Organic semiconducting layer formulations comprising polyacenes and organic binder polymers

The present invention<u style="single">Formulations for organic semiconductor layers</u>Take<u style="single">Prescription</u>Layers, take<u style="single">Prescription</u>And layers and take<u style="single">Prescription</u>The present invention relates to a method for manufacturing an electronic device (including organic field effect transistors (OFETs)) including.

In recent years, organic semiconductor materials have been developed for the production of more versatile and low-cost electronic devices. Such materials include a wide range of devices or devices, including organic field effect transistors (OFETs), organic light emitting diodes (OLEDs), photodetectors, photovoltaics (PV), sensors, memory devices and logic circuits, to name a few. Uses in the range have been found. Organic semiconductor materials are typically present in electronic devices in the form of thin layers, eg, less than 1 micron thick.

Pentacene is promising as an organic semiconductor material. Pentacene has been described as requiring a sophisticated liquid crystal structure to provide molecular orientation that results in good charge mobility. Therefore, in the prior art, in part, pentacene was deposited with a thin film of pentacene because it was somewhat insoluble in normal solvents. However, vapor deposition requires expensive and sophisticated equipment. Considering the latter problem, one approach has been the application of solutions containing pentacene precursors and chemical conversions, such as precursor compounds that are converted to pentacene by heat. However, the latter method is also complicated and difficult to control to obtain the ordered structure required for good charge mobility.

Soluble pentacene compounds have recently been described in the art as organic semiconductor compounds (see, eg, US 2003/0116755 A (Takahashi) and US 6,690,029 (Anthony)). The use of pentacene in FETs has been proposed in WO 03/016599 (Asahi), where a solution of soluble pentacene is laminated on a substrate and the solvent evaporates to form a thin film of pentacene. However, soluble pentacene is described in US 6,690,029 and WO 03/016599, which still requires a high degree of liquid crystal structure in the thin film due to acceptable charge mobility, especially when used in FETs. Means that pentacene still has to be stacked in a controlled manner. Therefore, in the prior art, care should be taken not to dilute pentacene by either method, otherwise the liquid crystal structure of pentacene is said to collapse, which reduces charge mobility.

Improved charge mobility is one goal of new electronic devices. Another goal is improved stability and integrity of the organic semiconductor layer. A potential way to improve the stability and integrity of the organic semiconductor layer in the device would be to include the organic semiconductor component in the organic binder. However, whenever an organic semiconductor component is combined with a binder, the binder is expected to be efficiently "diluted" and reduced in charge mobility. Diluting organic semiconductors, especially by mixing with binders, disrupts the molecular order of the semiconductor layer. For example, diluting the organic semiconductor component in the FET channel predicts the collapse of orbital overlap that reduces mobility between molecules in the immediate vicinity of the gate insulating film (the first few molecular films). , There is a particular problem. Electrons or holes force the undesired path to the majority of organic semiconductors. Some organic semiconductor materials are believed to be more sensitive to use in binders than others. Previously, the inclusion of pentacene in the binder was not desirable because pentacene has been required to have a highly ordered structure for effective charge mobility. WO At 03/030278 (Philips), the use of a binder was attempted, where the amount of binder (although less than 5% of the amount of binder) when mixed with (precursor) pentacene was A slow decrease in FET mobility was seen as it increased. Some low polarity binder resins used in FETs organic semiconductors are described in WO 02/45184 (Avecia). However, a decrease in charge mobility is still expected when the semiconductor is diluted with a binder.

An object of the present invention is to reduce or overcome the above-mentioned drawbacks of the organic semiconductor layer. The first object of the present invention is<u style="single">Formulations for organic semiconductor layers</u>Is to provide a layer<u style="single">Prescription</u>Contains an organic binder having a dielectric constant ε of 3.3 or less at 1,000 Hz and a polyacene compound of formula A:<chemistry num="1"><img file="JP5089986B2_D0001.tif" /></chemistry>

During the ceremony R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, And R₁₂Each of them may be the same or different, independently, hydrogen; optionally substituted C₁~ C₄₀Calvir or hydrocarbyl group; optionally substituted C₁~ C₄₀Alkoxy group; optionally substituted C₆~ C₄₀Aryloxy group of; optionally substituted C₇~ C₄₀Alkylaryloxy group of; optionally substituted C₂~ C₄₀Alkoxycarbonyl group of; optionally substituted C₇~ C₄₀Aryloxycarbonyl group; Cyan group (-CN); Carbamoyl group (-C (= O) NH₂); Haloformyl group (-C (= O) -X, where X represents a halogen atom in the formula); Formyl group (-C (= O) -H); Isocyano group; Isocyanate group; Thiosianate group or thio Isocyanate group; optionally substituted amino group; hydroxy group; nitro group; CF₃Group; halo group (Cl, Br, F); optionally substituted silyl group; and

In the formula, R₂And R₃And / or R₈And R₉Is C₄~ C₄₀It may be bridged to form a saturated or unsaturated ring of, and the saturated or unsaturated ring is an oxygen atom, a sulfur atom, the formula -N (Ra)-(in the formula, Ra is a hydrogen atom or It may be mediated by a group represented by an optionally substituted hydrocarbon group), or may be optionally substituted; and In the formula, one or more carbon atoms in the polyacene skeleton may be optionally substituted with heteroatoms selected from N, P, As, O, S, Se and Te; and In the formula, independently, any two or three or more substituents R located at the positions of adjacent rings of polyacenes.₁~ R₁₂Are both fused to polyacene, optionally interrupted with O, S or -N (Ra) (Ra is as defined above) and further C₄~ C₄₀May form a saturated or unsaturated ring or aromatic ring system of; and In the formula, n is 0, 1, 2, 3 or 4, preferably n is 0, 1 or 2, most preferably the polyacene compound is a pentacene compound (n = 2) or "pseudo-pentacene". "The compound (n = 0) n is 0 or 2.

More preferably, the pentacene compound is a compound selected from any one of the compound groups 1 to 9 or its isomers. here:<chemistry num="2"><img file="JP5089986B2_D0002.tif" /></chemistry>

<chemistry num="3"><img file="JP5089986B2_D0003.tif" /></chemistry>

<chemistry num="4"><img file="JP5089986B2_D0004.tif" /></chemistry>

And In the formula, in the case of compound group 1, R₆And R₁₃, In the case of compound group 2, R₅And R₁₄, In the case of compound group 3, R₂, R₃, R₉And R₁₀, In the case of compound group 4, R₂And R₃, In the case of compound group 5, R₂, R₃, R₁₁And R₁₂, In the case of compound group 6, R₂And R₉, In the case of compound group 7, R₅, R₇, R₁₂And R₁₄, In the case of compound group 8, R₁, R₂, R₃, R₄, R₈, R₉, R₁₀, R₁₁, R₁₅, R₁₆, R₁₇, And R₁₈, In the case of compound group 9, R₂, R₃, R₇, R₈, R₁₅, R₁₆, R₁₇Can be independently, identical or different, each independently, hydrogen; optionally substituted C₁~ C₄₀Calvir or hydrocarbyl group; optionally substituted C₁~ C₄₀Alkoxy group; optionally substituted C₆~ C₄₀Aryloxy group of; optionally substituted C₇~ C₄₀Alkylaryloxy group of; optionally substituted C₂~ C₄₀Alkoxycarbonyl group of; optionally substituted C₇~ C₄₀Aryloxycarbonyl group; Cyan group (-CN); Carbamoyl group (-C (= O) NH₂); Haloformyl group (-C (= O) -X, where X represents a halogen atom in the formula); Formyl group (-C (= O) -H); Isocyano group; Isocyanate group; Thiosianate group or thio Isocyanate group; optionally substituted amino group; hydroxy group; nitro group; CF₃Group; halo group (Cl, Br, F); or optionally substituted silyl group; and In the formula, R₁And R₂, R₂And R₃, R₃And R₄, R₈And R₉, R₉And R₁₀, R₁₀And R₁₁, R₁₅And R₁₆And R₁₆And R₁₇Is C₄~ C₄₀They may be bridged to each other to form a saturated or unsaturated ring of, and the saturated or unsaturated ring is an oxygen atom, a sulfur atom, the formula -N (Ra)-(in the formula, Ra is a hydrogen atom. Or a group represented by a hydrocarbon group) may be intervening; and In the formula, A is silicon or germanium.

R substituents (R) of compound groups 1-9₁, R₂Etc.) represent the substituent at the position of pentacene in the conventional nomenclature. ::<chemistry num="5"><img file="JP5089986B2_D0005.tif" /></chemistry> Surprisingly and beneficially, certain soluble polyacene compounds, especially pentacene compounds of compounds 1-9 (hereafter referred to as "polyacenes") and organic binder resins (hereafter simply referred to as "binders"). It has been found herein by the present invention that the combination with) causes little or no reduction in the charge mobility of polyacenes or in some cases increases. For example, soluble polyacenes can be dissolved and deposited in binder resins (eg poly (α-methylstyrene)) and have high charge mobilities (eg 0.5-1.5 cm).²V^-1s^-1) Is formed. This is particularly unexpected given that prior art has required strong molecular order in polyacene compounds to achieve such high mobilities. Dilution with binders in FETs is expected to result in at least a large reduction in mobility. Surprisingly, it was found here that the mobility was comparable to that of pure polyacene compounds used alone, even at a 1: 1 ratio of binder: polyacene. Therefore, the results obtained by the present invention are: a) maintain mobility despite the potential disruption of molecular order and b) maintain mobility despite the expected increase in intermolecular distance. It's amazing for both things. At the same time, the semiconductor layer formed thereby has good film forming properties and is particularly stable.

In a preferred embodiment of the present invention, it is used for an organic field effect transistor containing a compound selected from compound groups 1 to 9, more preferably groups 1 to 8; a binder; and optionally a solvent.<u style="single">Formulations for organic semiconductor layers</u>I will provide a. In a particularly preferred embodiment of the present invention, it is used for an organic field effect transistor containing a compound of formula 1; a binder; and a solvent.<u style="single">Formulations for organic semiconductor layers</u>I will provide a.<chemistry num="6"><img file="JP5089986B2_D0006.tif" /></chemistry> Here, the binder is selected from poly (α-methylstyrene), Topas® 8007, poly (4-methylstyrene), polystyrene and polystyrene-co-α-methylstyrene, most preferably poly (poly). (Α-Methylstyrene); Solvents are toluene, ethylcyclohexane, anisole and p-xylene; most preferably toluene.

In a more particularly preferred embodiment of the invention, it is used in an organic field effect transistor containing a compound of formula 2; a binder; and a solvent.<u style="single">Formulations for organic semiconductor layers</u>I will provide a.<chemistry num="7"><img file="JP5089986B2_D0007.tif" /></chemistry> Here, the binder is selected from poly (α-methylstyrene), polyvinyl chloride and poly (4-vinylbiphenyl), most preferably poly (α-methylstyrene); the solvent is 1 , 2-Dichlorobenzene.

In a more particularly preferred embodiment of the invention, it is used in an organic field effect transistor containing a compound of formula 3; a binder; and a solvent.<u style="single">Formulations for organic semiconductor layers</u>I will provide a.<chemistry num="8"><img file="JP5089986B2_D0008.tif" /></chemistry> Where n and m are independently 0, 1, 2, 3 or 4, more preferably 0, 1 or 2; and the binder is poly (α-methylstyrene). Yes; and the solvent is toluene.

High mobility once by combining polyacene and binder<u style="single">Formulations for organic semiconductor layers</u>Occurred when<u style="single">Prescription</u>Brings some other benefits. For example, polyacene is soluble and can be deposited in a liquid state, for example, from a solution. By using more binders<u style="single">Prescription</u>It was found here that can cover a large area in a highly uniform form. Without the use of binders, polyacenes cannot be spin-coated over large areas because they do not form a single membrane. In the prior art, pure polyacene layer spin and drop casting can provide relatively high mobility in some cases, but is wide with constant mobility across the substrate, which is a special requirement for electronic devices. It is difficult to provide a region membrane. In addition, the binder<u style="single">Prescription</u>When used in<u style="single">Prescription</u>Properties such as viscosity, solids, and surface tension can be controlled to adapt to the printing process. While not wanting to join by any particular theory<u style="single">Prescription</u>It is also expected that the use of a binder to will fill the volume between the otherwise void liquid crystal particles and make them less sensitive to air and moisture. For example, the layer formed in the first embodiment of the present invention exhibits very good stability in the atmosphere in an OFET device.

The present invention<u style="single">Formulations for organic semiconductor layers</u>Also provided is an organic semiconductor layer containing. The present invention further (i) A liquid layer of the above-mentioned polyacene compound; and an organic binder resin or precursor thereof; and a mixture optionally containing a solvent is laminated on the substrate, and (ii) A method for producing an organic semiconductor layer, which comprises forming a solid layer which is an organic semiconductor layer from a liquid layer, is also provided. The method will be described in more detail below.

