means a compound (eg, a polymer), material, or composition that can be used in various solution phase processes, including spin coating, printing (eg, ink jet printing, screen printing). Printing, pad printing, lithography, gravure printing, flexographic printing, lithographic printing, large-scale printing and the like), spraying, electrospray coating, dripping coating (drop casting), dip coating and knife coating.

In the description, the structure may or may not be presented under a chemical name. If there is any problem with the naming, the structure will prevail.

In a preferred embodiment of the invention, the organic semiconductor material is selected from the group consisting of: Wherein M ₁ is a naphthyl imine substituted by the following formula: M ₂ has a formula selected from the following: n is an integer between 2 and 5,000; and R ¹ , π-2, Ar, Z, m, m' and m" are as defined herein.

More specifically, in the form of M ₁ : R ¹ is independently selected from H, C _1-40 alkyl, C _2-40 alkenyl, C _1-40 haloalkyl and 1 to 4 cyclic moieties at each occurrence, wherein: C _1-40 alkane The group, C _2-40 alkenyl and C _1-40 haloalkyl are each optionally substituted with 1 to 10 substituents independently selected from the group consisting of halogen, -CN, NO ₂ , OH, -NH ₂ , -NH (C _1-20 alkyl), -N(C _1-20 alkyl) ₂ , -S(O) ₂ OH, -CHO, -C(O)-C _1-20 alkyl, -C(O) OH, -C(O)-OC _1-20 alkyl, -C(O)NH ₂ , -C(O)NH-C _1-20 alkyl, -C(O)N (C _1-20 alkyl) ₂ , -OC _1-20 alkyl, -SiH ₃ , -SiH(C _1-20 alkyl) ₂ , -SiH ₂ (C _1-20 alkyl) and -Si(C _1-20 alkyl) ₃ ; a C _1-40 alkyl group, a C _2-40 alkenyl group, and a C _1-40 haloalkyl group each covalently bonded to a quinone imine nitrogen atom via an optionally present linking moiety; and 1 to 4 cyclic moieties; Each may be the same or different and may be covalently bonded to each other or via a linking moiety as the case may be covalently bonded to the quinone imine nitrogen, and optionally substituted with from 1 to 5 substituents independently selected from halogen: Side oxy, -CN, NO ₂ , OH, =C(CN) ₂ , -NH ₂ , -NH(C _1-20 alkyl), -N(C _1-20 alkyl) ₂ , -S(O ) ₂ OH, -CHO, -C( O) OH, -C(O)-C _1-20 alkyl, -C(O)-OC _1-20 alkyl, -C(O)NH ₂ , -C(O)NH-C _1-20 alkane , -C(O)N(C _1-20 alkyl) ₂ , -SiH ₃ , -SiH(C _1-20 alkyl) ₂ , -SiH ₂ (C _1-20 alkyl), -Si(C _1-20 alkyl) ₃ , -OC _1-20 alkyl, -OC _1-20 alkenyl, -OC _1-20 haloalkyl, C _1-20 alkyl, C _1-20 alkenyl and C _{1- 20} haloalkyl.

In some embodiments, each R ¹ may be independently selected from H, C _1-40 alkyl, C _2-40 alkenyl, C _2-40 alkynyl, C _1-40 haloalkyl, -LR ^a , - L-Ar ¹ , -L-Ar ¹ -Ar ¹ , -L-Ar ¹ -R ^a , -L-Ar ¹ -Ar ¹ -R ^a , -L-Cy ¹ , -L-Cy ¹ -Cy ¹ , -L-Cy ¹ -R ^a and -L-Cy ¹ -Cy ¹ -R ^a ; wherein: L is independently selected from -YOY-, -Y-[S(O) _w ]-Y- at each occurrence , -YC(O)-Y-, -Y-[NR ^c C(O)]-Y-, -Y-[C(O)NR ^c ]-, -Y-NR ^c -, -Y-[SiR ^c ₂ ]-Y-, divalent C _1-20 alkyl, divalent C _1-20 alkenyl, divalent C _1-20 haloalkyl, and covalent bond; Ar ¹ is independently monovalent at each occurrence Or a divalent C _6-14 aryl group or a 5 to 14 membered heteroaryl group, each optionally substituted with 1 to 5 substituents independently selected from the group consisting of halogen, -CN, pendant oxy, =C(CN) ₂ , C _1-6 alkyl, C _1-6 alkoxy and C _1-6 haloalkyl; Cy ¹ is independently monovalent or divalent C _3-14 cycloalkyl or 3 to 14 at each occurrence a heterocycloalkyl group, each optionally substituted with from 1 to 5 substituents independently selected from the group consisting of halogen, -CN, pendant oxy, =C(CN) ₂ , C _1-6 alkyl, C _{1- 6} alkoxy and C _1-6 haloalkyl; and R ^a is independently in each occurrence selected from C _1-40 alkyl, C _2-40 alkenyl, C _2-40 alkynyl, C _1-40 haloalkyl, C _1-40 ^{alkoxy, -L'-R b, -L'-} Ar 2 , -L'-Ar ² -Ar ² , -L'-Ar ² -R ^b , -L'-Ar ² -Ar ² -R ^b , -L'-Cy ² , -L'-Cy ² -Cy ² -L'-Cy ² -R ^b , -L'-Cy ² -Cy ² -R ^b ; wherein: L' is independently selected from -YOY-, -Y-[S(O) _w at each occurrence ]-Y-, -YC(O)-Y-, -Y-[NR ^c C(O)]-Y-, -Y-[C(O)NR ^c ]-, -Y-NR ^c -,- Y-[SiR ^c ₂ ]-Y-, divalent C _1-20 alkyl, divalent C _1-20 alkenyl, divalent C _1-20 haloalkyl, and covalent bond; Ar ² at each occurrence Independently monovalent or divalent C _6-14 aryl or 5 to 14 membered heteroaryl, each optionally substituted with 1 to 5 substituents independently selected from the group consisting of halogen, -CN, pendant oxy, = C(CN) ₂ , C _1-6 alkyl, C _1-6 alkoxy and C _1-6 haloalkyl; Cy ² is independently monovalent or divalent C _3-14 cycloalkyl at each occurrence Or a 3 to 14 membered cycloheteroalkyl group, each optionally substituted with 1 to 5 substituents independently selected from the group consisting of halogen, -CN, pendant oxy, =C(CN) ₂ , C _1-6 alkyl , C _1-6 alkoxy and C _1-6 haloalkyl; R ^b is independently selected from C _1-40 alkyl, C _2-4 at each occurrence ₀ alkenyl, C _2-40 alkynyl, C _1-40 haloalkyl and C _1-40 alkoxy; R ^c is independently selected from H, C _1-6 alkyl and -YC ₆ at each occurrence _-14 aryl; Y is independently selected from the group consisting of a divalent C _1-6 alkyl group, a divalent C _1-6 haloalkyl group, and a covalent bond at each occurrence; and w is 0, 1, or 2.

In various embodiments, M _{1 can} be selected from: Wherein the naphthalene core may be optionally substituted with 1 to 2 substituents independently selected from the group consisting of halogen, -CN, NO ₂ , OH, -NH ₂ , -NH(C _1-20 alkyl), -N (C _{1 -20} alkyl) ₂ , -S(O) ₂ OH, -CHO, -C(O)OH, -C(O)-C _1-20 alkyl, -C(O)-OC _1-20 alkyl , -C(O)NH ₂ , -C(O)NH-C _1-20 alkyl, -C(O)N(C _1-20 alkyl) ₂ , -SiH ₃ , -SiH (C _1-20 Alkyl) ₂ , -SiH ₂ (C _1-20 alkyl), -Si(C _1-20 alkyl) ₃ , -OC _1-20 alkyl, -OC _1-20 alkenyl, -OC _1-20 Haloalkyl, C _1-20 alkyl, C _1-20 alkenyl, and C _1-20 haloalkyl; and R ¹ is as defined herein.

In some embodiments, substituting an alkyl chain (and similar groups such as haloalkyl, arylalkyl, heteroarylalkyl, etc.) on one or two quinone imine nitrogen atoms may improve the polymer in organic Solubility in solvents. Thus, in certain embodiments, R ¹ may be a straight or branched C _3-40 alkyl group, examples of which include n-hexyl, 1-methylpropyl, 1-methylbutyl, 1-methylpentyl Base, 1-methylhexyl, 1-ethylpropyl, 1-ethylbutyl, 1,3-dimethylbutyl and 2-octyldodecyl. In certain embodiments, R ¹ can be a straight or branched C _3-40 alkenyl group. In a particular embodiment, R ¹ can be a branched C _3-20 alkyl group or a branched C _3-20 alkenyl group. For example, R ¹ can be independently selected from the following each time it occurs:

In certain embodiments, R ¹ is at each occurrence may be straight-chain or branched C _6-40 alkyl or alkenyl group, the optionally substituted by straight-chain or branched C _6-40 alkyl or alkenyl group An arylalkyl group, an aryl group substituted with a linear or branched C _6-40 alkyl or alkenyl group (for example, a phenyl group) or, optionally, a linear or branched C _6-40 alkyl or alkenyl group Aryl (e.g., biphenyl) wherein each of these groups may be optionally substituted with from 1 to 5 halo groups (e.g., F). In some embodiments, R ¹ can be a biaryl group, wherein two aryl groups are covalently linked via a linking moiety (L'). For example, the linking moiety can be a divalent C _1-6 alkyl group or a carbonyl group. In a particular embodiment, R ¹ can be independently selected from each occurrence:

In some embodiments, R ¹ can be an optionally substituted C _6-14 cycloalkyl. For example, R ¹ can be independently selected from each occurrence:

In various embodiments, the polymers taught by the present invention can include a comonomer M ₂ having a formula selected from the group consisting of: Wherein: π-2 is a polycyclic moiety which is optionally substituted; Ar is independently a monocyclic aryl or heteroaryl which is optionally substituted at each occurrence; Z is a conjugated linear linking moiety; and m, m' and m" are independently 0, 1, 2, 3, 4, 5 or 6.

In some embodiments, π-2 may be a polycyclic C _8-24 aryl group or a polycyclic 8 to 24 membered heteroaryl group, wherein each of these groups may be optionally substituted with from 1 to 6 R ^e groups, wherein :R ^e is independently a) halogen at each occurrence, b)-CN, c)-NO ₂ , d) pendant oxy, e) -OH, f) = C(R ^f ) ₂ , g) C _1-40 alkyl, h) C _2-40 alkenyl, i) C _2-40 alkynyl, j) C _1-40 alkoxy, k) C _1-40 alkylthio, l) C _1-40 Haloalkyl, m)-YC _3-10 cycloalkyl, n)-YC _6-14 aryl, o)-YC _6-14 haloaryl, p)-Y-3 to 12 membered cycloalkyl, Or q)-Y-5 to 14 membered heteroaryl, wherein C _1-40 alkyl, C _2-40 alkenyl, C _2-40 alkynyl, C _3-10 cycloalkyl, C _6-14 aryl , C _6-14 haloaryl, 3 to 12 membered cycloheteroalkyl and 5 to 14 membered heteroaryl are each optionally substituted with 1 to 4 R ^f groups; R ^f is independently a at each occurrence Halogen, b)-CN,c)-NO ₂ ,d) pendant oxy, e)-OH,f)-NH ₂ ,g)-NH(C _1-20 alkyl),h)-N(C _1-20 alkyl) ₂ ,i)-N(C _1-20 alkyl)-C _6-14 aryl,j)-N(C _6-14 aryl) ₂ ,k)-S(O) _w H,l)-S(O) _w -C _1-20 alkyl, m)-S(O) ₂ OH,n)-S(O) _w -OC _1-20 alkyl, o)-S(O ) _w -OC _6-14 aryl, p)-CHO,q)-C(O)-C _{1 -20} alkyl, r)-C(O)-C _6-14 aryl, s)-C(O)OH, t)-C(O)-OC _1-20 alkyl, u)-C(O )-OC _6-14 aryl, v)-C(O)NH ₂ , w)-C(O)NH-C _1-20 alkyl, x)-C(O)N (C _1-20 alkyl) ₂ , y)-C(O)NH-C _6-14 aryl, z)-C(O)N(C _1-20 alkyl)-C _6-14 aryl, aa)-C(O) N(C _6-14 aryl) ₂ ,ab)-C(S)NH ₂ ,ac)-C(S)NH-C _1-20 alkyl,ad)-C(S)N(C _1-20 Alkyl) ₂ , ae)-C(S)N(C _6-14 aryl) ₂ , af)-C(S)N(C _1-20 alkyl)-C _6-14 aryl, ag)- C(S)NH-C _6-14 aryl, ah)-S(O) _w NH ₂ , ai)-S(O) _w NH(C _1-20 alkyl), aj)-S(O) _w N(C _1-20 alkyl) ₂ , ak)-S(O) _w NH(C _6-14 aryl),al)-S(O) _w N(C _1-20 alkyl)-C _{6- 14} aryl, am)-S(O) _w N(C _6-14 aryl) ₂ , an)-SiH ₃ , ao)-SiH(C _1-20 alkyl) ₂ , ap)-SiH ₂ (C _1-20 alkyl), aq)-Si(C _1-20 alkyl) ₃ , ar) C _1-20 alkyl, as) C _2-20 alkenyl, at) C _2-20 alkynyl, au) C _1-20 alkoxy, av) C _1-20 alkylthio, aw) C _1-20 haloalkyl, ax) C _3-10 cycloalkyl, ay) C _6-14 aryl, az) C _{6-14heteroaryl} , ba) 3 to 12 membered cycloheteroalkyl, or bb) 5 to 14 membered heteroaryl; and w is 0, 1 or 2.

For example, π-2 can have a planar and highly conjugated cyclic core that can be substituted as disclosed herein. In various embodiments, the reduction potential of π-2 (measured relative to the SCE electrode and in, for example, a THF solution) can be greater (i.e., both negative, but less absolute) about -3.0 volts. In certain embodiments, the reduction potential of π-2 can be greater than or equal to about -2.2 V. In a particular embodiment, the reduction potential of π-2 can be greater than or equal to about -1.2 V. Examples of suitable cyclic cores include naphthalene, anthracene, naphthacene, pentacene, anthracene, anthracene, anthracene, anthracene, dicyclopentadiene (indacene), anthracene and tetraphenylene, and the like. Where one or more carbon atoms may be replaced by a hetero atom such as O, S, Si, Se, N or P. In certain embodiments, π-2 can include at least one electron withdrawing group.

In certain embodiments, π-2 may include two or more (eg, 2 to 4) fused rings, such as thienothiophene or 3 to 7 fused thiophenes, wherein each ring may be 5, A 6 or 7 membered ring, optionally substituted with from 1 to 6 R ^e groups, wherein R ^e is as defined herein. For example, in various embodiments described herein, R ^e can be an electron withdrawing group such as halogen, -CN, pendant oxy, =C(R ^f ) ₂ , C _1-20 alkoxy, C _1-20 alkylthio or C _1-20 haloalkyl. In certain embodiments, R ^e can be halogen (eg, F, Cl, Br, or I), -CN, C _1-6 alkoxy, -OCF ₃ or -CF ₃ . In a particular embodiment, R ^e can be =0, -CN, =C(CN) ₂ , F, Cl, Br, or I.

In some embodiments, π-2 can include a single ring covalently bonded to a second monocyclic or polycyclic ring system via a spiro atom (eg, a spiro carbon atom) (eg, including optionally occurring substituents and/or ring moieties) Atomic 1,3-dioxolyl or a derivative thereof).

In some embodiments, π-2 can be selected from: Wherein: k, k', l and l' may be independently selected from -CR ² =, =CR ² -, -C(O)- and -C(C(CN) ₂ )-; p, p', q And q' may be independently selected from -CR ² =, =CR ² -, -C(O)-, -C(C(CN) ₂ )-, -O-, -S-, -N=, =N -, -N(R ² )-, -SiR ² =, =SiR ² - and -SiR ² R ² -; r and s may independently be -CR ² R ² - or -C(C(CN) ₂ ) -; u, u', v and v' may be independently selected from -CR ² =, =CR ² -, -C(O)-, -C(C(CN) ₂ )-, -S-, -S (O) -, - S ( O) 2 -, - O -, - N =, = N -, - SiR 2 =, = SiR 2 -, - SiR 2 R 2 -, - CR 2 R 2 -CR 2 R ² - and -CR ² =CR ² -; and R ² may independently be H or R ^e at each occurrence, wherein R ^e is as defined herein.

In certain embodiments, π-2 can be selected from:

Wherein k, l, p, p', q, q', r, s and R ² are as defined herein. In some embodiments, k and l may be independently selected from -CR ² =, =CR ² -, and -C(O)-; p, p', q, and q' may be independently selected from -O-, - ^{S -, - N (R 2} ) -, - N =, = N -, - CR 2 = and = CR ² -; u and v are independently selected from ^{-CR 2 =, = CR 2 -} , - C ( O) -, - C (C (CN) 2) -, - S -, - O -, - N =, = N -, - CR 2 R 2 -CR 2 R 2 - and -CR ² = CR ² - Wherein R ² is as defined herein. For example, R ² can be independently selected from H, halogen, -CN, -OR ^c , -N(R ^c ) ₂ , C _1-20 alkyl, and C _1-20 haloalkyl at each occurrence. Wherein R ^c is as defined herein. r and s each may be CH ₂ .

In certain embodiments, π-2 can be a polycyclic moiety comprising one or more thienyl, thiazolyl or phenyl groups, wherein each of these groups can be optionally substituted as disclosed herein. For example, π-2 can be selected from:

Wherein R ² is as defined herein. For example, R ^{2 can be} selected from the group _{consisting of} H, C _1-20 alkyl, C _1-20 alkoxy, and C _1-20 haloalkyl.

In some embodiments, Ar, at each occurrence, can independently be a single-ring moiety that is optionally substituted from: Wherein: a, b, c and d are independently selected from the group consisting of -S-, -O-, -CH=, =CH-, -CR ³ =, =CR ³ -, -C(O)-, -C(C (CN) ₂ )-, -N=, =N-, -NH- and -NR ³ -; R ³ is independently selected from each of a) halogen, b)-CN, c)-NO ₂ at each occurrence. d) -N(R ^c ) ₂ , e) -OR ^c ,f)-C(O)R ^c ,g)-C(O)OR ^c ,h)-C(O)N(R ^c ) ₂ , i) C _1-40 alkyl, j) C _2-40 alkenyl, k) C _2-40 alkynyl, l) C _1-40 alkoxy, m) C _1-40 alkylthio, n) C _1-40 haloalkyl, o)-YC _3-14 cycloalkyl, p)-YC _6-14 aryl, q)-Y-3 to 14 membered cycloheteroalkyl, and r)-Y-5 to 14 membered heteroaryl, wherein C _1-40 alkyl, C _2-40 alkenyl, C _2-40 alkynyl, C _3-14 cycloalkyl, C _6-14 aryl, 3 to 14 membered cyclohexane The base and the 5 to 14 membered heteroaryl are each optionally substituted with 1 to 5 R ^e groups; and Y, R ^c and R ^e are as defined herein.

Depending on whether Ar is located in the main chain of the polymerization or constitutes one terminal group of the polymer, Ar may be divalent or monovalent. In certain embodiments, each Ar can independently be a 5- or 6-membered aryl or heteroaryl group. For example, each Ar may be selected from the group consisting of phenyl, thienyl, furyl, pyrrolyl, isothiazolyl, thiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, and 1,2,5-thiadiazolyl, wherein each group may be a divalent or monovalent group, and may be optionally substituted with from 1 to 4 substituents independently selected from the group consisting of halogen, -CN, pendant oxy group. C _1-6 alkyl, C _1-6 alkoxy, C _1-6 haloalkyl, NH ₂ , NH(C _1-6 alkyl) and N(C _1-6 alkyl) ₂ . In a particular embodiment, each Ar may be selected from the group consisting of thienyl, isothiazolyl, thiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thia A oxazolyl group, a phenyl group and a pyrrolyl group, wherein each group may be optionally substituted with 1 to 2 substituents independently selected from the group consisting of halogen, -CN, pendant oxy, C _1-6 alkyl, C _{1- 6} alkoxy, C _1-6 haloalkyl, NH ₂ , NH(C _1-6 alkyl) and N(C _1-6 alkyl) ₂ . In some embodiments, Ar can be unsubstituted. In some embodiments, Ar can be thienyl, isothiazolyl, thiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, and 1,2,5-thiadiazole a group in which each is optionally substituted with 1 to 2 C _1-6 alkyl groups.

For example, (Ar) _m , (Ar) _{m '} and (Ar) _m" may be selected from: Wherein R ⁴ is independently H or R ³ at each occurrence, and R ³ is as defined herein. In a particular embodiment, Wherein R ^c is as defined herein.

In various embodiments, the connecting portion Z can be a self-conjugating system (eg, including two or more double bonds or reference bonds) or can form a conjugate system with its neighboring components. For example, in an embodiment where Z is a linear linking moiety, Z can be a divalent vinyl group (ie, having one double bond), a divalent ethynyl group (ie, having a single bond), including two or two More than one conjugated double bond or a bonded C _4-40 alkenyl or alkynyl group, or some other acyclic conjugated system which may include a hetero atom such as Si, N, P, and the like. For example, Z can be selected from: Wherein R ⁴ is as defined herein. In certain embodiments, Z can be selected from:

In some embodiments, M ₂ can include at least one optionally substituted monocyclic aryl or heteroaryl. For example, M ₂ can have the following formula: Wherein m "is selected from 2,4 or 6; and Ar are as defined herein based example, M ₂ selected from:

Wherein R ³ and R ⁴ are as defined herein. In a particular embodiment, M _{2 can} be selected from: Wherein R ³ may be independently selected from the group consisting of halogen, -CN, C _1-20 alkyl, C _1-20 alkoxy, and C _1-20 haloalkyl; and R ⁴ may be independently selected from H, halogen, -CN, C _1-20 alkyl, C _1-20 alkoxy and C _1-20 haloalkyl; and R ^c may independently be H or C _1-6 alkyl at each occurrence.

In some embodiments, M ₂ can include a linking moiety in addition to one or more optionally substituted monocyclic aryl or heteroaryl groups. For example, M ₂ can have the following formula: Wherein m and m' are selected from 1, 2, 4 or 6; m" is selected from 1, 2, 3 or 4; and Ar and Z are as defined herein. In certain embodiments, M _{2 is} optional from: Wherein R ⁴ and R ^c are as defined herein.

In some embodiments, M ₂ can include one or more optionally substituted polycyclic moieties in addition to one or more optionally substituted monocyclic aryl or heteroaryl groups. For example, M ₂ can have the following formula: Wherein m and m' are selected from 1, 2, 4 or 6; and Ar and π-2 are as defined herein. In certain embodiments, M _{2 can} be selected from: Wherein R ² and R ⁴ are as defined herein.

In some embodiments, M ₂ can include one or more linking moieties and/or optionally substituted polycyclic moieties in addition to one or more optionally substituted monocyclic aryl or heteroaryl groups. For example, M ₂ may have a formula selected from the following: Wherein m, m' and m" are independently 1, 2, 3 or 4; and Ar, π-2 and Z are as defined herein. In certain embodiments, M ₂ may be selected from: Wherein R ⁴ is as defined herein.

In other embodiments, M ₂ can have a formula selected from the group consisting of: Wherein π-2 and Z are as defined herein.

While the general teachings of the present invention is based on a copolymer of M ₁ and M _2, M ₁ of a homopolymer but within the scope of the teachings of the present invention.

For a variety of the polymers described above, n can be an integer ranging from 2 to 5,000. For example, n can be 2 to 1,000, 2 to 500, 2 to 400, 2 to 300, or 2 to 200. In certain embodiments, n can be from 2 to 100. In some embodiments, n can be an integer between 3 and 1,000. In certain embodiments, n can be 4 to 1,000, 5 to 1,000, 6 to 1,000, 7 to 1,000, 8 to 1,000, 9 to 1,000, or 10 to 1,000. For example, n can be 8 to 500, 8 to 400, 8 to 300, or 8 to 200. In certain embodiments, n can be from 8 to 100.

Thus, in certain embodiments, the polymers taught by the present invention may comprise repeating units of Formula Ia , Formula Ib, or both: Wherein R ¹ , R ⁴ and m" are as defined herein.

For example, in certain embodiments, the polymers taught by the present invention can include repeating units of one or more of Formula Ia' , Formula Ib' , Formula Ia", and Formula Ib" : Wherein R ¹ is as defined herein.

Certain embodiments of the polymers taught by the present invention can include repeating units of one or more of Formula Ia", Formula Ib", Formula Ia", and Formula Ib"":

Wherein R ¹ and R ³ are as defined herein. For example, R ³ can be independently selected from halogen, -CN, C _1-40 alkyl, C _1-40 alkoxy, and C _1-40 haloalkyl at each occurrence.

In some embodiments, the polymers taught by the present invention may include one or more repeating units of Formula Ic , Formula Id , Formula Ie, and Formula If : Wherein R ¹ and R ⁴ are as defined herein.

For example, in certain embodiments, the polymers taught by the present invention can include repeating units of one or more of Formula Ic' , Formula Id' , Formula Ie', and Formula If' :

Wherein R ¹ is as defined herein.

In certain embodiments, the polymers taught by the present invention may comprise repeating units of Formula Ig , Formula Ih, or both: Wherein R ¹ and m" are as defined herein.

In certain embodiments, the polymers taught by the present invention may comprise repeating units of Formula Ii' , Formula Ij', or both: Wherein R ¹ is as defined herein.

Other examples of polymers of the present teachings may include repeating one or more of Formula IIIa' , Formula IIIa" , Formula Va' , Formula Va" , Formula Vb' , Formula Vb" , Formula Vc', and Formula Vc" unit: Wherein R ¹ and R ⁴ are as defined herein.

Certain embodiments of the polymers of the present invention can be prepared according to the procedures outlined in Scheme 1 below:

Referring to Scheme 1, certain embodiments of the polymers of the present invention can be synthesized via metal catalyzed Stille polymerization. In particular, 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NDA) can be reacted with dibromoisocyanuric acid (DBI) to give dibromonaphthalene-1,4,5,8-double (dimethylimine) (NDI-Br ₂ ). The quinone imine functionalization can be obtained, for example, by reacting NDI-Br ₂ with an appropriate amine (R-NH ₂ ) to give, for example, N,N'-dialkylnaphthalene-1,4,5,8-bis(dimethylimine) ) (NDI2R-Br ₂ ) to achieve. The NDI2R-Br _{2 is} polymerized with a suitable organotin compound in the presence of a metal catalyst such as dichloro-bis(triphenylphosphine)palladium(II) (Pd(PPh ₃ ) ₂ Cl ₂ ) to give the desired polymer.