The present invention further provides an electronic device including an organic semiconductor layer. Electronic devices may include, without limitation, organic field effect transistors (OFETs), organic light emitting diodes (OLEDs), photodetectors, sensors, logic circuits, memory devices, capacitors or photocells (PV) cells. For example, the active semiconductor channel between the drain and source in the OFET may include the layers of the invention. As another example, the charge (pore or electron) injection or carrier layer in an OLED device may include the layer of the invention. Of the present invention<u style="single">Prescription</u>And the layers formed thereby have specific effectiveness in OFETs that are particularly relevant to the preferred embodiments described herein. Certain polyacene compounds are described in US 2003/0116755 A and US 6,690,029, and the polyacene synthesis methods described herein may be used in the present invention for the production of the polyacene compounds described herein. Methods for making polyacene are also described in US 3,557,233 (American Cyanamid). Alternative methods among those skilled in the art that can be used in the synthesis of the polyacene compounds of the present invention are described in Organic Letters 2004, 6th Edition, No. 10, pp. 1609-1612.

Compound groups 1-9 are described in detail here.<u style="single">Compound group 1</u>Compound group 1 is represented by the formula 1. ::<chemistry num="9"><img file="JP5089986B2_D0009.tif" /></chemistry> In the pentacene derivative of compound group 1, R₆And R₁₃Are independent, identical or different, independent and arbitrarily substituted C₁~ C₄₀Includes carbyl or hydrocarbyl groups. More preferably, the group R₆And R₁₃Is an arbitrarily substituted, arbitrarily unsaturated C₁~ C₄₀Includes carbyl or hydrocarbyl groups of, for example, groups such as optionally substituted alkenyl, alkynyl, aryl, etc. (optionally substituted alkynyl is a preferred group, particularly optionally substituted ethynyl). Preferably R₆And R₁₃The substituent has a pentacene ring structure and is π-conjugated. But the base R₆And R₁₃Most preferably contain the same substituents on each other. In the pentacene derivative of Compound Group 1, the positions of the pentacene rings other than the 6th and 13th positions are preferably occupied by hydrogen, which is not substituted at all.

An example of compound group 1 is shown below. ::<chemistry num="10"><img file="JP5089986B2_D0010.tif" /></chemistry>In the formula, R_aIs an arbitrarily replaced C_1~40Calvir or hydrocarbyl groups, more preferably optionally substituted C_1~10Alkyl groups; and n are 0, 1, 2, 3, 4 or 5, most preferably 1, 2 or 3.

<u style="single">Compound group 2</u>Compound group 2 is represented by the formula 2. ::<chemistry num="11"><img file="JP5089986B2_D0011.tif" /></chemistry> In the pentacene derivative of compound group 2, R₅And R₁₄Are independent, identical or different, independent and arbitrarily substituted C₁~ C₄₀Includes carbyl or hydrocarbyl groups. More preferably, the group R₅And R₁₄Is an arbitrarily substituted unsaturated C₁~ C₄₀Contains, for example, optionally substituted alkenyl, alkynyl, aryl, aralkyl groups (optionally substituted alkynyl is a preferred group, particularly optionally substituted ethynyl). Preferably R₅And R₁₄The substituent has a pentacene ring structure and is π-conjugated. But the base R₅And R₁₄Most preferably contain the same substituents on each other. In the pentacene derivative of compound group 2, the position of one or more rings of the pentacene derivative other than the 5th and 14th positions may be substituted, but is preferably occupied by hydrogen, which is not substituted at all. ..

<u style="single">Compound group 3</u>Compound group 3 is represented by the formula 3. ::<chemistry num="12"><img file="JP5089986B2_D0012.tif" /></chemistry> In the pentacene derivative of compound group 3, R₂, R₃, R₉And R₁₀Are independent, identical or different, independent and arbitrarily substituted C₁~ C₄₀Includes carbyl or hydrocarbyl groups. More preferably, the group R₂, R₃, R₉And R₁₀Is an arbitrarily replaced C₁~ C₁₀Calvir or hydrocarbyl groups (particularly alkyl), such as methyl, ethyl, propyl, butyl, pentyl and the like. The positions of one or more rings of pentacene other than the 2, 3, 9 and 10 positions may be substituted, but are preferably occupied by unsubstituted, hydrogen. But R₂And R₃Are preferably the same substituents on each other, and R₉And R₁₀Are preferably the same substituents as each other. Most preferably R₂, R₃, R₉And R₁₀Are the same substituents on each other.

An example of compound group 3 is shown below. ::<chemistry num="13"><img file="JP5089986B2_D0013.tif" /></chemistry>

<u style="single">Compound group 4</u>Compound group 4 is represented by the formula 4. ::<chemistry num="14"><img file="JP5089986B2_D0014.tif" /></chemistry> In the pentacene derivative of compound group 4, R₂And R₃Are independently the same or different, but R₂And R₃Are preferably identical to each other. Preferably R₂And R₃Is an arbitrarily replaced C₁~ C₄₀Contains a calvir or hydrocarbyl group or a halo. In the pentacene derivative of compound group 4, the position of one or more rings of pentacene other than the 2nd and 3rd positions may be substituted, but it is preferably occupied by hydrogen which is not substituted at all.

Examples of compound group 4 are shown below. ::<chemistry num="15"><img file="JP5089986B2_D0015.tif" /></chemistry>

<u style="single">Compound group 5</u>Compound group 5 is represented by the formula 5. ::<chemistry num="16"><img file="JP5089986B2_D0016.tif" /></chemistry> In the pentacene derivative of compound group 5, R₂, R₃, R₁₁And R₁₂Are independently the same or different. But R₂And R₃Are preferably identical to each other and R₁₁And R₁₂Are preferably identical to each other. R₂, R₃, R₁₁And R₁₂Are preferably all identical to each other. Preferably, the group R₂, R₃, R₁₁And R₁₂Is an arbitrarily replaced C₁~ C₄₀Includes carbyl or hydrocarbyl groups. More preferably, the group R₂, R₃, R₁₁And R₁₂Is an arbitrarily replaced C₁~ C₄₀Includes calvir or hydrocarbyl groups such as methyl, ethyl, propyl, butyl, pentyl and the like. In the pentacene derivative of compound group 5, the position of one or more rings of the pentacene derivative other than the 2, 3, 11 and 12 positions may be substituted, but not substituted, that is, occupied by hydrogen. It is preferable to have.

Examples of compound group 5 are shown below. ::<chemistry num="17"><img file="JP5089986B2_D0017.tif" /></chemistry><u style="single">Compound group 6</u>Compound group 6 is represented by the formula 6. ::<chemistry num="18"><img file="JP5089986B2_D0018.tif" /></chemistry> In the pentacene derivative of compound group 6, R₂And R₉Are independently the same or different. But R₂And R₉Are preferably identical to each other. Preferably R₂And R₉Is an arbitrarily replaced C₁~ C₄₀Includes carbyl or hydrocarbyl groups. In the pentacene derivative of compound group 6, the position of one or more rings of pentacene other than the 2 and 9 positions may be substituted, but is preferably not substituted, that is, occupied by hydrogen. Examples of compound group 6 are shown below. ::<chemistry num="19"><img file="JP5089986B2_D0019.tif" /></chemistry>

<u style="single">Compound group 7</u>Compound group 7 is represented by the formula 7. ::<chemistry num="20"><img file="JP5089986B2_D0020.tif" /></chemistry> In the pentacene derivative of compound group 7, R₅, R₇, R₁₂And R₁₄Are independently the same or different. But R₅And R₁₄Are preferably identical to each other and R₇And R₁₂Are preferably identical to each other. More preferably, R₅, R₁₄, R₇And R₁₂Are all identical to each other. Preferably R₅, R₁₄, R₇And R₁₂Is an arbitrarily replaced C₁~ C₄₀Includes carbyl or hydrocarbyl groups. In the pentacene derivatives of compound group 7, the positions of one or more rings of pentacene other than the 5, 14, 7 and 12 positions may be substituted, but not substituted, i.e. occupied by hydrogen. Is preferable. Examples of compound group 7 are shown below. ::<chemistry num="21"><img file="JP5089986B2_D0021.tif" /></chemistry>

<u style="single">Compound group 8</u>Compound group 8 is represented by the formula 8. ::<chemistry num="22"><img file="JP5089986B2_D0022.tif" /></chemistry> In the pentacene derivative of compound group 8, R₁, R₂, R₃, R₄, R₈, R₉, R₁₀, R₁₁, R₁₅, R₁₆And R₁₇Are independently the same or different. But R₁, R₂, R₃, R₄, R₈, R₉, R₁₀, R₁₁, R₁₅, R₁₆, And R₁₇Are independently H and optionally substituted C₁~ C₄₀Includes carbyl or hydrocarbyl groups of, eg, optionally substituted groups such as alkenyl, alkyaryl, aryl, or halo groups such as F, Cl, Br. More preferably, R₁, R₂, R₃, R₄, R₈, R₉, R₁₀And R₁₇Is an arbitrarily replaced C₁~ C₁₀Alkyl groups of, such as methyl, ethyl, propyl, butyl, pentyl, etc., most preferably methyl; halogens, such as F, Cl, Br, most preferably F, R.₂And R₃And R₉And R₁₀C with the carbon atoms to which they are bonded₄~ C₄₀Form a saturated or unsaturated ring of, more preferably optionally substituted C₄~ C₁₀Is a saturated or unsaturated ring of, and is mediated by one or more oxygen atoms, a sulfur atom or a group represented by the formula -N (Ra)-(where Ra is a hydrogen atom or a hydrocarbon group). .. In the pentacene derivative of formula 8, R₁₅, R₁₆And R₁₇May be the same or different from each other, preferably R₁₅, R₁₆And R₁₇Are the same, for example optionally substituted with a halogen atom, optionally substituted C₁~ C₄₀Calvir or hydrocarbyl groups, eg C₁~ C₄₀Alkyl group (preferably C₁~ C₄Alkyl, most preferably methyl, ethyl, n-propyl or isopropyl); for example optionally substituted with a halogen atom, C₆~ C₄₀Aryl group (preferably phenyl); for example optionally substituted with a halogen atom, C₆~ C₄₀Arylalkyl groups of; eg optionally substituted with halogen atoms, C₁~ C₄₀Alkoxy group; for example, optionally substituted with a halogen atom, C₆~ C₄₀Contains an arylalkyloxy group of R₁₅And R₁₆Or R₁₆And R₁₇C with, for example, the atoms to which they are bonded₄~ C₄₀Form a saturated or unsaturated ring of, and also one or more oxygen atoms, sulfur atoms or the formula -N (Ra)-(in the formula, Ra is a hydrogen atom or hydrocarbon group and / or an isomer thereof. ) Intervenes. Preferably R₁₅, R₁₆And R₁₇Are arbitrarily replaced C, independent of each other_1~10Alkyl (more preferably C_1~4And more preferably C_1~3Alkyl (eg, isopropyl) and optionally substituted C_6~10Is selected from aryl (preferably phenyl). In the pentacene derivative of formula 8, X is preferably silicon or germanium, most preferably silicon.

In one preferred embodiment where X is silicon forming a silyl group, R₁₅, R₁₆And R₁₇Are identical groups to each other, eg, the same optionally substituted alkyl group, such as triisopropylsilyl. Preferably, in this embodiment, the group R₁₅, R₁₆And R₁₇Is the same arbitrarily replaced C_1~10Alkyl group (more preferably C_1~4, And more preferably C_1~3Is). The preferred alkyl group in this case is isopropyl. The above equation-Si (R)₁₅) (R₁₆) (R₁₇The silyl group of) is C₁~ C₄₀It is a preferred arbitrary substituent such as a calvir or hydrocarbyl group. Moreover, in an extension of this further preferred embodiment, R₂, R₃, R₉And R₁₀Is C_1~10Alkyl group of 1 or 2 or more R₂, R₃, R₉And R₁₀Is preferably methyl and has an R of 1 or 2 or greater.₁, R₂, R₃, R₄, R₈, R₉And R₁₀Is F. In a more preferred embodiment of compound group 8, R₁, R₂, R₃, R₄, R₈, R₉, R₁₀And R₁₁Are H respectively. R₁₅, R₁₆And R₁₇Is C_1~10Alkyl, more preferably C_1~5Alkyl, such as methyl, ethyl or propyl. In a further aspect of Group 8, any two or three or more substituents present at the position of the adjacent ring of the polyacene are fused to the polyacene compound together at the position of the adjacent ring to which they are attached, an aromatic ring system. Alternatively, the heterocyclic system may be arbitrarily configured. An example of this type of group 8 is R₁And R₂, R₃And R₄, R₈And R₉And R₁₀And R₁₁Each set of adjacent substituents of the group 8 constitutes a benzene ring fused to pentacene, as shown below in Example 6. ::

In the pentacene derivative of compound group 8, the position of one or more rings of the pentacene derivative other than the 1, 2, 3, 4, 6, 8, 9, 10, 11 and 13 positions may be substituted. , It is preferably not substituted, i.e. occupied by hydrogen. R₁₅, R₁₆And R₁₇Examples of the above-mentioned compound group 8 compounds in which n and m are shown are shown below. ::<chemistry num="23"><img file="JP5089986B2_D0023.tif" /></chemistry>

<u style="single">Compound group 9</u>Compound group 9 is represented by the formula 9. ::<chemistry num="24"><img file="JP5089986B2_D0024.tif" /></chemistry> In the pentacene derivative of compound group 9, R₂, R₃, R₇, R₈, R₁₅, R₁₆And R₁₇Are independently, identical or different, each independently, H or optionally substituted C₁~ C₄₀Includes carbyl or hydrocarbyl groups. R₂And R₃May be the same or different, but are preferably the same substituents on each other. R₇And R₈Are also the same or different, but preferably the same substituents on each other. Preferably R₂, R₃, R₇And R₈Are the same substituents on each other. Most preferably R₂And R₃And R₇And R₈Is one or more oxygen atoms, sulfur atoms or carbon atoms to which they are bonded, interspersed with groups represented by the formula -N (Ra)-(in the formula, Ra is a hydrogen atom or a hydrocarbon group). With C₄~ C₄₀It forms a saturated or unsaturated ring of sushi and thus forms a pseudo-pentacene compound. Preferred pseudo-pentacene derivatives of compound group 9 are formulas 9a and 9b and their isomers, in which one or more carbon atoms in the polyacene skeleton contain N, P, As, O, S, Se and Te, Preferably, it may be substituted with a heteroatom selected from N or S.

<chemistry num="25"><img file="JP5089986B2_D0025.tif" /></chemistry>

In the pseudopentacene derivative of compound group 9 represented by the formula 9a, R₁₉And R₂₀Is preferably the same substituent and optionally substituted C_1~40Includes carbyl or hydrocarbyl groups. More preferably, R₁₉And R₂₀Are independently substituted, arbitrarily substituted, arbitrarily unsaturated C_1~40Calvir or hydrocarbyl group, eg, optionally substituted alkyl, alkenyl, alkynyl, aryl or aralkyl group, or R₁₉And R₂₀Are optionally substituted either with the carbon atom to which they are attached or independently in combination with substituents on appropriately adjacent atoms.₄~ C₄₀Any group represented by one or more oxygen atoms, sulfur atoms or the formula -N (Ra)-(where Ra is a hydrogen atom or a hydrocarbon group) forms a saturated or unsaturated ring of Intervene. Most preferably (R with the carbon atoms to which they are attached)₁₉And R₂₀The ring is mediated by one or more oxygen atoms. But most preferably R₁₉And R₂₀Are the same substituents, hydrogen, or saturated or unsaturated C_1~4Alkyl groups of, for example, methyl, ethyl, propyl, or butyl, most preferably R.₁₉And R₂₀Are independently methyl groups or hydrogen atoms.

In the pseudopentacene derivatives of compound groups 9a and 9b, R₁₅, R₁₆, R₁₇May be the same or different, most preferably R₁₅, R₁₆And R₁₇Are the same and are as described in relation to the compounds of formula 8 above. In the pseudopentacene derivative of compound group 9, the ring positions of one or more compounds may be substituted, for example to form a more optionally substituted ring, preferably the position of the other ring. Is not substituted, i.e. occupied by hydrogen. In the polyacenes of the present invention (particularly compound groups 1 to 9), C₁~ C₄₀The calvir or hydrocarbyl group may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. Unsaturated acyclic or cyclic groups are preferred, especially alkenyl and alkynyl groups (particularly ethynyl). C₁~ C₄₀When the calvir or hydrocarbyl group of is acyclic, the group may be straight or branched. C₁~ C₄₀The calvir or hydrocarbyl group of, for example: C₁~ C₄₀Alkyl group, C₂~ C₄₀Alkenyl group, C₂~ C₄₀Alkynyl group, C₃~ C₄₀Allyl group, C₄~ C₄₀Alkyldienyl group, C₄~ C₄₀Polyenyl group, C₆~ C₁₈Aryl group, C₆~ C₄₀Alkylation aryl group, C₆~ C₄₀Aryl Alkyl Group, C₄~ C₄₀Cycloalkyl group, C₄~ C₄₀Includes cycloalkenyl groups and the like. C in the above group₁~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl group, C₂~ C₂₀Alkynyl group, C₃~ C₂₀Allyl group, C₄~ C₂₀Alkyldienyl group, C₆~ C₁₂Aryl group, C₄~ C₂₀Each of the polyenyl groups in is preferred; C₁~ C₁₀Alkyl group, C₂~ C₁₀Alkenyl group, C₂~ C₁₀Alkynyl groups (especially ethynyl), C₃~ C₁₀Allyl group, C₄~ C₁₀Alkyldienyl group, C₆~ C₁₂Aryl group, C₄~ C₁₀Each of the polyenyl groups in is even more preferred; C₂~ C₁₀The alkynyl group of is most preferred.

Examples of alkyl groups, but not limited to, are methyl, ethyl, propyl, n-butyl, t-butyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, benzyl, For example, 2-phenoxyethyl. Examples of alkynyl groups are ethynyl and propynyl. Examples of aryl groups are, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, naphthyl, biphenyl, 4-phenoxyphenyl, 4-fluorophenyl, 3-carbomethoxyphenyl, 4-carbo. Such as methoxyphenyl. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, 2-methoxyethoxy, t-butoxy and the like. Examples of aryloxy groups include, but are not limited to, phenoxy, naphthoxy, phenylphenoxy, 4-methylphenoxy and the like. Examples of amino groups include, but are not limited to, dimethylamino, methylamino, methylphenylamino, phenylamino and the like. In the polyacene of the present invention, R₁Such as C₁~ C₄₀Any substituents on the carbyl or hydrocarbyl groups of are preferably: silyl, sulfo, sulfonyl, formyl, amino, imino, nitrilo, mercapto, cyano, nitro, halo, C._1~4Alkyl, C_6~12Aryl, C_1~4Selected from alkoxy, hydroxy and / or all chemically possible combinations thereof. Of these arbitrary substituents, Cyril, C_6~12Aryl is preferred, and silyl is most preferred.

Arbitrarily substituted silyl groups herein are of formula-Si (R).₁₅) (R₁₆) (R₁₇) May be indicated by R₁₅, R₁₆And R₁₇Each of the Cs may be the same or different, independently substituted with hydrogen, optionally for example a halogen atom.₁~ C₄₀-Alkyl group (preferably C₁~ C₄Alkyl groups and most preferably methyl, ethyl, n-propyl or isopropyl); C optionally substituted with, for example, a halogen atom.₆~ C₄₀-Aryl group (preferably phenyl); C optionally substituted with, for example, a halogen atom₆~ C₄₀-Arralalkyl group; C optionally substituted with, for example, a halogen atom₁~ C₄₀-Alkoxy group; or optionally C substituted with, for example, a halogen atom₆~ C₄₀-Arylalkyloxy group. Preferably R₁₅, R₁₆And R₁₇Are independently and arbitrarily replaced C_1~10-Alkyl (more preferably C_1~4And even more preferably C_1~3-Alkyl, eg isopropyl) and optionally substituted C_6~10-Choice from aryl (preferably phenyl).

One of the preferred embodiments of the silyl group is R₁₅, R₁₆And R₁₇Are preferably the same groups with each other, such as the same optionally substituted alkyl group, such as triisopropylsilyl. Preferably, in such a preferred embodiment, the group R₁₅, R₁₆And R₁₇Is the same arbitrarily replaced C_1~10(More preferably, C₁₄And even more preferably C_1~3) Alkyl group. The preferred alkyl group in this case is isopropyl. The above equation-Si (R)₁₅) (R₁₆) (R₁₇) Is C₁~ C₄₀Is any preferred substituent, such as a calvir or hydrocarbyl group. The above equation-Si (R)₁₅) (R₁₆) (R₁₇) Examples of the silyl group are, but are not limited to, trimethylsilyl, triethylsilyl, tripropylsilyl, dimethylethylsilyl, diethylmethylsilyl, dimethylpropylsilyl, dimethylisopropylsilyl, dipropylmethylsilyl, diisopropylmethylsilyl, di. Propylethylsilyl, diisopropylethylsilyl, diethylisopropylsilyl, triisopropylsilyl, trimethoxysilyl, triethoxysilyl, triphenylsilyl, diphenylisopropylsilyl, diisopropylphenylsilyl, diphenylethylsilyl, diethylphenylsilyl, diphenylmethylsilyl, triphenoxy Cyril, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl and the like. In each of the examples listed above, the alkyl, aryl or alkoxy groups may be optionally substituted.

The most preferred pentacene compounds of the present invention are compound groups 1, 2, 8 and 9, and even more particularly preferably compound groups 1 and 8. Examples of compounds in groups 1 and 2 are, but are not limited to, 6,13-bis (trimethylsilylethynyl) pentacene, 6,13-bis (triethylsilylethynyl) pentacene, 6,13-bis (tripropylsilylethynyl) pentacene, 6,13-bis (dimethylethylsilylethynyl) pentacene, 6,13-bis (diethylmethylsilylethynyl) pentacene , 6,13-bis (dimethylpropylsilylethynyl) pentacene, 6,13-bis (dimethylisopropylsilylethynyl) pentacene, 6,13-bis (dipropylmethylsilylethynyl) -pentacene, 6,13-bis (diisopropylmethyl) Cyril ethynyl) pentacene, 6,13-bis (dipropylethylsilylethynyl) pentacene, 6,13-bis (diisopropylethylsilylethynyl) pentacene, 6,13-bis (dipropylisopropylsilylethynyl) pentacene, 6,13-bis (Triisopropylsilylethynyl) pentacene, 6,13-bis (trimethoxysilylethynyl) pentacene, 6,13-bis (triethoxysilylethynyl) pentacene, 6,13-bis (triphenylsilylethynyl) pentacene, 6,13 -Bis (diphenylisopropylsilylethynyl) pentacene, 6,13-bis (diisopropylphenylsilylethynyl) pentacene, 6,13-bis (diphenylethylsilylethynyl) -pentacene, 6,13-bis (diethylphenylsilylethynyl) pentacene, 6,13-bis (diphenylmethyl-silylethynyl) pentacene, 6,13-bis (triphenoxysilylethynyl) pentacene, 6,13-bis (dimethylmethoxysilylethynyl) pentacene, 13-bis (dimethylphenoxysilylethynyl) Pentacene, 6,13-bis (methylmethoxyphenylethynyl) pentacene, 6,13-bis (cyclopentamethylenesilane) -pentacene, 6,13-bis (cyclotetramethylenesilane) pentacene, 5,14-bis (trimethylsilylethynyl) )-Pentacene, 5,14-Bis (triethylsilylethynyl) pentacene, 5,14-bis (tripropylsilylethynyl) -pentacene, 5,14-bis (dimethylethylsilylethynyl) pentacene, 5,14-bis (diethylmethylsilylethynyl) pentacene, 5,14-bis (dimethylpropylsilylethynyl) pentacene , 5,14-bis (dimethylisopropylsilylethynyl) pentacene, 5,14-bis (dipropylmethylsilylethynyl) pentacene, 5,14-bis- (diisopropylmethylsilylethynyl) pentacene, 5,14-bis (dilopyr) Ethylsilylethynyl) pentacene, 5,14-bis (diisopropylethylsilylethynyl) pentacene, 5,14-bis (diethylisopropylsilylethynyl) -pentacene, 5,14-bis (triisopropylsilylethynyl) pentacene, 5,14- Bis (trimethoxysilylethynyl) -pentacene, 5,14-bis (triethoxysilylethynyl) pentacene, 5,14-bis (triphenylsilylethynyl) -pentacene, 5,14-bis (diphenylisopropylsilylethynyl) pentacene, 5,14-bis (diisopropylphenyl-silylethynyl) pentacene, 5,14-bis (diphenylethylsilylethynyl) pentacene, 5,14-bis (diethylphenylsilylethynyl) pentacene, 5,14-bis (diphenylmethylsilylethynyl) ) Pentacene, 5,14-bis (triphenoxysilylethynyl) pentacene, 5,14-bis (dimethylmethoxysilylethynyl) -pentacene, 5,14-bis (dimethylphenoxysilylethynyl) pentacene, 5,14-bis (methyl) It is methoxyphenylethynyl) pentacene.14-bis- (diisopropylmethylsilylethynyl) pentacene, 5,14-bis (dilopyrethylsilylethynyl) pentacene, 5,14-bis (diisopropylethylsilylethynyl) pentacene, 5,14-bis (diethylisopropylsilylethynyl) -Pentacene, 5,14-bis (triisopropylsilylethynyl) pentacene, 5,14-bis (trimethoxysilylethynyl) -pentacene, 5,14-bis (triethoxysilylethynyl) pentacene, 5,14-bis (tri) Phenylsilylethynyl) -pentacene, 5,14-bis (diphenylisopropylsilylethynyl) pentacene, 5,14-bis (diisopropylphenyl-silylethynyl) pentacene, 5,14-bis (diphenylethylsilylethynyl) pentacene, 5,14 -Bis (diethylphenylsilylethynyl) pentacene, 5,14-bis (diphenylmethylsilylethynyl) pentacene, 5,14-bis (triphenoxysilylethynyl) pentacene, 5,14-bis (dimethylmethoxysilylethynyl) -pentacene, 5,14-bis (dimethylphenoxysilylethynyl) pentacene and 5,14-bis (methylmethoxyphenylethynyl) pentacene.14-bis- (diisopropylmethylsilylethynyl) pentacene, 5,14-bis (dilopyrethylsilylethynyl) pentacene, 5,14-bis (diisopropylethylsilylethynyl) pentacene, 5,14-bis (diethylisopropylsilylethynyl) -Pentacene, 5,14-bis (triisopropylsilylethynyl) pentacene, 5,14-bis (trimethoxysilylethynyl) -pentacene, 5,14-bis (triethoxysilylethynyl) pentacene, 5,14-bis (tri) Phenylsilylethynyl) -pentacene, 5,14-bis (diphenylisopropylsilylethynyl) pentacene, 5,14-bis (diisopropylphenyl-silylethynyl) pentacene, 5,14-bis (diphenylethylsilylethynyl) pentacene, 5,14 -Bis (diethylphenylsilylethynyl) pentacene, 5,14-bis (diphenylmethylsilylethynyl) pentacene, 5,14-bis (triphenoxysilylethynyl) pentacene, 5,14-bis (dimethylmethoxysilylethynyl) -pentacene, 5,14-bis (dimethylphenoxysilylethynyl) pentacene and 5,14-bis (methylmethoxyphenylethynyl) pentacene.14-bis (diphenylethylsilylethynyl) pentacene, 5,14-bis (diethylphenylsilylethynyl) pentacene, 5,14-bis (diphenylmethylsilylethynyl) pentacene, 5,14-bis (triphenoxysilylethynyl) pentacene, 5,14-bis (dimethylmethoxysilylethynyl) -pentacene, 5,14-bis (dimethylphenoxysilylethynyl) pentacene, 5,14-bis (methylmethoxyphenylethynyl) pentacene.14-bis (diphenylethylsilylethynyl) pentacene, 5,14-bis (diethylphenylsilylethynyl) pentacene, 5,14-bis (diphenylmethylsilylethynyl) pentacene, 5,14-bis (triphenoxysilylethynyl) pentacene, 5,14-bis (dimethylmethoxysilylethynyl) -pentacene, 5,14-bis (dimethylphenoxysilylethynyl) pentacene, 5,14-bis (methylmethoxyphenylethynyl) pentacene.