Scheme 2 below shows an alternative synthesis for the preparation of certain embodiments of the polymers of the present invention:

Other polymers taught by the present invention can be prepared according to procedures similar to those described in Schemes 1 and 2. Alternatively, the polymers of the present invention can be prepared from commercially available starting materials, compounds known in the literature, or via other readily prepared intermediates using standard synthetic methods and procedures known to those skilled in the art. Standard synthetic methods and procedures for the preparation of organic molecules and functional group conversion and manipulation are readily available from relevant scientific literature or standard textbooks in the field. It should be understood that other process conditions may be used, given the typical or preferred process conditions (i.e., reaction temperature, time, mole ratio of reactants, solvent, pressure, etc.) unless otherwise stated. While optimal reaction conditions may vary with the particular reactants or solvents employed, such conditions can be determined by those skilled in the art by routine optimization procedures. Those skilled in the art of organic synthesis will recognize that the nature and sequence of the synthetic steps presented can be varied for the purpose of optimizing the formation of the polymers described herein.

The methods described herein can be monitored according to any suitable method known in the art. For example, product formation can be by spectroscopic methods such as nuclear magnetic resonance spectroscopy (NMR, such as ¹ H or ¹³ C), infrared spectroscopy (IR), spectrophotometry (eg, ultraviolet-visible), mass spectrometry ( MS) is monitored by chromatography, such as high pressure liquid chromatography (HPLC), gas chromatography (GC), gel permeation chromatography (GPC) or thin layer chromatography (TLC).

The reactions or methods described herein can be carried out in a suitable solvent which can be readily selected by those skilled in the art of organic synthesis. At the temperature at which the reaction is carried out, that is, at a temperature ranging from the solvent freezing temperature to the boiling temperature of the solvent, the appropriate solvent generally does not substantially react with the reactants, intermediates and/or products. The given reaction can be carried out in one solvent or a mixture of more than one solvent. Depending on the particular reaction step, a solvent suitable for the particular reaction step can be selected.

Without wishing to be bound by any particular theory, it is believed that the polymers of the teachings of the present invention having a region-regulated polymeric backbone can result in higher molecular weight, larger π-conjugated structures and thus better charge transport efficiency. Thus, in preparing the polymers of the present invention, the teachings of the present invention can include isolating at least one specific average molecular weight moiety and/or enriching and/or isolating NDIR- in concentrated or pure 2,6-diastereomeric form. Br ₂ (and corresponding dibromonaphthalene imine). Since the separation of 2,6-dibromonaphthalene-1,4,5,8-bis(dimethylimine) from an isomeric mixture can be carried out easily and efficiently, the polymer of the present invention includes Formula I' , Formula III' a polymer of the formula V' , the formula VII' , the formula IX' , the formula XI' , the formula XIII' or the formula XV' :

Where x is a real number and 0.5<x 1, and R ¹ , R ⁵ , R ⁶ , R ⁷ , π-2, Ar, Z, m, m′ and m′′ are as defined herein. In various embodiments, x is at least about 0.6, for example Greater than about 0.75, greater than about 0.80, greater than about 0.85, greater than about 0.90, or greater than about 0.95.

Certain embodiments disclosed herein are stable under ambient conditions ("surrounding stable") and are soluble in common solvents. As used herein, when a polymer storm When exposed to ambient conditions such as air, ambient temperature and humidity for a period of time, when the carrier mobility or reduction potential of the polymer is maintained at about its initial measurement, the polymer can be considered to be "surrounding stable" electronically or "Stability under ambient conditions." For example, if the polymer taught by the present invention changes its carrier mobility or redox potential beyond its initial value after exposure to ambient conditions including air, humidity, and temperature for 3, 5, or 10 days. The 20% or no more than 10%, the polymer can be described as being stable around. In addition, if the corresponding film of the polymer is exposed to ambient conditions including air, humidity and temperature for 3 days, 5 days or 10 days, the optical absorption change does not exceed 20% of its initial value (preferably not more than 10%) ), then the polymer can be considered to be stable around.

Without wishing to be bound by any particular theory, if the n-channel transmission is desired, the electron-consuming electronic structure and the region of the polymer of the present invention are highly achievable by copolymerizing M ₁ with a strongly electron-consuming M ₂ repeating unit. The π-conjugated polymer backbone allows the polymer of the present invention to be a peripherally stable n-channel semiconductor material without the need for additional π-core functionalization (i.e., core substitution of the naphthalene moiety) by the strong pull electron functional group. If a large light absorption (extinction coefficient) is required, the polymer of the present invention can have a highly π-conjugated polymerization backbone and the push-pull structure can be achieved by copolymerizing the M ₁ unit with the electron-donating M ₂ comonomer. If a bipolar polymer is desired, for example, in luminescent transistor applications, the polymer of the invention may have a highly π-conjugated polymerization master comprising a copolymer of M ₁ and electron neutral or electron-withdrawing (electron-rich) M ₂ units. chain.

The OTFT based on the polymer of the present invention can have long-term operability and continuous high performance under ambient conditions. For example, based on a certain polymer of the present invention The OTFTs of these embodiments maintain satisfactory device performance in extremely humid environments. Certain embodiments of the polymers of the present invention also exhibit excellent thermal stability over a wide range of annealing temperatures. Photovoltaic devices can maintain satisfactory power conversion efficiency over the long term.

As used herein, a compound can be considered to be soluble in a solvent when at least 0.1 mg of the compound is soluble in 1 mL of solvent. Examples of commonly used organic solvents include petroleum ether; acetonitrile; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane, and bis (2) -methoxyethyl)ether, diethyl ether, diisopropyl ether and tert-butyl methyl ether; alcohols such as methanol, ethanol, butanol and isopropanol; aliphatic hydrocarbons such as hexane; esters such as methyl acetate, Ethyl acetate, methyl formate, ethyl formate, isopropyl acetate and butyl acetate; decylamines such as dimethylformamide and dimethylacetamide; hydrazine, such as dimethyl hydrazine; halogenated fat Groups and aromatic hydrocarbons such as dichloromethane, chloroform, ethylene chloride, chlorobenzene, dichlorobenzene and trichlorobenzene; and cyclic solvents such as cyclopentanone, cyclohexanone and 2-methylpyrrolidone. As indicated in the examples below, the solubility of the polymers of the present invention in conventional organic solvents such as xylene, dichlorobenzene (DCB) and other chlorinated hydrocarbons (CHC) can be as high as 60 g/L.

In view of the high solubility of the polymers of the present invention in conventional solvents, in addition to other more expensive processes such as vapor deposition, they can be processed into various articles using solution processing techniques. A variety of solution processing techniques have been used in organic electronic devices. Common solution processing techniques include, for example, spin coating, drop coating, zone casting, dip coating, knife coating or spray coating. Another example of solution processing techniques is printing. As used herein, "printing" includes non-contact Methods such as ink jet printing, microdispensing and the like, and contact methods such as screen printing, gravure printing, lithography, flexographic printing, lithography, pad printing, microcontact printing, and the like . For example, many printed electronics technologies have focused on inkjet printing, primarily because of the better control of feature locations and multiple layers of overlap. Inkjet printing provides the benefit of not requiring the formation of a master (as compared to contact printing techniques) and digitally controlling ink ejection, thereby providing drop-on-demand printing. However, contact printing technology has the advantage of being very suitable for extremely fast roll processing. It should be noted that different printing techniques require substantially different ink rheological properties, ranging from very viscous formulations used in flexible letterpress printing to less viscous gravure inks to thinner inkjet printing. Solution. Thus, it is not always possible to a priori assume a polymer that works well in a spin coating apparatus, so that it can be processed by a solution and must be printable.

Thus, one of the unexpected properties of the polymers of the present invention includes the processing versatility as demonstrated in the examples below. Formulations comprising the polymers of the present invention can be printed via different types of printing techniques including gravure, flexographic and inkjet printing, thereby providing a smooth, for example, formation of a pinhole free dielectric film and thus a full printing device. And a uniform film.

One or more of the polymers taught by the present invention can be used to prepare an organic semiconductor material or a portion thereof, such as one or more layers of an organic semiconductor material.

Accordingly, the present teachings further provide methods of making organic semiconductor materials. The methods can include preparing to dissolve or disperse in, for example, a solvent or dissolve a composition of one or more of the polymers disclosed herein in a liquid medium, the composition is deposited on a substrate to obtain a semiconductor material precursor, and the semiconductor precursor is processed (eg, heated) to provide inclusion as herein Organic semiconductor materials of polymers such as thin film organic semiconductors are disclosed. In various embodiments, the liquid medium can be an organic solvent, an inorganic solvent such as water, or a combination thereof. In some embodiments, the composition may further comprise one or more additives, independently selected from the group consisting of viscosity modifiers, detergents, dispersants, binders, compatibilizers, curing agents, initiators, humectants, defoamers , humectants, pH adjusters, biocides and bacteriostatic agents. For example, surfactants and/or polymers (eg, polystyrene, polyethylene, polyalphamethylstyrene, polyisobutylene, polypropylene, polymethylmethacrylate, and the like) can be included as a dispersing agent. , adhesives, compatibilizers and / or defoamers. In some embodiments, the deposition step can be performed by printing, including ink jet printing and various contact printing techniques (eg, screen printing, gravure printing, lithography, pad printing, lithography, flexographic printing, and microcontact printing). ). In other embodiments, the depositing step can be performed by spin coating, drop coating, zone casting, dip coating, knife coating or spray coating.

As disclosed above, the organic semiconductor device can be selected from a variety of devices and device structures. With regard to possible polymers, their properties, the configuration of the semiconductor device (except for at least one intermediate layer), reference is made to WO 2009/098253 A1 and the apparatus and method of manufacture thereof. Therefore, the organic semiconductor device may be selected from the group consisting of an electronic device, an optical device, and an optoelectronic device, such as a field effect transistor (eg, a thin film transistor), a photovoltaic device, a photodetector, an organic light emitting device (such as an organic light emitting diode (OLED). And organic light-emitting transistors (OLET)), Complementary Metal Oxide Semiconductor (CMOS), Complementary Inverters, Diodes, Capacitors, Sensors, D-Rectifiers, Rectifiers, and Ring Oscillator. The organic semiconductor device preferably has an airport effect transistor or contains at least one organic field effect transistor. Various types of airport effect transistors are available, including top gate contact type capacitor structure, top gate bottom contact type capacitor structure, bottom gate top contact type capacitor structure and bottom gate bottom contact type capacitor structure. With regard to possible structures and possible methods of manufacturing such devices, reference is made to WO 2009/098253 A1. However, other organic semiconductor materials, other organic semiconductor devices, other structures, and other methods of making such devices are possible within the scope of the present invention.

In another preferred embodiment, the method of the present teachings can include an organic semiconductor material, wherein the organic semiconductor material is selected from the group consisting of: Wherein M ₁ is selected from: Wherein R ¹ is 2-octyldodecyl; and M ₂ is a polymer of the formula: Wherein m is selected from the range of 2 to 50, preferably 2 to 20 repeating units, or 2 to 10.

In another preferred embodiment, the intermediate layer is preferably produced by processing from at least one of a spin coating method and a dipping method from a solution comprising at least one solvent and at least one thiol compound. The at least one thiol compound can be dispersed and/or dissolved in at least one solvent. More than one solvent can be used. Depending on the type of the thiol compound, various solvents such as an aqueous solvent and/or an organic solvent may be used. An example will be given below. In addition to spin coating and dipping, other types of coating methods can be used, such as printing methods, blade scraping, or combinations of the methods and/or other methods.

In a preferred embodiment, the self-solution processing can include at least one step of applying a solution to at least one electrode, preferably two electrodes, and at least one step of removing the solvent. Therefore, it is preferred to apply the solution to at least one of the source electrodes and/or the at least one of the ruthenium electrodes. At least one step of removing the solvent may comprise a mechanical step (such as in spin coating) and/or a thermal step, such as by applying heat to the solution to partially or completely remove the solvent. The solution may comprise a thiol compound in an amount of preferably from 10 mM to 400 mM, preferably from 20 mM to 200 mM. Preferably, the at least one solvent is selected from the group consisting of ethanol, toluene, xylene.

In another aspect of the invention, an organic semiconductor device is disclosed. The organic semiconductor device has at least one organic semiconductor material and is suitable for Supporting charge carrier transport through at least two electrodes of the organic semiconductor material. The at least two electrodes preferably may comprise at least one source electrode and at least one germanium electrode. However, other embodiments are possible. Organic semiconductor materials inherently have bipolar semiconductor properties. At least one intermediate layer may be at least partially interposed between the organic semiconductor material and at least one electrode of the organic semiconductor device. The intermediate layer comprises at least one thiol compound of the formula HS-R, wherein R is an organic residue. The thiol compound has a dipole moment. The dipole moment has the same direction and at least the same magnitude as the dipole moment of 4-phenylthiophenol. The intermediate layer inhibits bipolar charge carrier transport between the electrodes to facilitate unipolar charge carrier transport.

The organic semiconductor device is preferably prepared by one or more of the methods of the above disclosed embodiments. Thus, with regard to definitions and with respect to possible embodiments, reference may be made to the disclosure of the method as given above.

In a preferred embodiment, the organic semiconductor device includes a channel between at least two electrodes for charge carrier transport. Thus, as outlined above, at least two electrodes can include at least one source electrode and at least one germanium electrode. The channel length of the channel is preferably from 1 μm to 500 μm and preferably from 5 μm to 200 μm. Additionally, the organic semiconductor device can have at least one other electrode, such as at least one gate electrode. At least one other electrode, such as at least one gate electrode, may be separated from the channel by at least one insulating material, preferably by at least one insulating layer. For other preferred embodiments, reference may be made to the methods disclosed above.