Examples of compounds in groups 8 and 9 are, but are not limited to, 2,3,9,10-tetramethyl-6,13-bis (triisopropylsilylethynyl) pentacene, 5,11-bis (triisopropylsilyl). Ethynyl) anthra [2,3-b: 6,7-b'] dithiophene, 5,11-bis (triisopropylsilylethynyl) anthra [2,3-b: 7,6-b'] dithiophene, 1,8 -Difluoro-6,13-bis (triisopropylsilylethynyl) pentacene, 1,11-difluoro-6,13-bis (triisopropylsilylethynyl) pentacene and 2,3,9,10-tetrafluoro-6,13- Bis (triisopropylsilylethynyl) pentacene.

In compound groups 1 and 8, compounds of formula 1A, 8A or 8B, particularly compounds of formula 1A, are preferred. ::<chemistry num="26"><img file="JP5089986B2_D0026.tif" /></chemistry>In the equation, each of R'may be independently replaced arbitrarily._2~40Alkyl group, C_2~40Alkoxy group, C_2~40Alkenyl group, C_2~40Alkynyl group, C_6~18Aryl or heteroaryl group, C₆~ C₄₀Aryloxy group, C₇~ C₄₀Alkylaryloxy group, C₂~ C₄₀Alkoxycarbonyl group, C₇~ C₄₀Aryloxycarbonyl group or silyl group, or cyano group (-CN), carbamoyl group (-C (= O) NH₂), Haloformyl group (-C (= O) -X, where X represents a halogen atom), formyl group (-C (= O) -H), isocyano group, isocyanate group, thiocianate group or thioisocyanate Selected from groups, optionally substituted amino groups, imino groups, hydroxy groups, halos, sulfo groups, sulfonyl groups, mercapto groups, nitro groups; and in formula 8B m and n are independently 0, respectively. It is 1, 2, 3 or 4, and more preferably 0, 1 or 2. Preferably, in Formulas 1A, 8A and 8B, R'is independently and arbitrarily substituted together._6~18Selected from aryl and silyl.

Preferably, in formulas 1A, 8A and 8B, at least one R'and most preferably both R's are silyls, where the silyl group is preferably as defined above, i.e. the formula-Si (R).₁₅) (R₁₆) (R₁₇) Is a silyl group. Therefore, these most preferred compounds of the latter are of the formulas 1A', 8A' and 8B'. ::<chemistry num="27"><img file="JP5089986B2_D0027.tif" /></chemistry>

In one of the preferred embodiments, in formulas 1A', 8A' and 8B', R15, R16 and R17 are preferably identical to each other and are alkyl such as, for example, 6,13-bis- (triisopropylsilylethynyl) pentacene. Is the basis. In this particularly preferred embodiment, R₁₅, R₁₆And R₁₇Is preferably the same C that may be optionally substituted_1~10(Preferably C_1~4And more preferably C_1~3) Alkyl group. Arbitrarily substituted isopropyl is the preferred alkyl group of such embodiments. In some cases, it is desirable to control the solubility of polyacene in common organic solvents to further facilitate the manufacture of the device. This is advantageous for the manufacture of FETs, for example solution coating, eg, dielectrics to the polyacene layer, tend to dissolve the polyacene. Also, once the device is formed, the less soluble polyacenes are less likely to "bleed" in the organic layer. In one embodiment of the method of controlling the solubility of the pentacene derivative of formula 1B above, at least one R.₁₅, R₁₆And R₁₇Is an optionally substituted aryl (preferably phenyl) group. Therefore, R₁₅, R₁₆And R₁₇At least one of the arbitrarily replaced C_6~18Aryl (preferably phenyl) group, optionally substituted C_6~18Aryloxy (preferably phenoxy) group, optionally substituted C_6~20Arylalkyl (eg, benzyl) group or optionally substituted C_6~20It is an arylalkyloxy (eg, benzyloxy) group. In such a case, any R₁₅, R₁₆And R₁₇The remaining groups of are arbitrarily substituted C_1~10(More preferably, C_1~4) Alkyl groups are preferred. An example in such an embodiment is Formula 1C, in which Ar is an aryl-containing group, eg, an optionally substituted C._6~18Aryl group, optionally substituted C_6~18Aryloxy group, optionally substituted C_6~20Arylalkyl group, optionally substituted C_6~20Indicates an arylalkyloxy group. ::

<chemistry num="28"><img file="JP5089986B2_D0028.tif" /></chemistry>

R in Equation 1C₁₅, R₁₆And R₁₇Is preferably the same group as each other, for example, an isopropyl group. Examples of compounds of formula 1C are, but are not limited to, 6,13-bis (triphenylsilylethynyl) pentacene, 6,13-bis (diphenylisopropylsilylethynyl) pentacene, 6,13-bis (diisopropylphenylsilylethynyl) pentacene, 6,13-bis (diphenylethylsilylethynyl) -pentacene, 6,13-bis (diethylphenylsilylethynyl) pentacene, 6,13-bis (diphenylmethylsilylethynyl) ) Pentacene, 6,13-bis (triphenoxysilylethynyl) pentacene, 6,13-bis (dimethylphenoxysilylethynyl) pentacene, 6,13-bis (methylmethoxyphenylethynyl) -pentacene, 5,14-bis (tri) Phenylsilylethynyl) pentacene, 5,14-bis (diphenylisopropylsilylethynyl) pentacene, 5,14-bis (diisopropylphenylsilylethynyl) pentacene, 5,14-bis- (diphenylethylsilylethynyl) pentacene, 5,14- Bis (diethylphenylsilylethynyl) pentacene, 5,14-bis (diphenylmethylsilylethynyl) pentacene, 5,14-bis (triphenoxysilylethynyl) pentacene, 5,14-bis (dimethylphenoxysilylethynyl) pentacene, 5, Contains 14-bis (methylmethoxyphenylethynyl) -pentacene. Preferred additional examples of groups 1 and 8 are those described above in the general description of the respective groups.

In a preferred embodiment of the invention, the semiconductor polyacene is 10^-5cm²V^-1s^-1Greater, preferably 10^-4cm²V^-1s^-1Greater, more preferably 10^-3cm²V^-1s^-1Greater, even more preferably 10^-2cm²V^-1s^-1Greater and most preferably 10^-1cm²V^-1s^-1It has a greater field effect mobility, μ. The binder, which is a polymer, may include either an insulating binder, a semiconductor binder, or a mixture thereof, and is referred to herein as an organic binder, a polymer binder, or simply a binder. The preferred binder of the present invention is a material having a low dielectric constant, that is, one having a dielectric constant of 3.3 or less, ε at 1,000 Hz. The organic binder preferably has a dielectric constant less than 3.0 at 1,000 Hz, more preferably 2.9 or less. Preferably, the organic binder has a dielectric constant greater than 1.7 at 1,000 Hz. It is particularly preferable that the dielectric constant of the binder is in the range of 2.0 to 2.9. We do not want to be bound by any particular theory, but we believe that the use of binders with dielectric constants greater than 3.3 at 1,000 Hz may reduce the mobility of the OSC layer of electronic devices, such as OFETs. Has been done. In addition, high dielectric constant binders can also result in undesired increased current hysteresis.

An example of an organic binder is polystyrene. Further examples are: In one preferred embodiment, the organic binder is composed of at least 95% of the atoms, more preferably at least 98%, particularly entirely of hydrogen, fluorine and carbon atoms. The binder usually preferably comprises a conjugated bond, particularly a conjugated double bond and / or an aromatic ring. The binder should preferably be able to form a membrane, more preferably a flexible membrane. Copolymers containing styrene and alpha-methylstyrene polymers, such as styrene, alpha-methylstyrene and butadiene, may be preferably used. The low dielectric constant binders used in the present invention have few invariant dipoles that would otherwise cause random variation in molecular site energies. The permittivity (dielectric constant) can be determined by the ASTM D 150 test method.

In the present invention, since this type of material has a low invariant dipole, a binder having a low bipolarity and a solubility parameter that contributes to hydrogen bonding is also preferred. The preferred range of solubility parameters of the binder used in the present invention is shown in Table 1 below.<tables num="1"><img file="JP5089986B2_D0029.tif" /></tables> The three-dimensional solubility parameters listed above are: Dispersion (δ)_d), Polarity (δ)_p) And hydrogen bonds (δ)_h) Ingredients (CM Hansen, Ind. Eng. And Chem., Prod. Res. And Devl., 9, No3, p282., 1970). These parameters can be determined empirically or calculated by the contribution of known molar groups described in the Handbook of Solubility Parameters and Other Cohesion Parameters ed. AFM Barton, CRC Press, 1991. .. Solubility parameters of many known polymers are also listed herein.

It is desirable that the permittivity of the binder is almost frequency independent. These are typical of non-polar materials. Polymers and / or copolymers can be selected as binders by the dielectric constant of their substituents. A list of low polarity binders suitable for use in the present invention is shown in Table 2 below (but not limited to these examples). ::<tables num="2"><img file="JP5089986B2_D0030.tif" /></tables>

Other polymers suitable as binders include: poly (1,3-butadiene) or polyphenylene. Copolymers containing repeating units of the above polymers are also suitable as binders. It improves compatibility with polyacenes and offers the possibility to change the morphology and / or glass transition temperature of the final layer structure. It is desirable that some of the materials in the table above are insoluble in the solvents commonly used to make layers. In these cases, the analog can be used as the copolymer. Some examples of copolymers are shown in Table 3 (but not limited to these). Both random and block copolymers can be used. It is also possible to add some of the more polar monomer components, provided that the composition remains less polar throughout.<tables num="3"><img file="JP5089986B2_D0031.tif" /></tables>

Other copolymers are: branched or unbranched polystyrene-block-polybutadiene, polystyrene-block (polyethylene-run-butylene) -block-polystyrene, polystyrene-block-polybutadiene-block-polystyrene, polystyrene- (ethylene-propylene) -Diblock-copolymers (eg, KRATONR®-G1701E, Shell), poly (propylene-co-ethylene) and poly (styrene-co-methylmethacrylate) may be included. Of the present invention<u style="single">Formulations for organic semiconductor layers</u>Preferred insulating binders used in are poly (α-methylstyrene), polyvinyl chloride, poly (4-vinylbiphenyl), poly (4-methylstyrene) and Topas® 8007. However, the most preferred insulating binders are poly (α-methylstyrene), polyvinyl chloride and poly (4-vinylbiphenyl). As described above, the organic binder can itself be a semiconductor and is referred to herein as a semiconductor binder. The semiconductor binder is more preferably a low dielectric constant binder as defined herein. The semiconductor binder used in the present invention has a number average molecular weight (Mn) of at least 1500-2000, more preferably at least 3000, even more preferably at least 4000, and most preferably at least 5000. The semiconductor binder is preferably at least 10^-5cm²V^-1s^-1, More preferably at least 10^-4cm²V^-1s^-1It has the charge carrier mobility of μ.

A preferred class of semiconductor binders has a repeating unit of formula 10. ::<chemistry num="29"><img file="JP5089986B2_D0032.tif" /></chemistry>During the ceremony, Ar¹, Ar²And Ar³Can be the same or different, but independently, in different repeating units, indicate an arbitrarily substituted aromatic group (monocyclic or polycyclic), and for semiconductor binders, n is at least 6, preferably at least 10, more preferably at least 15, and most preferably at least 20 integers. Ar¹, Ar²And Ar³In, the monocyclic aromatic group has only one aromatic ring, eg, phenyl or phenylene. Polycyclic aromatic groups have two or more aromatic rings and may be fused (eg, naphthyl or naphthalene), each may be covalently bonded (eg, biphenyl), and / Alternatively, it may be a combination of both a fusion and a covalently bonded aromatic ring. Preferably, Ar¹, Ar²And Ar³Each of these is an aromatic group that is substantially shared throughout the group.

A preferred class of semiconductor binders is those that substantially contain a shared repeating unit. The semiconductor polymer may be a homopolymer or a copolymer (including a block copolymer) of the general formula 11. :: A_(C)B_(d)... X_(z) Equation 11 In the formula, A, B, and Z represent monomer units, respectively, and (c), (d) ... (z) are the molar ratios of the polymers of each monomer, that is, (c), (d). .. (z) is a value from 0 to 1, and (c) + (d) + ... + (z) = 1. The monomer units A, B, ... Z include the units of the following formulas 10 and 12 to 17. ::

<chemistry num="30"><img file="JP5089986B2_D0033.tif" /></chemistry>In the formula, R1 and R2 are: H; optionally substituted alkyl; alkoxy; thioalkyl; acyl; optionally substituted aryl; fluorine atom; cyano group; nitro group; formula-N (R)._a) (R_{b b}) (In the formula, R_aAnd R_{b b}Are independently H, optionally substituted alkyl, aryl, optionally substituted aryl, alkoxy or polyalkoxy group), optionally substituted secondary or tertiary alkylamine or Arylamine; or other substituents, * are either terminal or endcapping groups containing hydrogen (optionally fluorine-substituted alkyl and aryl groups).

<chemistry num="31"><img file="JP5089986B2_D0034.tif" /></chemistry>In the formula, X is Se, Te, O, S or -N (R)_c), More preferably X is O, S or -N (R)_c) (In the formula, R_cMay indicate H, optionally substituted alkyl or optionally substituted aryl); and R1 and R2 are as described in Formula 12.

<chemistry num="32"><img file="JP5089986B2_D0035.tif" /></chemistry>In the formula, R1, R2 and X are as described in formulas 12 and 13, respectively. ;

<chemistry num="33"><img file="JP5089986B2_D0036.tif" /></chemistry>In the equation, R1, R2 and X are as described in equations 12 and 13, respectively; Z is -C (T).₁) = C (T)₂)-, -CC-, -N (R')-, -N = N-, (R') = N-, -N = C (R')-(In the formula, T₁And T₂Independently indicate -H, Cl, F, -CN or lower alkyl groups and R'indicates -H, alkyl, substituted alkyl, aryl or substituted aryl. ) Is shown. ;

<chemistry num="34"><img file="JP5089986B2_D0037.tif" /></chemistry>In the equation, R1 and R2 are as described in Equation 12. ;<chemistry num="35"><img file="JP5089986B2_D0038.tif" /></chemistry>In the formula, R1 to R4 may be independently selected from the list of the same groups as described in R1 and R2 of formula 12.

In the case of the polymer formulas described herein, such as Formulas 10-17, the polymer may end with any end group, i.e. an endcapping or leaving group containing hydrogen. In the case of block-copolymers, the monomers A, B ... Z may be conjugate oligomers of units of formula 12-17 or polymers containing, for example, numbers 2-50. Semiconductor binders are preferably: arylamines, fluorenes, thiophenes, It contains spirobifluorene and / or optionally substituted aryl (eg, phenylene), more preferably arylamines, and even more preferably triarylamine groups. The above-mentioned groups may be further bonded with a conjugated group such as vinylene. In addition, the semiconductor binder may include one or more of the above-mentioned arylamines, fluorene, thiophenes and / or polymers containing optionally substituted aryl groups (either homopolymers or copolymers containing block-copolymers). preferable. Preferred semiconductor binders include homopolymers or copolymers (including block-copolymers) containing arylamines (preferably triarylamines) and / or fluorene units. Other preferred semiconductor binders include homopolymers or copolymers (including block-copolymers) containing fluorene and / or thiophene units.

Semiconductor binders may also contain carbazole, stilbene repeating units. For example, polyvinylcarbazole or polystilbene polymers, copolymers can be used. The semiconductor binder may optionally include a polyacene moiety (eg, the repeating unit described in Formula A above) to improve compatibility with the soluble polyacene molecule. Of the present invention<u style="single">Formulations for organic semiconductor layers</u>The most preferred semiconductor binders used in are poly (9-vinylcarbazole) and PTAA1. For use in the semiconductor layer of p-channel FETs, the semiconductor binder should have a higher ionization potential than the polyacene semiconductor, otherwise the binder may form pore traps. For n-channel materials, semiconductor binders should have a lower electron affinity than n-type semiconductors to avoid electron capture.

Of the present invention<u style="single">Prescription</u>Is: (i) Both the polyacene compound and the organic binder are mixed first, preferably the mixing comprises mixing the two components with a solvent or solvent mixture. The solvent may be a single solvent or the polyacene compound and the organic binder are dissolved in separate solvents and the two resulting solutions are mixed to mix the compounds; (ii) Apply a solvent containing a polyacene compound and an organic binder to the substrate; (iii) It may be produced by a step including optionally evaporating the solvent to form the layer of the invention.

The binder, optionally in the presence of a solvent, mixes or dissolves polyacene in a precursor of the binder, such as a liquid monomer, oligomer or crosslinkable polymer, and the mixture or solution, for example, to form a liquid layer, for example. By dipping, spraying, coating or printing, it is laminated on a substrate and the liquid monomer, oligomer or crosslinked polymer is formed as-is by exposing it to light, heating or electron beam to form, for example, a solid layer and curing. May be good. When using a preformed binder, dissolve with polyacene in a suitable solvent, stack the solution by, for example, dipping, spraying, coating or printing to form a liquid layer and remove the solvent to obtain a solid layer. You may. It is desirable to select a solvent that is soluble in both binders and polyacenes and that forms a layer from the liquid mixture that does not have the drawback of stickiness during evaporation. The preferred solvent for the binder or polyacene can be determined by making contour plots of the materials described in ASTM Method D3132 at concentrations using the mixture. The material is added in a wide range as described in ASTM method. According to the present invention<u style="single">Prescription</u>May contain one or more polyacene compounds and / or one or more binders.<u style="single">Prescription</u>The manufacturing method of<u style="single">Prescription</u>It is also desirable to be used by.

Examples of organic solvents that can be considered are: CH₂Cl₂, CHCl₃, Monochlorobenzene o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxene, acetone, methylethylketone, 1,2-dichloroethane, 1,1,1- Trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetralin, decalin and / or mixtures thereof. After suitable mixing and curing, the solvent is evaluated as one of the following categories: complete solutions, solutions at its boundaries or insoluble. Contour lines are drawn to outline the solubility parameter-hydrogen bond limits that separate solubility and insolubility. "Complete" solvents that fit within the soluble region are "Crowley, JD, Teague, GS Jr and Lowe, JW. It can be selected by literature values as published in "Jr., Journal of Paint Technology, 38, No 496, 296 (1966)". Solvent mixtures can also be used and "Solvents, WHEllis, Federation of" It can be clarified by the description of Societies for Coatings Technology, p9-10, 1986 ". It is desirable that the mixture have at least one real solvent, but by such a procedure it dissolves in both the binder and polyacene. Can result in a mixture of "non" solvents. Organics of the invention for use in binders for both insulation and semiconductors and mixtures thereof<u style="single">Formulation for semiconductor layer</u>Suitable solvents for are: xylene, toluene, tetralin and o-dichlorobenzene.

Of the present invention<u style="single">Prescription</u>Alternatively, the ratio of binder to polyacene in the layer is typically 20: 1 to 1:20, preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, more by weight. It is preferably 3: 1 to 1: 3, more preferably 2: 1 to 1: 2, and particularly preferably 1: 1. Surprisingly and advantageously, it has been found that dilution of polyacene into the binder has little or no detrimental effect on charge mobility than previously predicted. According to the present invention<u style="single">Formulations for organic semiconductor layers</u>It has also been found that the solid content of is also a factor in achieving improved mobility values for electronic devices such as OFETs.<u style="single">Prescription</u>The solid content of is commonly shown below:<maths num="1"><img file="JP5089986B2_D0039.tif" /></maths>In the formula, a = mass of polyacene, b = mass of binder and c = mass of solvent.<u style="single">Prescription</u>The solid content of is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight.

Surprisingly and advantageously, it was found that dilution of polyacene into a binder had little or no effect on charge mobility than previously predicted. In modern microelectronics, providing smaller structures is desirable for cost savings (more devices / unit area) and reduced energy consumption. The layer patterning of the present invention can be performed by photolithography or electron beam lithography. Liquid coating of organic electronic devices such as electronic effect transistors is preferable to vacuum deposition techniques. The polyacene and binder mixture of the present invention allows the use of many liquid coating techniques. Organic semiconductor layers are, for example, but not limited to, dip coating, spin coating, inkjet printing, letter-press printing, screen printing, doctor blade coating; roller printing, reverse roller printing; offset lithography printing, flexography. Printing, web printing It can be incorporated into the final device structure by spray coating, brushing or pad printing. The present invention is particularly suitable for use in spin coating an organic semiconductor layer on a final device structure.

The selected polyacene and binder compositions of the present invention may be used on off-the-shelf device substrates by inkjet printing or microdispensing. Preferably, but not limited to, industrial piezoelectric printing heads such as those supplied by Aprion, Hitachi-Koki, InkJet Technology, On Target Technology, Picojet, Spectra, Trident, Xaar are used for coating organic semiconductor layers on substrates. May be good. In addition, semi-industrial heads such as those manufactured by Brother, Epson, Konica, Seiko Instruments Toshiba TEC or single nozzle microdispensers manufactured by Microdrop and Microfab may be used.

For application by inkjet printing or microdispensing, the polyacene and binder composition must first be dissolved in a suitable solvent. The solvent must meet the above requirements and must have no detrimental effect on the selected printhead. In addition, the solvent has a boiling point of&gt; 100 ° C, preferably&gt; 140 ° C, even more preferably&gt; 150 ° C, to prevent operability problems caused by the solvent drying inside the printhead. There must be. Suitable solvents are substituted and unsubstituted xylene derivatives, di-C._1-2-Alkylformamide, substituted and unsubstituted anisole, and substituted heterocycles such as substituted phenol-ether derivatives, substituted pyridine, pyrazine, pyrimidine, pyrrolidine, substituted and unsubstituted N, N-di-C_1-2-Includes alkylaniline and other fluorinated or chlorinated aromatics.

Binder / Polyacene by Inkjet Printing<u style="single">Prescription</u>Suitable solvents for laminating the mixture include benzene derivatives having a benzene ring substituted with 1 or 2 or more substituents having at least 3 total carbon atoms among 1 or 2 or more substituents. For example, a benzene derivative may be substituted with a propyl group or three methyl groups, all of which are at least three carbon atoms in total. Such solvents allow the inkjet liquid to be formed to contain a solvent, along with a binder and polyacene, that reduces or prevents jet clogging and component separation during spraying. The solvent may include those selected from the list of examples below. : Dodecylbenzene; 1-Methyl-4-tert-butylbenzene; Terpineol; Limonene; Isodurene; Terpineolene; Cymene; Diethylbenzene. The solvent may be a solvent mixture, i.e. one or a combination of two or more solvents, each solvent preferably having a boiling point of&gt; 100 ° C, more preferably&gt; 140 ° C. Such solvents also promote film formation of the layers to be laminated and reduce defects in the layers.