In another aspect of the invention, the use of an intermediate layer comprising at least one thiol compound for use in having at least one organic semiconductor material is disclosed The bipolar charge carrier transport is inhibited in an organic semiconductor device suitable for supporting charge carrier transport via at least two electrodes of an organic semiconductor material to facilitate unipolar charge carrier transport. The intermediate layer is at least partially interposed between the at least one electrode and the organic semiconductor material. The intermediate layer comprises at least one thiol compound of the formula HS-R, wherein R is an organic residue. The thiol compound forms an electric dipole having a dipole moment. The dipole moment can have the same direction and at least the same magnitude as the dipole moment of 4-phenylthiophenol. The intermediate layer inhibits bipolar charge carrier transport between the electrodes to facilitate unipolar charge carrier transport.

For other embodiments and definitions, reference may be made to the method as outlined above. Thus, as outlined above, suppressing bipolar charge carrier transport between electrodes to facilitate unipolar charge carrier transport refers to electrons and holes in organic semiconductor materials in devices that do not have at least one intermediate layer. The mobility differs by less than two orders of magnitude, and by using at least one intermediate layer in the same layer configuration (except for at least one intermediate layer), the electron and hole mobility can differ by two orders of magnitude or more by more than two orders of magnitude, and Preferably it is more than three orders of magnitude. Preferably, as outlined above, bipolar semiconductor characteristics are inhibited to facilitate unipolar negative charge carrier transport.

The method of the present invention, the use of the organic semiconductor device of the present invention, and the intermediate layer of the present invention are implicitly superior to many advantages of known methods, organic semiconductor devices, and uses. Thus, it has surprisingly been found that a method of implementing at least one intermediate layer of the type disclosed above, such as a method of forming at least one self-assembled monolayer, can be made unipolar by transferring the transmission characteristics from bipolar charge carrier transport Charge carrier transport, in particular, unipolar negative charge carriers Transmission significantly changes the charge carrier transport characteristics of the organic semiconductor device. Although all prior art documents report the work function of self-assembled monolayer adjustable electrodes on metal electrodes, the effects of such electrode treatments on bipolar materials have not been known so far. Thus, the use of the present invention preferably produces a unipolar device by establishing a suitable self-assembled monolayer process in combination with a preferred low band gap polymer. Therefore, the band gap of the organic semiconductor material is preferred, and the band gap of the polymer, that is, the energy difference between the HOMO level and the LUMO level is within the range given above. As outlined above, it is preferred to use P(NDI2OD-T2) in combination with at least one intermediate layer, and more preferably in combination with suitable SAM processing to produce a unipolar device, preferably a negative charge carrier unipolar device.

The method of forming the intermediate layer, preferably forming the self-assembled monolayer itself, may not significantly increase the manufacturing cost because the formation of the at least one intermediate layer typically utilizes steps similar to those used in conventional fabrication techniques, such as printing methods or Methods of forming other semiconductor structures. Thus, techniques such as the following may be employed: dissolving the thiol compound in at least one solvent to form a solution, applying the solution to the surface of the substrate, preferably to the surface of the metal, drying the coated film, and removing the solvent. Thus, the use of at least one intermediate layer, preferably at least one self-assembled monolayer, may be suitable for use with an airport effect transistor and/or other organic semiconductor devices.

As outlined above, the thiol compound has a dipole moment vector directed toward the dipole moment of the SH group remote from the thiol compound, wherein the electric dipole moment has at least the same magnitude as the electric dipole moment of the 4-phenylthiophenol. . This can be easily achieved by designing an electronic system of residues R in the thiol compound. Therefore, the electric dipole moment can be changed by using an electron-rich residue and an electron-deficient residue, and thus an electron-rich thiol compound and an electron-deficient thiol compound. As outlined above, the use of electron-rich and electron-deficient thiol compounds to treat gold and silver electrodes and low band gap polymers typically exhibits significant bipolarity without contact treatment. The polymer was deposited on top of the intermediate layer and the OTFT established in this manner was completed and tested. As outlined in the other details below, I _on,n :I _{on,p is} used as the figure of merit, I _on,n :I _on,p is the pass-to-state source-drain current ratio of the n-channel to p-channel of the transistor . In the absence of bipolar properties, this ratio of electron transport or n-channel semiconductor copolymers is expected to be higher.

Hereinafter, preferred embodiments of the present invention are disclosed by referring to the figures. However, the invention is not limited to the preferred embodiments.

Preferred embodiment

In Fig. 1, a cross-sectional view of a preferred embodiment of an organic semiconductor device 110 of the present invention is depicted. The organic semiconductor device can include a substrate 112, such as a glass substrate and/or a plastic substrate. Further, the organic semiconductor device 110 includes two electrodes 114, in which case the two electrodes 114 include a source electrode 116 and a germanium electrode 118. An intermediate layer 120 is deposited on top of the electrodes 114, at least one organic semiconductor material 122 is deposited on top of the intermediate layer 120, and an insulating layer 124 is placed on top of the at least one organic semiconductor material 122. A gate electrode 126 is deposited on top of at least one of the insulating layers 124.

It must be noted that the configuration disclosed in Figure 1 means a schematic configuration. The organic semiconductor device 110 may include other components not depicted in FIG. 1 or may include a different layer configuration than that depicted in this figure. Therefore, the configuration in Figure 1 reveals An illustrative embodiment of an organic thin film transistor 128 having a top gate bottom contact type (TGBC) configuration. However, it can be other device configurations.

Device manufacturing

A top gate bottom contact type (TGBC) thin film transistor is fabricated on a polyethylene terephthalate (PET) substrate 112 with reference to the configuration disclosed in FIG. Source electrode 116 and germanium electrode 118 are made of gold or silver and patterned by lithography. Preferably, in this configuration or in other embodiments of the invention, the channel length, that is, the spacing between the source electrode 116 and the drain electrode 118 is in the range of 1 μm to 500 μm, preferably 5 μm to 200 μm. Inside. Moreover, in this layout or in other embodiments of the invention, the w/l ratio of the ratio between the width of the characterization electrodes 116, 118 and the length of the channel may vary from 50 to 10,000.

After lithography of electrode 114, the remaining photoresist layer on electrode 114 is stripped just prior to use of the sample to minimize dust particle accumulation in the channel region and oxidation of electrode 114 (primarily silver electrode).

Prior to use, the substrate 112 having the electrodes 114 thereon is rinsed with acetone to remove the photoresist. Subsequently, the sample was dried by blowing with nitrogen. The sample was further dried by heating the sample with a hot plate at 90 ° C for 30 seconds to remove residual solvent. The substrate was further cleaned using RF plasma for 5 minutes.

At the same time, a thiol solution having a concentration ranging from 20 mM to 200 mM was prepared using an organic solvent (i.e., ethanol or toluene) and filtered (PTFE 0.45 μm) before use. The thiol compounds used in the illustrative examples are listed in Table 1.

In the second column of Table 1, the provision of the thiol compound used in the experiment is given. Where SA represents Sigma Aldrich, Inc. (www.sigmaaldrich.com); TCI stands for Tokyo Chemical Industry Co Ltd (http://www.tci-asiapacific.com); Fluorochem stands for Fluorochem Ltd. (www.fluorochem.co) .uk); Oakwood, Inc., Oakwood Products, Inc. (www.oakwoodchemical.com); ABCR, Abcr GmbH & Co. KG (www.abcr.de); and Enamine, Enamine Ltd. (www.enamine.net).

In the "Electrical Dipole moment" column, the magnitude (absolute value) of the dipole moment of each thiol compound is listed. As outlined above, these electric dipole moments are calculated using the Spartan '06 software.

In the "Direction of Electric Dipole Moment" column, information is given about the polarity of the electric dipole and the direction of the electric dipole moment vector. Therefore, the information "from R to SH" may mean a thiol compound having a negative polarity on the residue R side and a positive polarity on the thiol group SH side. The information "from SH to R" may mean a thiol compound having a positive polarity on the residue R side and a negative polarity on the thiol group SH side. As can be seen from Table 1, the polarity of the electric dipole strongly depends on the chemical nature of the residue R. A thiol compound having an R that strongly absorbs electrons (such as a fluorine group in PFBT) has an electric dipole moment vector directed toward the SH group, and the electron-withdrawing residue exhibits an electric dipole moment vector pointing away from the SH group. As outlined above, in the intermediate layer of the teachings of the present invention, the thiol compound has an electric dipole moment vector pointing away from the SH group of the thiol compound, and the electric dipole moment and the electric dipole of the 4-phenylthiophenol The moments have at least the same magnitude. In Table 1, the following thiol compounds meet this requirement: DT, MBT, MTBT, DMeOBT, BBT, PBT, TN, ABT, BM, PMBT.

For each sample, the intermediate layer 120 was processed on the electrode 114 by using the respective thiol compounds listed in Table 1, except for Comparative Example 1 in Table 1. For comparison, Sample 1 in Table 1 was left without the intermediate layer 120. Without wishing to be bound by this assumption, it is believed that these intermediate layers 120 form a self-assembled monolayer (SAM) and will be referred to hereinafter. The self-assembled monolayer is prepared on the silver electrode 116 by spin coating a conditionally warm solution onto the substrate 112 having the electrode 114 thereon or by immersing the substrate 112 having the electrode 114 thereon in a thiol solution. The thus processed sample was then rinsed with a pure organic solvent and blown dry with nitrogen. The sample was further dried by heating the sample with a hot plate at 90 ° C for 30 seconds.

The sample thus processed is then coated with an organic semiconductor material 122. For this purpose, P(NDI2OD-T2) is deposited by spin-coating a solution of P(NDI2OD-T2) in toluene at a concentration ranging from 5 mg/mL to 10 mg/mL in a spinning speed of 1500 rpm to 2000 rpm. Floor. As disclosed in WO 2009/098253 A1, P(NDI2OD-T2) will be synthesized by itself. The resulting film was dried on a hot plate at 90 ° C for 30 seconds.

Further, an insulating layer 124 is coated on top of the sample. For this purpose, a dielectric layer is deposited by spin coating a layer of polymethyl methacrylate (PMMA) or polystyrene (PS). The total thickness of the insulating layer 124 is about 400 nm to 600 nm.

The device structure is accomplished by vapor depositing a patterned Au junction as a gate electrode 126 via a shadow mask. The gate electrode 126 has a thickness of about 30 to 50 nm.

Device characterization

When electrically characterizing the organic semiconductor device 110, a Keithley 4200 semiconductor characterization system having three power supply measurement units (SMUs) and integrated capacitor voltage units (CVUs) configured with preamplifiers was used. In this configuration, All electrical characterizations are performed, including capacitance measurements of all fabricated OTFTs. As the second major component of the test system, a signatone probe station is used. Use a dark/metal case to avoid exposure and reduce ambient noise.

The charge carrier mobility (μ) of the OTFT is calculated by the standard field effect transistor equation. In conventional metal-insulator-semiconductor FETs (MISFETs), there is typically a linear and saturated region at different VGs in the IDS vs. VDS curve. Among them, IDS represents the source-drain saturation current, VDS is the potential between the source and the drain, and VG is the gate voltage. Under large VDS, the current is saturated and is obtained by ( I _DS ) _sat = ( WC _i /2 L ) μ ( V _G - V _t ) ² . Where L represents the channel length, i.e., the spatial spacing between electrodes 116 and 118, and W represents the channel width, i.e., the width of electrodes 116, 118 in a direction perpendicular to the interconnect between electrodes 116, 118. Ci is the specific capacitance of the gate insulator, and Vt is the threshold voltage. The charge carrier mobility μ in the saturation region is calculated by adapting the above equation to the following equation: The device parameters were obtained by applying a gate voltage of 50 V and a source-drain voltage of 50 V operating in the saturation region and are summarized in Table 2.

The information provided in Table 2 is obtained from a top gate bottom contact type architecture device on a PET substrate having a silver electrode. The organic semiconductor layer was deposited by spin coating a solution of 5 mg/ml P(NDI2OD-T2) in toluene to obtain a layer thickness of 50 nm. The dielectric layer was deposited by spin coating a solution of 4% by weight of polystyrene in isopropyl acetate to obtain a dielectric layer having a thickness of 600 nm.

In Table 2, I _on,n represents the n-channel characteristic, that is, the starting current of the negative charge carrier transmission. I _on,p represents the p-channel characteristic, that is, the starting current of positive charge carrier transport. In the column labeled I _on,n :I _on,p , the ratio of these starting currents is given, which is a measure of the ratio of negative charge carrier mobility to positive charge carrier mobility. The value marked with " ^* " in Table 2 indicates that the value in the column "I _on,n :I _on,p " indicates the measurement of the I _on /I _off ratio of the n-channel performance only, that is, the start current and I _off The ratio indicates that the lowest current is obtained during the measurement.