Inkjet liquids (ie, mixtures of solvents, binders and polyacenes) preferably have a viscosity of 1-100 mPa.s, more preferably 1-50 mPa.s, most preferably 1-30 mPa.s, at 20 ° C. Has. The use of binders in the present invention also makes it possible to adjust the viscosity of the coating solution to suit the requirements of a particular printhead. The semiconductor layer of the present invention can be thicker if desired, but is typically up to 1 micron (= 1 μm) thick. The exact thickness of the layer depends, for example, on the requirements of the electronic device that uses the layer. For use in OFETs or OLEDs, the layer thickness may typically be 500 nm or less. For the semiconductor layer of the present invention, 2 or 3 or more different polyacene compounds of formulas 1 to 9 may be used. Further or instead, two or three or more organic binders of the present invention may be used in the semiconductor layer.

As described above, the present invention further comprises (i) laminating a liquid layer of a mixture containing a polyacene compound, an organic binder resin or a precursor thereof and optionally a solvent on a substrate, and (ii) from a liquid layer to an organic semiconductor layer. Provided is a method for producing an organic semiconductor layer, which comprises forming a solid layer. In that method, the solid layer may be formed by evaporation of the solvent and / or by reacting the binder resin precursor (if present) as is to form the binder resin. The substrate may include any basic device layer, electrodes such as silicon wafers or separate substrates or polymer substrates. In one particular aspect of the invention, the binder can be aligned and, for example, can form a liquid crystal phase. In such cases, the binder may aid in the alignment of polyacenes, for example, the polyacene scaffolds preferentially align in the direction of charge transport. Suitable methods for aligning binders include those used for aligning polymerized organic semiconductors as described in WO 03/007397 (Plastic Logic).

The present invention also<u style="single">Formulation for semiconductor layer</u>Or provide use in layer electronic devices.<u style="single">Prescription</u>May be used as a high mobility semiconductor material for various devices and devices.<u style="single">Prescription</u>May be used, for example, in the form of a semiconductor layer or film. Thus, in other respects, the invention provides a semiconductor layer for use in electronic devices, where the layer is of the invention.<u style="single">Prescription</u>including. The layer or membrane may be less than about 30 microns. For various electronic device applications, the thickness may be less than about 1 micron. The layers can be laminated, for example, on a portion of an electronic device by either the solution coating or printing technique described above.

<u style="single">Prescription</u>For example, in field effect transistors (FETs) as semiconductor channels, for example, in pores or electron injection or transport layers or organic light emitting diodes (OLEDs) as electron emitting layers, photodetectors, chemical detectors, photocells (PVs), capacitors. It can also be used in sensors, logic circuits, displays, memory devices, etc., for example as a layer or membrane.<u style="single">Prescription</u>Can also be used in electrophotographic (EP) devices.<u style="single">Prescription</u>Is preferably a solution applied to form a layer or film on the above-mentioned device or apparatus to give cost advantage and versatility in manufacture. Of the present invention<u style="single">Prescription</u>The improved charge mobility of such devices allows such devices or devices to operate faster and / or more effectively. Of the present invention<u style="single">Prescription</u>And layers are particularly suitable for use as semiconductor channels in organic field effect transistors OFETs. Accordingly, the invention also provides an organic field effect transistor (OFET) that includes a source electrode, a drain electrode and an organic semiconductor channel connecting the source and drain electrodes, the organic semiconductor channel comprising the organic semiconductor layer of the present invention. Other features of OFET are well known to those skilled in the art.

Here, definitions and explanations of terms used in the present specification will be given. In the equations herein, markers written to indicate a list of groups or numbers (eg, R).₁, R₂If there is a list of indicators (eg,'n') and it says "independently in each case", this means that the respective signs and / or indicators are independent of each other. Means that one of the listed groups can be indicated independently within each repeating unit, independently within the range of each expression, and / or independently with each appropriately substituted group. To do. Therefore, in each of these cases, many different groups are single labels (eg R).₅). The terms "substituent," "substituent," "arbitrary substituent," and / or "arbitrarily substituted," as used herein, refer to the following groups (or these, unless otherwise listed): Indicates at least one (replaced by a group of). : Cyril, sulfo, sulfonyl, formyl, amino, imino, nitrilo, mercapto, cyano, nitro, halo, C_1~4Alkyl, C_6~12Aryl, C_1~4Alkoxy, hydroxy and / or combinations thereof. Any of these groups can be chemically the same group and / or a plurality of the groups described above (preferably 2) (eg, when amino and sulfonyl are directly attached to each other, they indicate a sulfamoyl group). It may include all possible combinations. Any preferred substituent is; C_1~4Includes alkyl; methoxy (any of these optionally substituted by at least one halo) and / or ethoxy; amino; and / or halo (arbitrarily substituted by at least one methyl and / or ethyl).

As used herein, the term "carbyl group" contains no non-carbon atoms (eg, -CC-) or is optionally combined with at least one other non-carbon atom (eg, alkoxy, carbonyl, etc.). ) Indicates either a monovalent or polyvalent organic group moiety containing at least one carbon atom. The terms "hydrocarbon group", "hydrocarbyl" or such terms are used herein interchangeably. The hydrocarbon group may be optionally substituted. Hydrocarbon groups Also, it may contain a heteroatom containing at least one of the following: oxy, thio, sulfinyl, sulfonyl, amino, imino, nitrilo and / or a combination thereof. Terms such as "alkyl" and "aryl" used herein may have already been replaced, and optionally, frequencies with different valencies, such as polyvalent species (eg, alkylene, arylene, etc.), are also indicated by this term. Is done. The term "halo" as used herein refers to fluoro, chloro, bromo and iodine.

Unless otherwise explicitly stated in the context, a group here containing a chain of 3 or 4 or more carbon atoms, the chain forms a straight line, a branch and / or a ring completely or partially (spiro and). Indicates a group that may (/ or include a fusion ring). Unless otherwise stated in the context, the plural forms of the terms used herein should be construed as including the singular and vice versa. Throughout the detailed description and claims herein, "includes" and "includes" and variations of the term, such as "includes" and "includes," are "included without limitation." It means that it is not intended to exclude (exclude) other components. It is highly appreciated that the modification of the above-described aspect of the present invention can be performed as long as it falls within the scope of the present invention. Each feature described herein may be replaced by alternative features of the same, equivalent or similar purpose, unless otherwise stated. Thus, unless otherwise stated, each feature described is only one example of a comprehensive set of equivalent or similar features.

All features described herein may be combined in any combination, except for combinations in which at least some of such features and / or steps are incompatible with each other. In particular, the preferred features of the present invention can be applied in all aspects of the present invention and may be used in any combination. Similarly, features described in non-essential combinations may be used separately (without combination). It is highly appreciated that many of the above features, especially preferred embodiments, are inventive in their own right and are not merely a part of the embodiments of the present invention. Independent protection may be sought for these features in addition to or instead of any of the inventions in the current claim.

The present invention will be described in more detail here with reference to the following examples, but it is merely a description and does not limit the scope of the present invention.<u style="single">Example</u><u style="single">Synthesis of organic semiconductor materials</u><u style="single">1. 6, 13-Synthesis of Bis (Triisopropylsilylethynyl) Pentacene-Compound 1</u><chemistry num="36"><img file="JP5089986B2_D0040.tif" /></chemistry>

Isopropylmagnesium chloride (2M in THF (10 mol equal to 6,13-pentacenequinone)) in a thermal drying flask with a mechanical stirrer, nitrogen inlet and outlet, condenser and suba-seal. Added. The solution was cooled during the addition of triisopropylsilyl acetylene using a cold water bath that served as a cooling trap to absorb all heat. Triisopropylsilyl acetylene (10.1 molar equivalent relative to 6, 13-pentacenequinone) was added dropwise to the reaction flask over 30 minutes and THF (10 ml for every 10 mmol of TIPS acetylene) was added. The cold water bath was removed and the solution was heated at 60 ° C for 20 minutes. The flask was then cooled to room temperature. 6, 13-Pentacenequinone (1 molar equivalent) was added to the Grignard reagent and the resulting cloudy suspension was heated at 60 ° C. (up to 3 hours) until the reaction appeared to be complete by HPLC. The flask was cooled to room temperature. A 10% aqueous HCl saturated with tin (II) chloride was carefully added to the brown / red reaction solution until the solution did not generate heat upon addition. (Note that when the tin (II) chloride solution is added, the reaction solution changes from brown / red to dark blue.) The resulting solution was heated at 60 ° C. for 30 minutes before cooling to room temperature. This crude mixture is sulphated from a water / DCM mixture.₄The organic phase was isolated by drying in), filtered and concentrated under vacuum to give a blue / black solid. Purification by column chromatography (silica gel, 5% DCM in hexanes) followed by recrystallization from acetone gave the title compound as a dark blue plate.

<u style="single">2.6, 13-Bis (triisopropylsilyl) alternative synthetic method for ethynylpentacene compound 1</u><u style="single">Compound 1</u><chemistry num="37"><img file="JP5089986B2_D0041.tif" /></chemistry>

(Triisopropylsilyl) acetylene (6 molar equivalents (2.18 ml, 9.72 mmol)) and tetrahydrofuran (THF) (15 ml) were added to the thermal dry flask and the solution was cooled to -78 ° C. 2.5 Mn-butyllithium in hexane (5.5 molar equivalents (3.56 ml, 8.91 mmol)) was subsequently added dropwise over 20 minutes. The resulting solution was cooled for an additional 45 minutes at -78 ° C. 6, 13-Pentacenequinone (1 molar equivalent (0.50 g, 1.62 mmol)) was added and the reaction mixture was warmed to room temperature with stirring overnight. SnCl₂A 10% aqueous HCl saturated with (5 ml) was added at room temperature and the reaction mixture was stirred at 50 ° C. for 30 minutes. 2MNa when cooling₂CO₃An aqueous solution (5 ml) was added, and the resulting crude solution was filtered through Celit and concentrated under vacuum. Purification by chromatography (flash silica, hexane: DCM, 95: 5) followed by acetone washing gave the title compound (0.73g, 70%) in dark blue powder, with a purity greater than 99% by HPLC. ..<tables num="4"><img file="JP5089986B2_D0042.tif" /></tables>

<u style="single">Synthesis of 3.2,3,9,10-tetramethyl-6,13-bis (triisopropylsilylethynyl) pentacene-compound 4</u><u style="single">3a.4,5-Synthesis of dimethylphthalaldehyde-Compound 2</u><chemistry num="38"><img file="JP5089986B2_D0043.tif" /></chemistry>

Dimethyl sulfoxide (DMSO) in DCM (10 ml) (7.5 ml, 105.8 mmol, 4.4 mol) in a solution of 2M oxalyl chloride (26.5 ml, 53.0 mmol, 2.2 molar equivalents) in dichloromethane (DCM) cooled to -78 ° C. Equivalent) The solution was added dropwise. The solution was stirred at -78 ° C for 5 minutes and 4,5-dimethylbenzene-1,2-dimethanol (4.0 g, 24.1 mmol, 1.0 molar equivalent) dissolved in a mixture of DCM-DMSO (2 ml-4 ml). It was added dropwise. The reaction mixture was stirred at 78 ° C. for 1 hour and triethylamine (20 ml) was added slowly dropwise. The reaction mixture was stirred at 78 ° C. for 10 minutes and slowly warmed to room temperature. Ice water (100 ml) was added to the reaction mixture and the aqueous layer was extracted with DCM (100 ml 3 times). The organic components were mixed, dried over magnesium sulphate, filtered and concentrated under vacuum to give a brown oil. Purification by column chromatography on silica gel (eluent: hexane-ethyl acetate 8: 2) gave the title compound (3.2 g, 82%) as white needles.¹1 H NMR (300.13 MHz, CDCl₃) δ (ppm) 2.42 (s, 6H) 7.73 (s, 2H) 10.50 (s, 2H)

<u style="single">3b. Synthesis of 2,3,9,10-tetramethyl-6,13-pentacenequinone-compound 3</u><chemistry num="39"><img file="JP5089986B2_D0044.tif" /></chemistry>