In Figures 2 and 3, an example of a measurement curve for an OTFT is shown which is used to derive the values listed in Table 2. In Figure 2, the source-drain current (I _SD , left vertical axis) and gate leakage current (I _G , right vertical axis) are plotted as a function of gate voltage U _G , using equal gate-source Voltage and drain-source voltage U _G = U _GS = U _DS . Where ‧ curve 210 represents the typical measurement of the source-drain current of the sample without the intermediate layer (sample type 1), and ‧ curve 212 represents the source-drain current of the sample with the ABT intermediate layer (sample type 10) Typical measurement, ‧ curve 214 represents the typical measurement of the source-drain current of the sample with the MBT interlayer (sample type 4), and ‧ the curve 216 represents the gate of the sample without the intermediate layer (sample type 1) Typical measurement of leakage current, ‧ point curve 218 represents a typical measurement of the gate leakage current of a sample with an ABT intermediate layer (sample type 10), and ‧ point curve 220 represents a sample with an MBT intermediate layer (sample type 4) Typical measurement of the gate leakage current.

Opposite to curve 210, transfer curves 212 (ABT) and 214 (MBT) in Figure 2 demonstrate p-channel suppression. Regarding the gate leakage current, curves 218 (ABT) and 220 (MBT) show that these gate leakage currents are equal to the p-channel current, indicating that the p-channel current is completely suppressed.

To demonstrate the effect of the dipole moment of the thiol compound, in Figure 3, the source-drain current I _{SD of the} electron-electron residue (PFBT) and the electron-withdrawing residue (ABT) is depicted as a function of the gate voltage U _G . . Where: ‧ curve 222 represents the typical measurement of the source-drain current of the sample without the intermediate layer (sample type 1), and ‧ curve 224 represents the source-drain current of the sample with the intermediate layer of ABT (sample type 10) A typical measurement, ‧ curve 226 represents a typical measurement of the source-drain current of a sample with a PFBT interlayer (sample type 2).

In contrast to the sample without the intermediate layer (curve 222), the ABT treated sample (curve 224) clearly exhibited p-channel inhibition, while the PFBT treated sample (curve 226) clearly exhibited the opposite effect, i.e., n-channel inhibition.

In summary, the results in Table 2 and Figures 2 and 3 are clearly shown. As can be seen from the higher I _{on, n} :I _on,p ratio, the thiol compound with the electron-retarding residue R exhibits p-channel performance significantly Suppress, while achieving improved n-channel performance. In particular, MBT and ABT processing is completely suppressed to suppress hole injection. On the other hand, by using an electron-electron thiol compound, the reaction of enhancing p-channel efficiency can be achieved. Thus, by using the intermediate layer of the thiol compound taught by the present invention, the bipolar nature of the OTFT can be suppressed to facilitate unipolar charge carrier transport, in particular for unipolar n-type charge carrier transport.

This result was further confirmed by various capacitance measurements, which are depicted in Figures 4A-4B. When a voltage is applied to the top electrode (gate electrode 126), charge will be injected from a bottom electrode 114 into the organic semiconductor material 122 (OS), followed by an interface between the insulating layer 124 (dielectric) and the organic semiconductor material 122. It accumulates and is therefore measured as a capacitor in series with the dielectric. The increase in capacitance in the positive and negative applied voltages represents the accumulation of electrons and holes at the dielectric/OS interface, respectively. The difference in capacitance value (ΔC) indicates how easy the charge is injected. The higher the value, the lower the injection barrier.

4A-4B show capacitance measurements C (in Farah (F)) as a function of gate voltage U _{G for} various device configurations with different types of thiol compounds. Where: ‧ Figure 4A shows the typical capacitance measurement of the sample without the intermediate layer (sample type 1), ‧ Figure 4B shows the typical capacitance measurement of the sample with the PFBT intermediate layer (sample type 2), ‧ Figure 4C shows the middle with ABT Typical capacitance measurements of the sample of the layer (sample type 10), and ‧ Figure 4D shows a typical capacitance measurement of the sample with the MBT interlayer (sample type 4).

Figures 4A through 4D show that the untreated sample (without the intermediate layer, Figure 4A) shows charge accumulation at both positive and negative applied voltages indicating bipolarity. The PFBT treated sample (PFBT interlayer, Figure 4B) shows a stronger charge buildup at the negative gate voltage, indicating that hole injection is more efficient. ABT treated samples (ABT intermediate layer, Figure 4C) and MBT treated samples (MBT intermediate layer, Figure 4D) showed accumulation only under positive applied voltage, confirming the unipolar n-channel performance of these OTFTs.

Examples of organic semiconductor materials

In the following, an example of the preparation of a polymer of an organic semiconductor material for an organic semiconductor device is given. However, the examples are provided to further illustrate and assist in understanding the teachings of the present invention and are not intended to limit the invention in any way. Further reference is made to WO 2009/098253 A1.

All reagents were purchased from commercial sources and were used without further purification unless otherwise stated. Certain words, for dielectric and semiconductor dioxane formulations, the dichlorobenzene (the DCB), chloroform (CHCl _3), and other chlorinated hydrocarbons (CHC) were purchased from Sigma Aldrich and distilled prior to use. Anhydrous tetrahydrofuran (THF) was distilled from Na/benzophenone. Use of conventional Schlenk techniques, and unless otherwise stated, reaction was carried out under N _2. The compound 5,5'-bis(trimethylstannyl)-2,2'-bithiophene is according to the procedure described by Goto et al., Angew. Chem. Int. Ed., Vol. 44: 4322 (2005). preparation.

In some cases, the characterization data is provided by ¹ H-NMR, ¹³ C-NMR, and/or elemental analysis. NMR spectra were recorded on an Inova 500 NMR spectrometer ( ¹ H, 500 MHz). Elemental analysis was performed by Midwest microlab, LLC. The molecular weight of the polymer was determined on a Waters GPC system (Waters Pump 510) at room temperature in THF versus polystyrene standards.

Example 1: Polymer Synthesis

The following examples describe the preparation of certain polymers and related intermediates of the teachings of the present invention.

Example 1A. Preparation of poly{[N,N'-bis(2-ethylhexyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5'-( 2,2'-bithiophene)}[P(NDI2EH-T2)]

2,6-Dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride (NDA-Br ₂ ) was prepared. Oleum _{(20% SO 3, 100 mL} ) The mixture was stirred for 2 hours 1,4,5,8-naphthalene tetracarboxylic acid dianhydride (2.8 g, 10.3 mmol) and at 55 ℃. A solution of dibromoisocyano cyanide (3.0 g, 10.5 mmol) in fuming sulfuric acid (50 mL) was added to this mixture over 40 min. The resulting mixture was then warmed to 85 ° C and maintained at this temperature for 43 hours. After cooling to room temperature, the reaction mixture was poured on EtOAc (EtOAc) (EtOAc). The resulting precipitate was collected by centrifugation, washed with water and methanol, and then evaporated, and then evaporated to give a yellow solid (3.6 g, 8.5 mmol, yield: 82.2%). Elemental analysis (calc. C, 39.47; H, 0.47; N, 0.00): calcd. C, 38.20; H, 0.79;

Preparation of N,N'-bis(2-ethylhexyl)-2,6-dibromonaphthalene-1,4,5,8-bis(dimethylimineimine) (NDI2EH-Br ₂ ). A mixture of NDA-Br ₂ (above, 1.6 g, 3.9 mmol), 2-ethylhexylamine (1.4 mL, 8.5 mmol), o-xylene (6 mL) and propionic acid (2 mL) was stirred at 140 °C. 1 hour. After cooling to room temperature, MeOH (10 mL) was evaporated. Further purification by hydrazine gel column chromatography using a mixture of chloroform:hexane (5:1, v/v) as a solvent to give a pale yellow solid as a product (0.61 g, 0.94 mmol, yield 24.4%).

¹ H NMR (CDCl ₃ , 500 MHz): δ 9.01 (s, 2H), 4.10-4.25 (m, 4H), 19.4-1.97 (m, 2H), 1.20-1.40 (m, 16H), 0.87-1.03 ( m, 12H). ¹³ C NMR (CDCl ₃ , 125 MHz): δ 161.4, 161.2, 139.4, 128.6, 127.9, 125.5, 124.3, 45.3, 38.0, 30.8, 28.7, 24.2, 23.3, 14.3, 10.8.

The copolymer P (NDI2EH-T2) was prepared. Stir NDI2EH-Br ₂ (above, 98 mg, 0.15 mmol), 5,5'-bis(trimethylstannyl)-2,2'-bithiophene (74 mg) at 90 ° C under argon , 0.15 mmol) and a mixture of Pd(PPh ₃ ) ₂ Cl ₂ (3.5 mg, 0.005 mmol) in anhydrous toluene (5 mL) for 4 days. Bromobenzene (0.3 mL) was then added to the reaction and the resulting mixture was stirred for further 12 hours. After cooling to room temperature, a solution of potassium fluoride (1.2 g) in water (2.5 mL) was added. The mixture was stirred at room temperature for 2 hours and the precipitate was collected by filtration. The solid was dissolved with a small amount of chloroform, methanol was added and the solid was collected by filtration. This procedure was repeated using chloroform and acetone to give a dark blue solid as crude. This crude product was purified by Soxhlet extraction with acetone (80 mg, yield 80.7%).

¹ H NMR (CDCl ₃ , 500 MHz): δ 8.82 (br, 2H), 7.35 (br, 4H), 4.15 (br, 4H), 1.97 (br, 2H), 1.18-1.70 (m, br, 16H) , 0.80-1.12 (m, br, 12H). Elemental analysis (calc. C, 69.91; H, 6.18; N, 4.29): C, 69.63; H, 5.66; N, 3.71.

Example 1B. Preparation of poly{[N,N'-bis(2-ethylhexyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternate-2,5-thiophene} [P(NDI2EH-T1)]

The copolymer P (NDI2EH-T1) was prepared. Stirring NDI2EH-Br ₂ (Example 1A, 84 mg, 0.13 mmol), 2,5-bis(trimethylstannyl)thiophene (53 mg, 0.13 mmol) and Pd (PPh) at 90 ° C under argon ₃ ) A mixture of ₂ Cl ₂ (3.0 mg, 0.004 mmol) in anhydrous toluene (5 mL). Bromobenzene (0.3 mL) was then added and the resulting mixture was stirred at 90 ° C for further 12 hours. After cooling to room temperature, a solution of potassium fluoride (1.2 g) in water (2.5 mL) was added. The mixture was stirred at room temperature for 2 hours and the precipitate was collected by filtration. The solid was dissolved with a small amount of chloroform, methanol was added and the obtained solid was collected by filtration. This procedure was repeated using chloroform and acetone to give a dark blue solid (20.0 mg, yield: 20.7%). Elemental analysis (calc. C, 71.55; H, 6.71; N, 4.91): C, 71.59; H, 6.00; N, 4.56.

Example 1C. Preparation of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5 '-(2,2'-bithiophene)}[P(NDI2OD-T2)]

1-Iodo-2-octyldodecane was prepared. Iodine (12.25 g, 48.3 mmol) was added to 2-octyl-1-dodecanol (12.42 g, 41.6 mmol), triphenylphosphine (13.17 g, 50.2 mmol) and imidazole (3.42 g) at 0 °C. , 50.2 mmol) in a solution of 80 mL of dichloromethane. After stirring for 30 minutes, the reaction mixture was allowed to warm to room temperature over 4 hours, then 12 mL of saturated Na ₂ SO ₃ (aq.). The organics were concentrated by evaporation and the mixture was dissolved in 500 mL pentane, washed three times with 200 mL water and once with 150 mL brine. The mixture was then passed through a 3 cm silicone plug and dried over Na ₂ SO ₄ . The organics were concentrated by evaporation to give a colourless oil (15.78 g, yield: 92.9%).

¹ H NMR (CDCl ₃ 500 MHz): δ: 2.60 (d, J = 5.0 Hz, 2H), 2.00 (t, J = 5.0 Hz, 1H), 1.30-1.20 (b, 32H), 0.89 (t, J) = 7.5 Hz, 6H); MS (EI): m/z (%) 408.23 (100) [M ⁺ ]. Elemental analysis (calc. C, 58.81; H, 10.12): Found C, 58.70; H, 9.97.

Preparation of 2-octyldodecylamine. 1-Iodo-2-octyldodecane (5.90 g, 14.5 mmol) and potassium phthalimide (2.94 g, 15.9 mmol) were dissolved in 25 mL DMF and stirred vigorously at 25 ° C for 72 hours. . The reaction mixture was poured into 200 mL of pentane and washed 4 times with 100 mL of water. The mixture was then passed through a 3 cm silica gel and concentrated to give a colourless oil. The oil was then dissolved in 150 mL of ethanol and 4 mL of hydrazine hydrate was added to give a mixture which was refluxed overnight. The resulting precipitate was collected by filtration, dissolved in 100 mL of water and basified by adding 6 M NaOH (aqueous). The resulting mixture was dissolved in 200 mL pentane, and washed four times with 100 mL of water, washed once with 70 mL brine, dried over MgSO ₄ and concentrated to give a colorless oil (3.08 g, yield 72%).

¹ H NMR (CDCl ₃ 500 MHz): δ: 2.60 (d, J = 5.0 Hz, 2H), 2.00 (t, J = 5.0 Hz, 1H), 1.30-1.20 (b, 32H), 0.89 (t, J) = 7.5 Hz, 6H); MS (EI): m/z (%) 297.34 (100) [M ⁺ ]. Elemental analysis (calc. C, 80.73; H, 14.57): Found C, 80.78;

Preparation of N,N'-bis(2-octyldodecyl)-2,6-dibromonaphthalene-1,4,5,8-bis(dimethylimineimine) (NDI2OD-Br ₂ ). Stirring NDA-Br ₂ (Example 1A, 2.34 g, 5.49 mmol), 2-octyldodecylamine (4.10 g, 13.78 mmol), o-xylene (18 mL) and propionic acid (6 mL) at 140 °C a mixture of 1 hour. After cooling to room temperature, most of the solvent was removed in vacuo, and the residue was purified eluting with chloroform:hexane (1:1, v/v) as a solvent. (1.98 g, 2.01 mmol, yield 36.7%).