5% in solution of 4,5-dimethylphthalaldehyde (Compound 2) (1.59 g, 9.8 mmol, 2 eq) and 1,4-cyclohexanedione (0.54 g, 4.8 mmol, 1 eq) in ethanol (150 ml) Aqueous NaOH solution (3 ml) was added at room temperature. The reaction mixture was stirred for 30 minutes at room temperature and warmed to 60 ° C. After 1 hour at 60 ° C., the reaction mixture was cooled to room temperature. The resulting precipitate was filtered and washed with water (25 ml), ethanol (50 ml) and diethyl ether (50 ml) to give the title compound (1.63 g, 93%) as a yellow powder. IR (selected band) 1672 (quinone), 1579, 1452, 1396, 1221, 738 cm^-1

<u style="single">3c. Synthesis of 2,3,9,10-tetramethyl-6,13-bis (triisopropylsilylethynyl) pentacene-compound 4</u><chemistry num="40"><img file="JP5089986B2_D0045.tif" /></chemistry>

A solution of triisopropylsilylacetylene (3.7 ml, 16.4 mmol, 6 molar equivalents) in tetrahydrofuran (THF) (100 ml) cooled to -78 ° C and a 2.5 Mn-butyllithium solution in hexanes (6 ml, 5 mmol, 5.5). (Molar equivalent) was added dropwise. The solution was stirred at 78 ° C. for 45 minutes and 2,3,9,10-tetramethyl-6,13-pentacenequinone (Compound 3) (1 g, 2.7 mmol, 1 molar equivalent) was added. The reaction mixture was warmed and stirred at room temperature overnight. SnCl₂A 10% aqueous HCl (10 ml) saturated with water was added at room temperature and the reaction mixture was stirred at 50 ° C. for 45 minutes. 2MNa when cooling₂CO₃Aqueous solution (10 ml) was added and the resulting solution was stirred with Celit for 5 minutes. The solution was filtered through Celit and concentrated under vacuum to give a dark blue solid. Purification by column chromatography on silica gel (eluent, hexane: DCM 6: 4) followed by acetone washing gave the title compound (0.8 g, 42%) in dark blue powder. The purity was greater than 99% by HPLC.<tables num="5"><img file="JP5089986B2_D0046.tif" /></tables>

<u style="single">4.5,11-bis (triisopropylsilylethynyl) anthra [2,3-b: 6,7-b'] dithiophene- and 5,11-bis (triisopropylsilylethynyl) anthra [2,3-b: 7,, 6-b'] Synthesis of dithiophene-compound 8</u><u style="single">4a. Anthra [2,3-b: 6,7-b'] dithiophene-5,11-dione-Compound 5 and Anthra [2,3-b: 7,6-b'] dithiophene-5,11-dione -Synthesis of compound 6</u><chemistry num="41"><img file="JP5089986B2_D0047.tif" /></chemistry>

5% NaOH in a solution of thiophene-2,3-dicarbaldehyde (1.00 g, 7.1 mmol, 2 molar equivalents) and 1,4-cyclohexanedione (0.40 g, 3.6 mmol, 1 molar equivalent) in ethanol (100 ml). A (3 ml) aqueous solution was added at room temperature. The reaction mixture was stirred at room temperature for 30 minutes and warmed to 60 ° C. After 1 hour at 60 ° C., the reaction mixture was cooled to room temperature. The resulting precipitate was filtered and washed with water (20 ml), ethanol (40 ml) and diethyl ether (40 ml) to give the title compound (1.02 g, 89%) as a yellow powder. IR (selected band) 1667 (quinone), 1573, 1318, 1283 cm^-1

<u style="single">4b.5,11-bis (triisopropylsilylethynyl) anthra [2,3-b: 6,7-b'] dithiophene-compound 7 and 5,11-bis (triisopropylsilylethynyl) anthra [2,3-b' b: 7,6-b'] Synthesis of dithiophene-compound 8</u><chemistry num="42"><img file="JP5089986B2_D0048.tif" /></chemistry>

A 2.5 Mn-butyl lithium solution (3.4 ml, 8.5 mmol, 5.5) in hexane in a solution of triisopropylsilylacetylene (2.1 m1, 9.4 mmol, 6 mol equivalents) in tetrahydrofuran (THF) (50 ml) cooled to -78 ° C. (Molar equivalent) was added dropwise. The solution was stirred at -78 ° C for 45 minutes and anthradithiophene-5,11-dione (Compounds 5 and 6) (0.5 g, 1.6 mmol, 1 molar equivalent) was added. The reaction mixture was warmed and stirred at room temperature overnight. SnCl₂A 10% aqueous HCl (5 ml) saturated with water was added at room temperature and the reaction mixture was stirred at 50 ° C. for 45 minutes. 2MNa when cooling₂CO₃Aqueous solution (5 ml) was added and the resulting solution was stirred with Celit for 5 minutes. The solution was filtered through Celit and concentrated under vacuum to give a dark red solid. Purification by column chromatography on silica gel (eluent, hexane: DCM 8: 2) followed by washing with acetone gave the title compound (0.45 g, 44%) as a dark red powder. Purity was greater than 99% by HPLC (both syn and anti-isomer outflow).<tables num="6"><img file="JP5089986B2_D0049.tif" /></tables>

<u style="single">Synthesis of 5.6, 13-bis (trimethylsilyl) ethynyl pentacene-compound 9</u><chemistry num="43"><img file="JP5089986B2_D0050.tif" /></chemistry>

(Trimethylsilyl) acetylene (6 molar equivalents (13.7 ml, 97.3 mmol)) and tetrahydrofuran (THF) (110 ml) were added to the thermal dry flask and the solution was cooled to -78 ° C. 2.5 Mn-butyllithium in hexanes (5.5 molar equivalents (36.0 ml, 89.2 mmol)) was subsequently added dropwise over 20 minutes. The resulting solution was stirred for an additional 45 minutes at -78 ° C. 6, 13-Pentacenequinone (1 molar equivalent (5.0 g, 16.2 mmol)) was added and the reaction mixture was warmed to room temperature with stirring overnight. SnCl₂A 10% aqueous HCl (50 ml) saturated with water was added at room temperature and the reaction mixture was stirred at 50 ° C. for 30 minutes. 2MNa when cooling₂CO₃A (50 ml) aqueous solution was added and the resulting crude solution was filtered through Celit and concentrated under vacuum. Purification by chromatography (flash silica, hexane: DCM, 80:20) followed by acetone washing gave the title compound (3.8 g, 50%) in dark blue powder, with a purity greater than 99% by HPLC. ..¹1 H NMR (CDCl₃) δ 9.21 (4H, s, H-Ar), 8.05 (4H, m, H-Ar), 7.42 (4H, m, H-Ar) and 0.53ppm (18H, s, H-aliphatic)

<u style="single">6.6, 13-Synthesis of bis (triethylsilyl) ethynylpentacene-compound 10</u><chemistry num="44"><img file="JP5089986B2_D0051.tif" /></chemistry>

Isopropylmagnesium chloride (2M solution in THF; 10 molar equivalents (13.7 ml, 27.4 mmol)) and tetrahydrofuran (THF) (60 ml) were added to a thermal dry flask. Triethylsilyl acetylene (10 molar equivalents, 5.6 ml, 31.3 mmol) was added dropwise. The mixture was reflux heated for 20 minutes. The resulting solution was cooled to room temperature and 6,13-pentacenequinone (1 molar equivalent (1.0 g, 3.24 mmol)) was added. The reaction mixture was reflux heated for 1 hour and cooled to room temperature. SnCl₂A 10% aqueous HCl (50 ml) saturated with water was added at room temperature and the reaction mixture was stirred at 50 ° C. for 30 minutes. Saturated potassium bicarbonate solution (KHCO) when cooled₃) (25 ml) was added and the resulting crude solution was filtered through Celit and concentrated under vacuum. Purification by flash column chromatography (eluent 20% CH₂Cl₂Purification with (: hexane) followed by washing with acetone gave the title compound (1.1 g, 61%) in dark blue powder, which was more than 99% pure by HPLC.<tables num="7"><img file="JP5089986B2_D0052.tif" /></tables>

<u style="single">Synthesis of 7.6, 13-bis (4'-pentylphenyl) ethynylpentacene-compound 11</u><chemistry num="45"><img file="JP5089986B2_D0053.tif" /></chemistry>

Isopropylmagnesium chloride (2M solution in THF; 10 molar equivalents (32.4 ml, 64.8 mmol)) and tetrahydrofuran (THF) (60 ml) were added to a thermal dry flask. 1-Etinyl-4-pentylbenzene (10 molar equivalents, 12.4 mL, 63.7 mmol) was added dropwise. The mixture was reflux heated for 20 minutes. The resulting solution was cooled to room temperature and pentasenquinone (1 molar equivalent (2.0 g, 6.5 mmol)) was added. The reaction mixture was reflux heated for 30 minutes. The mixture was cooled to room temperature. SnCl₂A 10% aqueous HCl (20 ml) saturated with water was added at room temperature and the reaction mixture was stirred at 50 ° C. for 30 minutes. When cooling, Na₂CO₃The solution (50 ml) was added slowly. Transfer material to 1 L separatory funnel, water (100 ml) and CH₂Cl₂(50 ml) was added. Separate the organic and aqueous phases and CH the aqueous phase₂Cl₂Extracted with (3 x 50 ml). The mixed organic phase was then washed with water (100 ml), filtered through Whatman No. 1 filter paper and concentrated to give a blue solid. The material was stirred with acetone (50 ml) and filtered to give a blue powder (3.0 g, 75%). Purification of 1 g of this material by flash column chromatography (flash silica, eluent 40% CH₂Cl₂Purification with (: hexane) gave a blue solid product (0.8 g, 80% recovery) with a purity greater than 99% by HPLC.<tables num="8"><img file="JP5089986B2_D0054.tif" /></tables>

<u style="single">8. Synthesis of naphtho [2,1,8-cla (qra)] naphthacene-7,12- (triisopropylsilyl) ethynyl-compound 12</u><chemistry num="46"><img file="JP5089986B2_D0055.tif" /></chemistry>

In a flame-dried flask (g added Li triisopropylsilyl) acetylene (6 molar equivalents (2.03 ml, 9.03 mmol)) and tetrahydrofuran (THF) (50 ml), the solution was cooled to -78 ° C. 2.5 Mn-butyllithium in hexane (5.5 molar equivalents (5.16 ml, 8.25 mmol)) was added dropwise over 20 minutes. The resulting solution was cooled for an additional 45 minutes at -78 ° C. Naft [2,1,8-cla] naphthacene-7,12-dione (1 molar equivalent (0.50 g, 1.50 mmol)) was added and the reaction mixture was warmed to room temperature with stirring overnight. SnCl₂A 10% aqueous HCl (10 ml) saturated with water was added at room temperature and the reaction mixture was stirred at 50 ° C. for 30 minutes. 2MNa when cooling₂CO₃An aqueous solution (5 ml) was added, and the resulting crude solution was filtered through Celit and concentrated under vacuum. Purification by chromatography (flash silica, hexane: DCM, 95: 5) followed by acetone washing gave the title compound (0.23g, 23%) in red powder, which was greater than 99% pure by HPLC. ..<tables num="9"><img file="JP5089986B2_D0056.tif" /></tables>

<u style="single">Synthesis of 9.5, 14- (triisopropylsilyl) acetylene pentacene-compound 14</u><u style="single">9a.5, 14-Synthesis of Pentacenequinone-Compound 13</u><chemistry num="47"><img file="JP5089986B2_D0057.tif" /></chemistry>

Add 2,3-naphthalenedicarboxyaldehyde (1 mol equivalent (0.29 g, 1.57 mmol)) and 1,4-dihydroxynaphthalene (1 mol equivalent (0.25 g, 1.57 mmol)) to a thermal drying flask and add these reagents. Was rinsed with nitrogen for 15 minutes and anhydrous pyridine (5 ml) was added. The resulting solution was stirred at 120 ° C. for 24 hours. Upon cooling, the solid product was filtered, washed successively with methanol (10 ml), 10% copper sulphate solution (10 ml), water (10 ml) and acetone (10 ml) and dried in a vacuum oven. The product was an orange / brown solid (0.14 g, 29%) with a purity greater than 99% by HPLC.<tables num="10"><img file="JP5089986B2_D0058.tif" /></tables>

<u style="single">Synthesis of 9b.5, 14- (triisopropylsilyl) acetylene pentacene-compound 14</u><chemistry num="48"><img file="JP5089986B2_D0059.tif" /></chemistry>