¹ H NMR (CDCl ₃ 500 MHz): δ: 8.95 (s, 2H), 4.12 (d, J = 7.5 Hz, 4H), 1.97 (m, 2H), 1.20-1.40 (m, 64H), 0.84-0.89 (m, 12H). ¹³ C NMR (CDCl ₃ , 125 MHz): δ: 161.3, 161.1, 139.3, 128.5, 127.8, 125.4, 124.2, 45.6, 36.6, 32.1, 32.0, 31.7, 30.2, 29.9, 29.8, 29.7, 29.6, 29.5, 26.5 , 22.9, 22.8, 14.3. Elemental analysis (calc. C, 65.84; H, 8.60; N, 2.84):

The copolymer P (NDI2OD-T2) was prepared. Stir NDI-2OD-Br ₂ (95 mg, 0.096 mmol), 5,5'-bis(trimethylstannyl)-2,2'-bithiophene (48 mg, at 90 ° C under argon). A mixture of 0.096 mmol) and Pd(PPh ₃ ) ₂ Cl ₂ (3.5 mg, 0.005 mmol) in dry toluene (5 mL) Bromobenzene (0.2 mL) was then added and the reaction mixture was maintained at 90 °C for an additional 12 hours. After cooling to room temperature, a solution of potassium fluoride (1 g) in water (2 mL) was added. The mixture was stirred at room temperature for 2 hours and then extracted with chloroform (60 mL×2). The combined organic layers were washed with water (50 mLs The residue was dissolved in a small amount of chloroform and precipitated in methanol and acetone. The obtained blue solid product was purified by Soxhlet extraction with acetone for 48 hours. The remaining solid residue was redissolved in chloroform (50 mL) and the mixture was evaporated to boiling. After cooling to room temperature, the chloroform solution was filtered through a 5 μm filter, and the filtrate was slowly added to methanol (50 mL). The precipitate was collected by filtration, washed with methanol and dried in vacuo to give a dark blue solid as product (88.0 mg, yield 92.1%).

¹ H NMR (CDCl ₃ 500 MHz): δ: 8.53 - 8.84 (m, br, 2H), 7.20-7.48 (br, 4H), 4.13 (s, br, 2H), 2.00 (s, br, 4H), 1.05-1.30 (s, br, 64H), 0.87 (s, br, 12H). GPC: M _n = 47.8 K Da, M _w = 264.4 K Da, PDI = 5.53. Elemental analysis (calc. C, 75.26; H, 8. <RTI ID=0.0>;</RTI></RTI></RTI></RTI></RTI><RTIgt;

Example 1D. Preparation of poly{[N,N'-bis(1-methylhexyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5'-( 2,2'-bithiophene)}[P(NDI1MH-T2)]

Preparation of N,N' -bis(1-methylhexyl)-2,6-dibromonaphthalene-1,4,5,8-bis(dimethylimineimine) (NDI1MH-Br ₂ ). Under an argon atmosphere, NDA-Br ₂ (Example 1A, 2.42 g, 5.68 mmol), 1-methylhexylamine (2.5 mL, 16.55 mmol), propionic acid (12 mL) and o-xylene were stirred at 140 °C. A mixture of 36 mL) was used for 17 hours. After cooling to room temperature, the solvent was removed in vacuo, and the residue was subjected to hexane column chromatography eluting with CHCl ₃ : hexane (1:1, v/v) as a solvent. 0.24 g, 0.39 mmol, yield 6.9%).

¹ H NMR (CDCl ₃ , 500 MHz): δ 8.96 (s, 2H), 5.24 (m, 2H), 2.13 (m, 2H), 1.94 (m, 2H), 1.56 (d, J = 7.0 Hz, 6H) ), 1.10 - 1.40 (m, 12H), 0.81 - 0.86 (t, J = 7.0 Hz, 6H). ¹³ C NMR (CDCl ₃ , 125 MHz): δ: 161.3, 161.3, 139.3, 128.3, 127.8, 125.7, 124.5, 51.5, 33.5, 31.8, 26.9, 22.7, 18.3, 14.2.

The copolymer P (NDI1MH-T2) was prepared. Stirring NDI1MH-Br ₂ (above, 151 mg, 0.24 mmol), 5,5'-bis(trimethylstannyl)-2,2'-bithiophene (120 mg) at 90 ° C under argon , 0.24 mmol) and a mixture of Pd(PPh ₃ ) ₂ Cl ₂ (6.5 mg, 0.009 mmol) in anhydrous toluene (12 mL). Bromobenzene (0.2 mL) was then added and the reaction mixture was maintained at 90 °C for an additional 12 hours. After cooling to room temperature, the reaction mixture was slowly added to methanol (50 mL) and the mixture was stirred at room temperature for 10 min. The precipitate was collected by filtration and washed with methanol. The separated solid was then dissolved in chloroform (30 mL) and sonicated for 5 min. A solution of potassium fluoride (4 g) in water (8 mL) was added and the mixture was stirred vigorously at room temperature for one hour. The mixture was then diluted with chloroform (100 mL) and washed with water (100 mL×2). The organic layer was concentrated on a rotary evaporator. The residue was dissolved in chloroform (30 mL) and then sonicated for 5 min. The mixture was precipitated from EtOAc (EtOAc) (EtOAc)EtOAc. Further purification involves soxler extraction with acetone followed by precipitation in methanol.

¹ H NMR (CDCl ₃ , 500 MHz): δ 8.70-8.82 (br, 2H), 7.05-7.73 (m, br, 3H), 6.64 (br, 1H), 5.15-5.50 (m, br, 2H), 0.71-2.43 (m, br, 28H).

Example 1E. Preparation of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5 '''-(tetrathiophene)}[P(NDI2OD-T4)]

Preparation of N,N'-bis(2-octyldodecyl)-2,6-bis(2-thienyl)naphthalene-1,4,5,8-bis(dimethylimine) (NDI2OD- T1). Stirring NDI2OD-Br ₂ (Example 1A, 280.0 mg, 0.28 mmol), 2-trimethylstannylthiophene (400.0 mg, 1.62 mmol), Pd(PPh ₃ ) ₂ Cl ₂ at 90 ° C under argon (28.0 mg, 0.04 mmol) in EtOAc (20 mL)EtOAc After cooling to room temperature, diluted with chloroform (100 mL) and the reaction mixture was washed with water (80 mL × 2) The resultant mixture was washed, dried over anhydrous sodium sulfate (Na ₂ SO _4), and concentrated on a rotary evaporator. The residue was subjected to EtOAc EtOAc EtOAc (EtOAc)

¹ H NMR (CDCl ₃ 500 MHz): δ: 8.77 (s, 2H), 7.57 (d, J = 5.0 Hz, 2H), 7.31 (d, J = 3.5 Hz, 2H), 7.21 (m, 2H), 4.07 (d, J = 7.5 Hz, 4H), 1.95 (m, 2H), 1.18-40 (m, br, 64H), 0.84-0.88 (m, 12H); ¹³ C NMR (CDCl ₃ 125 MHz): δ :162.8,162.6,141.1,140.4,136.8,128.4,128.2,127.7,127.6,125.6,123.6,45.0,36.6,32.1,31.7,30.3,29.9,29.8,29.7,29.6,29.5,26.6,22.9,14.4,14.3 .

Preparation of N,N'-bis(2-octyldodecyl)-2,6-bis(5-bromo-2-thienyl)naphthalene-1,4,5,8-bis(dimethylimine) ) (NDI2OD-BrT1). The mixture of NDI2OD-T1 (200.0 mg, 0.20 mmol) and NBS (125.0 mg, 0.70 mmol) in DMF (20 mL) was stirred for 25 hr. After cooling to room temperature, the reaction mixture was poured into water (100 mL), and the mixture was extracted with chloroform (100 mL). The organic layer was separated, washed with water (100 mL × 2), dried over anhydrous Na ₂ SO ₄ dried and concentrated on a rotary evaporator. The residue was chromatographed eluting with chloroform:hexane (2:3 v/v, slowly 1:1) as a solvent to give a red solid as product (145.0 mg, 0.13 mmol, 62.5%) .

¹ H NMR (CDCl ₃ , 500 MHz): δ: 8.73 (s, 2H), 7.15 (d, J = 4.0 Hz, 2H), 7.09 (d, J = 4.0, 2H), 4.08 (d, J = 7.5) Hz, 4H), 1.93-1.98 (m, 2H), 1.20-1.40 (br, m, 64H), 0.83-0.89 (m, 12H). Elemental analysis (calc. C, 64.79; H, 7.72; N, 2.44): C, 64.50; H, 7.74; N, 2.49.

The copolymer P (NDI2OD-T4) was prepared. Stirring NDI2OD-BrT1 (92.1 mg, 0.08 mmol), 5,5'-bis(trimethylstannyl)-2,2'-bithiophene (39.4 mg, 0.08 mmol) at 90 ° C under argon in anhydrous toluene and the mixture (5 mL) of the _{Pd (PPh 3) 2 Cl 2} (2.8 mg, 0.004 mmol) 4 days. Bromobenzene (0.3 mL) was then added and the resulting mixture was stirred for additional 12 hours. After cooling to room temperature, a solution of potassium fluoride (1 g) in water (2 mL) was added. The mixture was stirred at room temperature and shaken for 1 hour, then diluted with chloroform (150 mL). Washed with water (100 mL × 3) the resulting mixture was washed, dried over anhydrous Na ₂ SO ₄ and concentrated on a rotary evaporator. The residue was dissolved in chloroform (30 mL) andEtOAc This procedure was repeated using chloroform and acetone to give a dark blue solid as crude. This crude product was purified by Soxhlet extraction with acetone for 48 hours. The separated solid was dissolved in chloroform (50 mL) and then heated to boiling. After cooling to room temperature, the chloroform solution was passed through a syringe filter (5 μm), and the filtrate was precipitated from methanol (50 mL). The precipitate was collected by filtration, washed with methanol and dried in vacuo to give a dark blue solid (87.0 mg, 94.1%).

¹ H NMR (CDCl ₂ CDCl ₂ , 500 MHz): δ: 8.70-8.81 (m, br, 2H), 7.10-7.40 (m, br, 8H), 4.10 (br, 4H), 1.99 (s, br, 2H), 1.10 - 1.45 (m, br, 64H), 0.86 (m, br, 12H). GPC: M _n = 67.4 K Da, M _w = 170.3 K Da, PDI = 2.5. Elemental analysis (calc. C, 72.87; H, 8.04; N, 2.43): Found: C, 72.69; H, 8.06; N, 2.47.

Example 1F. Preparation of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5 '-(2,2'-bithiazole)}[P(NDI2OD-TZ2)]

The copolymer P (NDI2OD-TZ2) was prepared. Stir NDI2OD-Br ₂ (Example 1A, 235 mg, 0.239 mmol), 5,5'-bis(trimethylstannyl)-2,2'-bithiazole (118 mg) at 90 ° C under argon , 0.239 mmol) and a mixture of Pd(PPh ₃ ) ₂ Cl ₂ (7.0 mg, 0.010 mmol) in anhydrous toluene (12 mL) for 3 days. Bromobenzene (0.3 mL) was then added and the resulting mixture was stirred for additional 12 hours. After cooling to room temperature, a solution of potassium fluoride (2 g) in water (4 mL) was added. The mixture was stirred at room temperature and shaken for 1 hour, then diluted with chloroform (150 mL). Washed with water (100 mL × 3) the resulting mixture was washed, dried over anhydrous Na ₂ SO ₄ and concentrated on a rotary evaporator. The residue was dissolved in chloroform (50 mL) andEtOAc This procedure was repeated using chloroform and acetone to give a dark red solid as crude. This crude product was purified by Soxler extraction with acetone for 72 hours. The isolated solid was dissolved in chloroform (80 mL) and then heated to boiling. After cooling to room temperature, the chloroform solution was passed through a syringe filter (5 μm), and the filtrate was precipitated from methanol (80 mL). The precipitate was collected by filtration, washed with methanol and dried in vacuo to give a dark red solid (222 mg, 93.7%).

¹ H NMR (CDCl ₃ , 500 MHz): δ: 7.71 (m, br, 2H), 7.54 (m, br, 2H), 4.20 - 4.25 (m, br, 4H), 1.69 (m, br, 2H) , 1.15 - 1.50 (m, br, 64H) 0.80 - 0.95 (m, br, 12H). Elemental analysis (calc. C, 72.68; H, 8.74; N, 5.65).

Example 1G. Preparation of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5 -(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)}[P(NDI2OD-TBT)]

A copolymer P (NDI2OD-TBT) (Suzuki Coupling Reaction) was prepared. N,N' -bis(2-octyldodecyl)-2,6-bis(5'-bromo-2'-thienyl)naphthalene-1,4 was stirred at 100 ° C under argon. 5,8-bis(dimethylimine imine) (NDI2OD-BrT1) (Example 1E, 85.0 mg, 0.074 mmol), 4,7-bis (4,4,5,5-tetramethyl-1,3, 2-diboron -2-yl)-2,1,3-benzothiadiazole (28.7 mg, 0.074 mmol), potassium carbonate (81.0 mg, 0.586 mmol) and Pd(PPh ₃ ) ₄ (1.8 mg, 0.002 mmol) in anhydrous A mixture of toluene (4 mL) and DMF (2 mL) was taken for 3 days. Bromobenzene (0.3 mL) was then added and the resulting mixture was stirred for additional 12 hours. After cooling to room temperature, the reaction mixture was poured into methanol (200 mL) and the mixture was stirred at room temperature for 15 min. The precipitate was collected by filtration, washed with methanol and dried in vacuo to give a dark solid as product (62.0 mg, 74.6%). Elemental analysis (calc. C, 72.68; H, 8. 7.; N, 4.49): C, 72.41; H, 7.90; N, 5.00.

Copolymer P (NDI 2 OD-TBT) (Stille Coupling Reaction) was prepared. Stirring NDI ₂ OD-Br ₂ (Example 1A, 84.3 mg, 0.086 mmol), 5,5'-bis(trimethylstannyl)-4',7'-di-2- at 90 ° C under argon Thienyl)-2',1',3'-benzothiadiazole (53.6 mg, 0.086 mmol) and Pd(PPh ₃ ) ₂ Cl ₂ (2.5 mg, 0.004 mmol) in anhydrous toluene (6.5 mL) The mixture was 3 days. Bromobenzene (0.3 mL) was then added and the resulting mixture was stirred for additional 12 hours. After cooling to room temperature, a solution of potassium fluoride (1 g) in water (2 mL) was added. The mixture was stirred at room temperature and shaken for 1 hour, then diluted with chloroform (150 mL). Washed with water (100 mL × 3) the resulting mixture was washed, dried over anhydrous Na ₂ SO ₄ and concentrated on a rotary evaporator. The residue was dissolved in chloroform (50 mL) andEtOAc This procedure was repeated using chloroform and acetone to give a dark solid (58.0 mg, 60.3%).

Example 1H. Preparation of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5 -(1',4'-di-2-thienyl-2',3',5',6'-tetrafluorobenzene)}[P(NDI2OD-TFBT)]

Copolymer P (NDI2OD-TFBT) was prepared. Stirring NDI2OD-BrT1 (Example 1E, 94.3 mg, 0.082 mmol), 1,4-bis(trimethylstannyl)-2,3,5,6-tetrafluorobenzene under argon at 90 °C A mixture of 39.0 mg, 0.082 mmol) and Pd(PPh ₃ ) ₂ Cl ₂ (1.8 mg, 0.003 mmol) in anhydrous toluene (6 mL) Bromobenzene (0.3 mL) was then added and the reaction mixture was maintained at 90 °C for an additional 12 hours. After cooling to room temperature, a solution of potassium fluoride (1 g) in water (2 mL) was added. The mixture was stirred at room temperature and shaken for 1 hour, then diluted with chloroform (150 mL). Washed with water (100 mL × 3) the resulting mixture was washed, dried over anhydrous Na ₂ SO ₄ and concentrated on a rotary evaporator. The residue was dissolved in chloroform (20 mL). The precipitate was collected by filtration, washed with methanol and dried in vacuo to give a purple/blue solid as product (134 mg, yield 94.4%).

¹ H NMR (CDCl ₃ , 500 MHz): δ: 8.72 - 8.75 (m, 2H), 7.14 - 7.16 (m, 2H), 7.09-7.11 (m, 2H), 4.08 (m, 4H), 1.96 (s) , br, 2H), 1.15 - 1.45 (m, br, 64H) 0.80 - 0.92 (m, br, 12H). Elemental analysis (calc. C, 71.80; H, 7.80; N, 2.48).

Example 1I. Preparation of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5 '-(1,2-bis(2'-thienyl)vinyl)}[P(NDI2OD-TVT)]

A copolymer P (NDI2OD-TVT) was prepared. Stirring NDI2OD-Br ₂ (86.5 mg, 0.088 mmol), 5,5'-bis(trimethylstannyl)-(1,2-bis(2'-thienyl) at 90 ° C under argon a mixture of vinyl (45.5 mg, 0.088 mmol) and Pd(PPh ₃ ) ₂ Cl ₂ (3.1 mg, 0.004 mmol) in anhydrous toluene (7 mL) for 3 days, followed by the addition of bromobenzene (0.3 mL) and stirring The mixture was allowed to stand for 12 hours. After cooling to room temperature, a solution of potassium fluoride (1.5 g) in water (3 mL) was added, and the mixture was stirred at room temperature and the mixture was shaken for 1 hour, then diluted with chloroform (150 mL). (80 mL × 3) the resulting mixture was washed, ₂ SO ₄ dried and concentrated on a rotary evaporator. the residue was dissolved in chloroform (50 mL) and methanol (100 mL) of Na over anhydrous precipitated. the precipitate was collected by filtration This was re-dissolved in chloroform (50 mL). The chloroform solution was re-precipitated from acetone (100 mL) to give a dark blue solid as crude product. The separated solid was dissolved in chloroform (60 mL) and then heated to boiling. After cooling to room temperature, the chloroform solution was passed through a syringe filter (5 μm) and the filtrate was allowed to dissolve in methanol (60 mL) The precipitate was collected by filtration, washed with methanol and dried in vacuo to give a blue solid (84.0 mg, 94.2%).

¹ H NMR (CDCl ₂ CDCl ₂ , 500 MHz): δ: 8.79 (br, 2H), 7.33 (br, 2H), 7.20 (br, 4H), 4.10 (br, 4H), 2.00 (br, 2H), 1.20-1.60 (br, 64H), 0.80-91 (br, 12H). GPC: M _n = 185.6 K Da, M _w = 713.0 K Da, PDI = 3.8. Elemental analysis (calc. C, 75.69; H, 8.93; N, 2.76):

Example 1K. Preparation of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5 '-[2,6-bis(2'-thienyl)naphthalene]}[P(NDI2OD-TNT)]

A copolymer P (NDI2OD-TNT) was prepared. Stirring N,N' -bis(2-octyldodecyl)-2,6-bis(2'-(5'-bromothienyl))naphthalene-1,4 at 90 ° C under argon ,5,8-bis(dimethylimine) (39.1 mg, 0.034 mmol), 2,6-bis(trimethylstannyl)naphthalene (15.4 mg, 0.034 mmol) and Pd(PPh ₃ ) ₂ Cl A mixture of ₂ (1.2 mg, 0.002 mmol) in anhydrous toluene (4 mL). Bromobenzene (0.3 mL) was then added and the reaction mixture was maintained at 90 °C for an additional 12 hours. After cooling to room temperature, a solution of potassium fluoride (1 g) in water (2 mL) was added. The mixture was stirred at room temperature and shaken for 1 hour, then diluted with chloroform (100 mL). Washed with water (80 mL × 3) the resulting mixture was washed, dried over anhydrous Na ₂ SO ₄ and concentrated on a rotary evaporator. The residue was taken up in EtOAc (5 mL) The precipitate was collected by filtration, washed with methanol and dried in vacuo to give a blue solid, which was further purified by EtOAc. The separated solid residue was redissolved in THF (2 mL) and the resulting solution was applied to a syringe filter (5 m). The filtrate was precipitated in methanol (70 mL). The precipitate was collected by filtration, washed with methanol and dried in vacuo to give a dark blue solid as product (33.2 mg, yield 87.5%).

¹ H NMR (CDCl ₂ CDCl ₂ , 500 MHz): δ: 8.80-8.90 (m, br, 2H), 6.83-8.20 (m, br, 10H), 4.11 (s, br, 4H), 2.02 (br, 2H), 1.10- 1.50 (br, 64H) 0.76-0.92 (br, 12H). Elemental analysis (calc. C, 77.51; H, 8.49; N, 2.51): C, 76.89; H, 8.65; N, 2.16.

Example 1L. Preparation of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alternative-5,5 '-(1,1'-Dimethyl-2,2'-bipyrrole)}[P(NDI2OD-Py2)]

Preparation of N,N'-bis(2-octyldodecyl)-2,6-bis(1-methyl-1H-pyrrol-2-yl)naphthalene-1,4,5,8-bis (two Formamidine (NDI2OD-Py). Stirring NDI2OD-Br ₂ (489.7 mg, 0.50 mmol), 1-methyl-2-trimethylstannylpyrrole (736.1 mg, 1.99 mmol), Pd(PPh ₃ ) ₂ at 90 ° C under argon _{cl 2 (35.0 mg, 0.050 mmol} ) in anhydrous toluene mixture 48 hours (35 mL) in the. After cooling to room temperature, the reaction mixture was poured into water (100 mL), and the mixture was extracted with chloroform (100 mL×2). The organic layers were washed with water (100 mL × 2), dried over anhydrous sodium sulfate (Na ₂ SO ₄₎ dried and concentrated on a rotary evaporator. The residue was chromatographed eluted with EtOAc EtOAc (EtOAc:EtOAc)

¹ H NMR (CDCl ₃ 500 MHz): δ: 8.77 (s, 2H), 6.91 (m, 2H), 6.38 (m, 4H), 4.08 (d, J = 7.0 Hz, 4H), 3.41 (s, 6H) ), 1.98 (m, 2H), 1.16-1.40 (m, br, 64H), 0.83-0.90 (m, 12H); ¹³ C NMR (CDCl ₃ 125 MHz): δ: 163.1, 162.6, 137.7, 137.4, 132.3 , 127.4, 125.5, 125.0, 123.2, 110.7, 109.1, 45.2, 36.6, 34.6, 32.1, 31.7, 30.3, 29.9, 29.8, 29.7, 29.6, 29.5, 26.6, 22.9, 14.3.

The copolymer P (NDI2OD-Py2) was prepared. Under argon, the NDI2OD-Py (70.0 mg, 0.071 mmol) in dry chlorobenzene (3.5 mL) in added dropwise to a solution of _{FeCl 3 (65 mg, 0.40 mmol} ) in chlorobenzene (2.5 mL) and suspended in In the liquid. The resulting mixture was allowed to warm to 65 ° C and maintained at this temperature for 48 hours. After cooling to room temperature, chlorobenzene (10 mL) was added to the reaction mixture, which was then precipitated from methanol (100 mL). The mixture was sonicated for 10 min and filtered to abr. EtOAc (EtOAc).

Example 2: Characterizing a polymer

With a plurality of dissolution - precipitation procedure was purified P (NDI2OD-T2) and by elemental analysis, GPC measurement (M _w = about 265 k, PD = 5.5) and ¹ H NMR fully characterized spectroscopy. The solubility of this polymer in conventional organic solvents such as xylene, dichlorobenzene (DCB), CHCl ₃ and other chlorinated hydrocarbons (CHC) was found to be as high as 60 g/L. The differential scanning calorimetry (DSC) of P(NDI2OD-T2) exhibits no thermal transition up to about 300 °C.

To study the redox characteristics of the new polymer, THF-(NBu) ₄ PF ₆ solvent-electrolyte solution was used, Pt was used as the working electrode, silver was used as the pseudo reference electrode and ferrocene (0.54 V vs. SCE) was used as the internal standard. P(NDI2OD-T2), P(NDI1MH-T2), P(NDI2EH-T2), P(NDI2EH-T1), P(NDI1MH-T2), P(NDI2OD-TZ2), and P(NDI2OD-T4) are cycled Voltammetry experiment. The Pt working electrode was coated with a polymer film by dropping a CHCl ₃ solution. Cyclic voltammetry and exemplary redox potential data are given in WO 2009/098253 A1 (see Figures 1 to 3 and Tables 1a and 1b of WO 2009/098253 A1).

Two semi-reversible reductions were observed for all polymers, but no oxidation was observed, indicating that all polymers are essentially n-doped. Analysis of the half-wave potential reveals the importance of the naphthyl imine functionalization of the polymer backbone in regulating the reduction characteristics, and thus the LUMO energy. The first and second reduction potentials of such polymers are independent of the N-alkyl functionalization and comonomer type, and are located at about 0.5 V and about 1 V, respectively. These values are the lowest values recorded for the semiconducting polymer and are close to, for example, the value of the electron-consuming core cyanide. These values also confirm the stability of the corresponding transistor under ambient conditions.

With regard to the optical absorption spectrum of the film polymer of the polymer and possible device configurations (except for at least one intermediate layer and its preparation) and for device characterization including the measurement of charge carrier mobility, reference is made to WO 2009/098253 A1.

110‧‧‧Organic semiconductor devices

112‧‧‧Substrate

114‧‧‧Electrode

116‧‧‧ source electrode

118‧‧‧汲 electrode

120‧‧‧Intermediate

122‧‧‧Organic semiconductor materials

124‧‧‧Insulation

126‧‧ ‧ gate electrode

128‧‧‧Organic film transistor

No sample 210‧‧‧ I _SD intermediate layer

212‧‧‧ I _SD sample having ABT intermediate layer

214‧‧‧ I _SD sample having an intermediate layer of MBT

221‧‧‧ Gate leakage current without sample in the middle layer

218‧‧‧ Gate leakage current with samples of ABT interlayer

220‧‧‧gate leakage current of samples with MBT interlayer

No sample 222‧‧‧ I _SD intermediate layer

224‧‧‧ I _SD sample having ABT intermediate layer

226‧‧‧ I _SD samples having intermediate layers PFBT

1 discloses a basic layer configuration of a preferred embodiment of the organic semiconductor device of the present invention; 2 and 3 depict source-drain current measurements of various organic semiconductor devices as a function of gate voltage; and FIGS. 4A-4D depict capacitance measurements of various organic semiconductor devices.

110‧‧‧Organic semiconductor devices

112‧‧‧Substrate

114‧‧‧Electrode

116‧‧‧ source electrode

118‧‧‧汲 electrode

120‧‧‧Intermediate

122‧‧‧Organic semiconductor materials

124‧‧‧Insulation

126‧‧ ‧ gate electrode

128‧‧‧Organic film transistor

Claims (16)

A method for preparing an organic semiconductor device (110) having at least one organic semiconductor material (122) and at least two suitable for supporting charge carrier transport through the organic semiconductor material (122) An electrode (114), wherein the organic semiconductor material (122) has bipolar semiconductor properties in nature, wherein the method includes at least one step of producing at least one intermediate layer (120), the at least one intermediate layer (120) being at least partially interposed Between the organic semiconductor material (122) of the organic semiconductor device (110) and at least one of the electrodes (114), wherein the intermediate layer (120) comprises at least one thiol compound of the formula HS-R, wherein R is An organic residue, wherein the thiol compound has an electric dipole moment directed away from the SH group of the thiol compound, the electric dipole moment having at least the same magnitude as the electric dipole moment of the 4-phenylthiophenol, wherein The intermediate layer (120) inhibits bipolar charge carrier transport between the electrodes (114) to facilitate unipolar charge carrier transport. The method of claim 2, wherein the bipolar charge carrier transport is inhibited to facilitate negative charge carrier transport. The method of any one of the preceding claims, wherein R is selected from the group consisting of alkyl, wherein the alkyl group is a linear, cyclic or branched chain and may comprise from 1 to 20 carbon atoms, more preferably 10 to 20 carbon atoms, preferably decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and cyclohexyl ; benzyl, phenyl; An alkylphenyl group, wherein the alkyl group of the phenyl group may contain 1 to 20 carbon atoms, which is a linear, cyclic or branched chain and is preferably located at the 2-position or 4 of the thiol group. a position such as 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,6-di Methylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,3,4-trimethylphenyl, 2,4,5-trimethylphenyl, 2 ,4,6-trimethylphenyl, 2,3,5,6-tetramethylphenyl, 2,3,4,6-tetramethylphenyl or 2,3,4,5-tetramethyl Phenyl, 2,3,4,5,6-pentamethylphenyl, n-butylphenyl (preferably 2-n-butylphenyl, 4-n-butylphenyl), tert-butylbenzene , pentylphenyl, hexylphenyl, cyclohexylphenyl, heptylphenyl, octylphenyl, ethylhexylphenyl, and more preferably 4-methylphenyl or 4-butylphenyl; Alkoxyphenyl, preferably methoxyphenyl, more preferably 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl; dimethoxyphenyl, preferably Is 2,3-dimethoxyphenyl, 2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl, 3,4-dimethoxyphenyl or 3,5-di Methoxy Phenyl; trimethoxyphenyl, preferably 2,3,4-trimethoxyphenyl, 2,4,5-trimethoxyphenyl or 2,4,6-trimethoxyphenyl, 2, 3,5,6-tetramethoxyphenyl, 2,3,4,6-tetramethoxyphenyl or 2,3,4,5-tetramethoxyphenyl, 2,3,4,5 , 6-pentamethoxyphenyl; alkylthiophenyl, preferably methylthiophenyl, more preferably 2-methylthiophenyl, 3-methylthiophenyl or 4-methylthiobenzene Base, benzylphenyl, arylphenyl, preferably 4-phenylphenyl, 2-thionaphthyl, 4-(dimethylamino)phenyl; heteroaryl, preferably 2-thienyl . The method of claim 1 or 2, wherein the thiol compound is selected from the group consisting of 1-indole thiol; 4-methylthiophenol; 4-(methylthio)thiophenol; 3,4-di Methoxythiophenol; 4-butylthiophenol; 4-phenylthiophenol; 2-naphthylthiophenol; 4-(dimethylamino)thiophenol; benzyl mercaptan; 2,3,4,5,6 - pentamethylbenzene-1-thiol. The method of claim 1 or 2, wherein the thiol compound forms at least one self-assembled monolayer. The method of claim 1 or 2, the method further comprising the step of providing at least one gate electrode (126), wherein the gate electrode (126) is adapted to affect charge carriers between the electrodes (114) by an electric field transmission. The method of claim 1 or 2, wherein the electrodes (114) comprise a material selected from the group consisting of silver and gold. The method of claim 1 or 2, wherein the organic semiconductor material (122) comprises at least one semiconducting polymer. The method of claim 1 or 2, wherein the organic semiconductor material (122) is selected from the group consisting of polymers of the formula Wherein: M ₁ is a naphthyl imine substituted according to the following conditions: R ¹ at each occurrence are independently selected H, C _1-40 alkyl, C _2-40 alkenyl, C _1-40 haloalkyl group, and 1-4 cyclic moieties, wherein: the C _{1- The 40} alkyl group, the C _2-40 alkenyl group and the C _1-40 haloalkyl group may each optionally be substituted with 1 to 10 substituents independently selected from the group consisting of halogen, -CN, NO ₂ , OH, -NH. ₂ , -NH(C _1-20 alkyl), -N(C _1-20 alkyl) ₂ , -S(O) ₂ OH, -CHO, -C(O)-C _1-20 alkyl, - C(O)OH, -C(O)-OC _1-20 alkyl, -C(O)NH ₂ , -C(O)NH-C _1-20 alkyl, -C(O)N (C _{1 -20} alkyl) ₂ , -OC _1-20 alkyl, -SiH ₃ , -SiH(C _1-20 alkyl) ₂ , -SiH ₂ (C _1-20 alkyl) and -Si (C _1-20 Alkyl) ₃ ; the C _1-40 alkyl group, the C _2-40 alkenyl group, and the C _1-40 haloalkyl group may each be covalently bonded to the quinone imine nitrogen atom via an optionally present linking moiety; The 1 to 4 cyclic moieties may each be the same or different and may be covalently bonded to each other or covalently bonded to the quinone imine nitrogen via an optionally present linking moiety, and may optionally be selected from 1 to 5 independently from 1 to 5 The following substituents are substituted: halogen, oxo (oxo), -CN, NO ₂ , OH, =C(CN) ₂ , -NH ₂ , -NH(C _1-20 alkyl), -N (C _{1 -20} alkyl) ₂ , -S(O) ₂ OH, -CHO, -C(O)OH, -C(O)-C _1-20 alkyl, -C(O)-OC _1-20 alkyl, -C(O NH ₂ , -C(O)NH-C _1-20 alkyl, -C(O)N(C _1-20 alkyl) ₂ , -SiH ₃ , -SiH(C _1-20 alkyl) ₂ , -SiH ₂ (C _1-20 alkyl), -Si(C _1-20 alkyl) ₃ , -OC _1-20 alkyl, -OC _1-20 alkenyl, -OC _1-20 haloalkyl, C _1-20 alkyl, C _1-20 alkenyl and C _1-20 haloalkyl; M ₂ is a repeating unit comprising one or more monocyclic moieties; and n is an integer between 2 and 5,000, wherein M ₂ Selected from: Wherein: π-2 is a polycyclic moiety substituted by 1 to 6 R ^e groups as the case may be; Ar is independently 5 or 6 members of aryl or heteroaryl at each occurrence, wherein each of these groups Substituted by 1 to 6 R ^e groups; wherein each occurrence of R ^e is independently a) halogen, b)-CN, c)-NO ₂ , d) pendant oxy, e)-OH, f) = C(R ^f ) ₂ , g) C _1-40 alkyl, h) C _2-40 alkenyl, i) C _2-40 alkynyl, j) C _1-40 alkoxy, k) C _1-40 alkylthio, l) C _1-40 haloalkyl, m)-YC _3-10 cycloalkyl, n)-YC _6-14 aryl, o)-YC _6-14 haloaryl, p a Y-3 to 12 membered cycloheteroalkyl group, or a q)-Y-5 to 14 membered heteroaryl group, wherein the C _1-40 alkyl group, the C _2-40 alkenyl group, the C _2-40 alkyne a C _3-10 cycloalkyl group, the C _6-14 aryl group, the C _6-14 haloaryl group, the 3 to 12 membered cycloheteroalkyl group, and the 5 to 14 membered heteroaryl group, as the case may be 1 to 4 R ^f groups are substituted; R ^f is independently a) halogen at each occurrence, b)-CN, c)-NO ₂ , d) pendant oxy, e)-OH, f)-NH ₂ , g)-NH(C _1-20 alkyl), h)-N(C _1-20 alkyl) ₂ ,i)-N(C _1-20 alkyl)-C _6-14 aryl,j )-N(C _6-14 aryl) ₂ ,k)-S(O) _w H,l)-S(O) _w -C _1-20 alkyl,m)-S(O) ₂ OH,n )-S( O) _w -OC _1-20 alkyl, o)-S(O) _w -OC _6-14 aryl, p)-CHO, q)-C(O)-C _1-20 alkyl, r)- C(O)-C _6-14 aryl, s)-C(O)OH, t)-C(O)-OC _1-20 alkyl, u)-C(O)-OC _6-14 aryl , v)-C(O)NH ₂ , w)-C(O)NH-C _1-20 alkyl, x)-C(O)N(C _1-20 alkyl) ₂ ,y)-C( O) NH-C _6-14 aryl, z)-C(O)N(C _1-20 alkyl)-C _6-14 aryl, aa)-C(O)N(C _6-14 aryl ₂ , ab)-C(S)NH ₂ , ac)-C(S)NH-C _1-20 alkyl, ad)-C(S)N(C _1-20 alkyl) ₂ , ae)- C(S)N(C _6-14 aryl) ₂ , af)-C(S)N(C _1-20 alkyl)-C _6-14 aryl, ag)-C(S)NH-C _{6 -14} aryl, ah)-S(O) _w NH ₂ , ai)-S(O) _w NH(C _1-20 alkyl), aj)-S(O) _w N (C _1-20 alkyl) ₂ , ak)-S(O) _w NH(C _6-14 aryl),al)-S(O) _w N(C _1-20 alkyl)-C _6-14 aryl, am)-S (O) _w N(C _6-14 aryl) ₂ , an)-SiH ₃ , ao)-SiH(C _1-20 alkyl) ₂ , ap)-SiH ₂ (C _1-20 alkyl), aq -Si(C _1-20 alkyl) ₃ ,ar)C _1-20 alkyl, as) C _2-20 alkenyl, at) C _2-20 alkynyl, au) C _1-20 alkoxy, Av) C _1-20 alkylthio, aw) C _1-20 haloalkyl, ax) C _3-10 cycloalkyl, ay) C _6-14 aryl, az) C _6-14 haloaryl, ba a 3 to 12 membered cycloheteroalkyl group, or bb) 5 to 14 membered heteroaryl; Y Each occurrence is independently selected from the group consisting of a divalent C _1-6 alkyl group, a divalent C _1-6 haloalkyl group, and a covalent bond; and w is 0, 1 or 2; Z is a conjugated linear linking moiety; And m, m' and m" are independently 1, 2, 3 or 4. The method of claim 9, wherein the organic semiconductor material (122) is selected from the group consisting of polymers of the formula Wherein M ₁ is selected from: Wherein R ¹ is 2-octyldodecyl; and M ₂ is a polymer of the formula: Wherein m is selected from the range of 2 to 50, preferably 2 to 20 repeating units, or 2 to 10. The method of claim 1 or 2, wherein the intermediate layer (120) is produced by processing from a solution comprising at least one solvent and the thiol compound. The method of claim 11, wherein the processing from the solution comprises at least one of the step of applying the solution to at least one of the electrodes (114) and removing the solvent. An organic semiconductor device (110) having at least one organic semiconductor material (122) and at least two electrodes (114) adapted to support charge carrier transport through the organic semiconductor material (122), wherein the organic semiconductor material ( 122) essentially having bipolar semiconductor characteristics, wherein at least one intermediate layer (120) is at least partially interposed in the organic semiconductor device (110) Between the semiconductor material (122) and at least one of the electrodes (114), wherein the intermediate layer (120) comprises at least one thiol compound of the formula HS-R, wherein R is an organic residue, wherein the thiol compound has An electric dipole moment pointing away from the SH group of the thiol compound, the electric dipole moment having at least the same magnitude as the electric dipole moment of the 4-phenylthiophenol, wherein the intermediate layer (120) inhibits the electrodes Bipolar charge carrier transport between (114) to facilitate unipolar charge carrier transport. The organic semiconductor device (110) of claim 13, wherein the organic semiconductor device (110) is prepared by the method of any one of the preceding claims. The organic semiconductor device (110) of claim 13 or 14, wherein the organic semiconductor device (110) comprises a channel for charge carrier transport between the electrodes (114), the channel length of the channel being 1 μm Up to 500 μm and preferably 5 μm to 200 μm. Use of an intermediate layer (120) comprising at least one thiol compound that inhibits bipolar charge carrier transport in an organic semiconductor device (110) to facilitate unipolar charge carrier transport, The organic semiconductor device (110) has at least one organic semiconductor material (122) and at least two electrodes (114) adapted to support the transport of charge carriers through the organic semiconductor material (122), the intermediate layer (120) being at least partially inserted Between at least one of the electrodes (114) and the organic semiconductor material (122), wherein the intermediate layer (120) comprises at least one thiol compound of the formula HS-R, wherein R is an organic residue, wherein the sulfur The alcohol compound has an electric dipole moment directed away from the SH group of the thiol compound, the electric dipole moment and 4-phenylthiophenol The electric dipole moments have at least the same magnitude, wherein the intermediate layer (120) inhibits bipolar charge carrier transport between the electrodes (114) to facilitate unipolar charge carrier transport.