(Triisopropylsilyl) acetylene (6 molar equivalents (1.31 ml, 5.84 mmol)) and tetrahydrofuran (THF) (10 ml) were added to the thermal dry flask and the solution was cooled to -78 ° C. 2.5 Mn-butyllithium in hexane (5.5 molar equivalents (3.34 ml, 5.35 mmol)) was added dropwise over 20 minutes. The resulting solution was cooled for an additional 45 minutes at -78 ° C. 5,14-Pentacenequinone (Compound (13)) (1 molar equivalent (0.30 g, 0.97 mmol)) was added and the reaction mixture was warmed to room temperature with stirring overnight. SnCl₂A 10% aqueous HCl (5 ml) saturated with water was added at room temperature and the reaction mixture was stirred at 50 ° C. for 30 minutes. 2MNa when cooling₂CO₃An aqueous solution (5 ml) was added, and the resulting crude solution was filtered through Celit and concentrated under vacuum. Purification by chromatography (flash silica, hexane: DCM, 90:10) followed by acetone washing gave the title compound (0.22 g, 35%) in dark blue powder, which was greater than 99% pure by HPLC. ..<tables num="11"><img file="JP5089986B2_D0060.tif" /></tables>

<u style="single">Synthesis of 10.1,8-difluoro-6,13-bis (triisopropylsilylethynyl) pentacene-compound 19 and 1,11-difluoro-6,13-bis (triisopropylsilylethynyl) pentacene-compound 20</u><u style="single">10a. Synthesis of 3-fluorobenzene-1,2-dimethanol-compound 15</u><chemistry num="49"><img file="JP5089986B2_D0061.tif" /></chemistry>

LiAlH cooled to -78 ° C₄ A solution of 3-fluorophthalic acid (5.0 g, 27.2 mmol, 1 eq) in THF (25 ml) was added dropwise to a solution of (1 M in tetrahydrofuran) (54 ml, 54.0 mmol, 2.0 eq). The reaction mixture was warmed to room temperature and stirred at 70 ° C. for 2 hours. 2M sodium hydroxide solution (25 ml) was added to the resulting solution cooled to 0 ° C, and cold water (25 ml) and THF (50 ml) were added. The reaction mixture was further extracted with THF (3x50 ml). The organic components were mixed, washed with brine, dried over magnesium sulfate, filtered and concentrated under vacuum to give a pale yellow solid. Purification by recrystallization from acetone / hexane gave the title compound in the form of white needles (3.3 g, 79%).<tables num="12"><img file="JP5089986B2_D0062.tif" /></tables>

<u style="single">10b.3-Synthesis of 3-fluorophthalaldehyde-Compound 16</u><chemistry num="50"><img file="JP5089986B2_D0063.tif" /></chemistry> Dimethyl sulfoxide (DMSO) (3.10 ml, 44 mmol, 4.4 eq) solution in DCM (10 ml) to a 2 M oxalyl chloride solution (11 m 1, 22 mmol, 2.2 eq) in dichloromethane (DCM) cooled to -78 ° C. It was added dropwise. The solution was stirred at -78 ° C for 5 minutes and dissolved in a mixture of DCM-DMSO (1-2 ml) 3-fluorobenzene-1,2-dimethanol (Compound 17) (1.55 g, 10 mmol, 1.0 molar equivalent). ) Was added dropwise. The solution was then stirred at -78 ° C for 1 hour and triethylamine (25 ml) was added slowly at -78 ° C. The reaction mixture was stirred at 78 ° C. for 10 minutes and slowly warmed to room temperature. Ice water (50 ml) was added to the reaction mixture and the aqueous layer was extracted with DCM (50 ml 3 times). The organic components were mixed, dried over magnesium sulphate, filtered and concentrated under vacuum to give a brown oil. Purification by distillation gave the title compound as a pale yellow solid (1.10 g, 73%).<tables num="13"><img file="JP5089986B2_D0064.tif" /></tables>

<u style="single">10c. Synthesis of 1,8-difluoro-6,13-pentacenequinone-compound 17 and 1,11-difluoro-6,13-pentacenequinone-compound 18</u><chemistry num="51"><img file="JP5089986B2_D0065.tif" /></chemistry> 5% aqueous NaOH solution in a solution of 3-fluorophthalaldehyde (Compound 18) (0.42 g, 2.8 mmol, 2 eq) and 1,4-cyclohexanedione (0.15 g, 1.4 mmol, 1 eq) in ethanol (45 ml) (0.6 ml) was added at room temperature. The reaction mixture was stirred at room temperature for 30 minutes and warmed to 60 ° C. After 1 hour at 60 ° C., the reaction mixture was cooled to room temperature. The resulting precipitate was filtered and washed with water (15 ml), ethanol (30 ml) and diethyl ether (30 ml) to give the title compound in yellow powder for use as a recovery (0.40 g, 87%).<tables num="14"><img file="JP5089986B2_D0066.tif" /></tables>

<u style="single">Synthesis of 10d.1,8-difluoro-6,13-bis (triisopropylsilylethynyl) pentacene-compound 19 and 1,11-difluoro-6,13-bis (triisopropylsilylethynyl) pentacene-compound 20</u><chemistry num="52"><img file="JP5089986B2_D0067.tif" /></chemistry> Triisopropylsilyl acetylene (1.2 m, 5.3 mmol, 6 mol eq) in THF (30 ml) cooled to -78 ° C with a 2.5 Mn-butyllithium solution in hexanes (1.9 ml, 4.8 mmol, 5.5 eq). It was added dropwise. The solution was stirred for 45 minutes-78 ° C and difluoro-6,13-pentacenequinones (Compounds 17 and 18) (0.3 g, 0.9 mmol, 1 molar equivalent) were added. The reaction mixture was warmed and stirred overnight at room temperature. SnCl₂A 10% aqueous HCl (3 ml) saturated with water was added at room temperature and the reaction mixture was stirred at 50 ° C. for 45 minutes. 2MNa when cooling₂CO₃An aqueous solution (3 ml) was added. The resulting solution was filtered through Celit and concentrated under vacuum to give a dark red solid. Purification by column chromatography on silica gel (eluent, hexane: DCM 9: 1) followed by washing with acetone gave the title compound (0.38 g, 65%) in dark blue powder, with HPLC (both syn and anti-isomer). The purity was greater than 99% due to spillage).<tables num="15"><img file="JP5089986B2_D0068.tif" /></tables>

<u style="single">11.2,3,9,10-Tetrafluoro-6,13-bis (triisopropylsilylethynyl) pentacene-Compound 24 synthesis</u><u style="single">11a.4,5-Synthesis of difluorobenzene-1,2-dimethanol-Compound 21</u><chemistry num="53"><img file="JP5089986B2_D0069.tif" /></chemistry> LiAlH cooled to -78 ° C₄ A solution of 4,5-difluorophthalic anhydride (1.0 g, 5.4 mmol, 1 molar equivalent) in THF (5 ml) was added dropwise to a solution of (1 M in tetrahydrofuran) (11 ml, 11.0 mmol, 2.0 molar equivalents). .. The reaction mixture was warmed to room temperature and stirred at 70 ° C. for 2 hours. 2M sodium hydroxide solution (5 ml) was added to the resulting solution cooled to 0 ° C, and cold water (5 ml) and THF (10 ml) were added. The reaction mixture was further extracted with THF (50 ml 3 times). The organic components were mixed, washed with brine, dried over magnesium sulfate, filtered and concentrated under vacuum to give a pale yellow solid. Purification by recrystallization from acetone / hexane gave the title compound in the form of pale yellow needles (0.8 g, 85%).<tables num="16"><img file="JP5089986B2_D0070.tif" /></tables>

<u style="single">11b.4,5-Difluorophthalaldehyde-Synthesis of Compound 22</u><chemistry num="54"><img file="JP5089986B2_D0071.tif" /></chemistry> Dimethyl sulfoxide (DMSO) in DCM (5 ml) (1.25 ml, 17.7 mmol, 4.4 eq) in 2M oxalyl chloride solution (4.5 ml, 8.8 mmol, 2.2 eq) in dichloromethane (DCM) cooled to -78 ° C. ) The solution was added dropwise. The solution was stirred at -78 ° C for 5 minutes and dissolved in a mixture of DCM-DMSO (1-2 ml) 4,5-difluorobenzene-1,2-dimethanol (Compound 21) (0.70 g, 4.0 mmol, 1.0 molar equivalent) was added dropwise. The solution was stirred at -78 ° C for 1 hour and triethylamine (15 ml) was added slowly at -78 ° C. The reaction mixture was stirred at 78 ° C. for 10 minutes and slowly warmed to room temperature. Ice water (25 ml) was added to the reaction mixture and the aqueous layer was extracted with DCM (30 ml 3 times). The organic components were mixed, dried over magnesium sulphate, filtered and concentrated under vacuum to give a yellow oil. Purification by column chromatography on silica gel (eluent, hexane: DCM 2: 8) gave the title compound as a pale yellow solid (0.58 g, 85%).<tables num="17"><img file="JP5089986B2_D0072.tif" /></tables>

<u style="single">11c. Synthesis of 2,3,9,10-tetrafluoro-6,13-pentacenequinone-compound 23</u><chemistry num="55"><img file="JP5089986B2_D0073.tif" /></chemistry> 5% in solution of 4,5-difluorophthalaldehyde (Compound 22) (0.48 g, 2.8 mmol, 2 eq) and 1,4-cyclohexanedione (0.16 g, 1.4 mmol, 1 eq) in ethanol (40 ml) Aqueous NaOH solution (0.6 ml) was added at room temperature. The reaction mixture was stirred at room temperature for 30 minutes and warmed to 60 ° C. After 1 hour at 60 ° C., the reaction mixture was cooled to room temperature. The resulting precipitate was filtered and washed with water (15 ml), ethanol (30 ml) and diethyl ether (30 ml) to give the title compound in yellow powder for use as a recovery (0.35 g, 64%).

<u style="single">11d. Synthesis of 2,3,9,10-tetrafluoro-6,13-bis (triisopropylsilylethynyl) pentacene-compound 24</u><chemistry num="56"><img file="JP5089986B2_D0074.tif" /></chemistry> Triisopropylsilyl acetylene (0.7 ml, 3.2 mmol, 6 mol eq) in THF (20 ml) cooled to -78 ° C with a 2.5 Mn-butyllithium solution in hexanes (1.2 ml, 2.9 mmol, 5.5 eq). It was added dropwise. The solution was stirred for 45 minutes at -78 ° C and 2,3,9,10-tetrafluoro-6,13-pentacenequinone (Compound 23) (0.2 g, 0.5 mmol, 1 molar equivalent) was added. The reaction mixture was warmed to room temperature overnight. SnCl₂A 10% aqueous HCl (2 ml) saturated with water was added at room temperature and the reaction mixture was stirred at 50 ° C. for 45 minutes. 2MNa when cooling₂CO₃An aqueous solution (2 ml) was added. The resulting solution was filtered through Celit and concentrated under vacuum to give a dark blue solid. Purification by column chromatography on silica gel (eluent, hexane: DCM 9: 1) followed by acetone washing gave the title compound (0.13 g, 35%) in dark blue powder.<tables num="18"><img file="JP5089986B2_D0075.tif" /></tables>

<u style="single">Examples 12 ~ 15-Measurement of mobility of OFETs produced in the absence and presence of (polymerized) binder</u><u style="single">Determining field effect mobility</u> The field-effect mobilities of the following organic semiconductor materials were measured using the method described in Holland et al, J. Appl. Phys. Vol.75, p.7954 (1994). In the example below, a test field effect transistor was manufactured using standard techniques, such as a PEN substrate with Pt / Pd source and drain electrodes patterned with a shadow mask.<u style="single">Formulation for semiconductor layer</u>Was produced using Compound 1 (Example 12) and Compound 4 (Example 14) mixed with an inert polymerization binder resin (poly (alpha-methylstyrene) (p-αMS)).<u style="single">Formulation for semiconductor layer</u>One portion was then dissolved in 99 parts of solvent (Examples 12 and 13 in toluene, Examples 14 and 15 in 1,2-dichlorobenzene) and spin coated onto the substrate at 500 rpm for 18 seconds. The sample was placed in the oven at 100 ° C for 20 minutes to ensure complete drying. For comparison, a film of pure organic semiconductor compound (OSC) in the absence of a binder was applied to the substrate by spin coating (Comparative Example 13 for Compound 1 and Comparative Example 15 for Compound 4). These samples were also dried in the oven at 100 ° C for 20 minutes. Insulator material (Cytop 107M available from Asahi Glass) 3 parts perfluorosolvent (FC75, Acros Catalog No. 12380) Two parts were mixed and typically spin coated onto a semiconductor about 1 μm thick. The sample was placed in the oven once more at 100 ° C. for 20 minutes to evaporate the solvent from the insulator. Gold gate contact was determined across device channels by evaporation through a shadow mask. Many devices were manufactured consisting of unpatterned Pt / Pd base layers, insulator layers manufactured in a manner similar to FET devices, and top electrodes of known shapes to determine the capacitance of the insulator layer. Capacitance was measured using a portable multimeter connected to the metal on both sides of the insulator. Other decisive parameters of the transistor are the length of the drain and source electrodes facing each other (W = 30 mm) and their distance from each other (L = 130 mm).

The voltage applied to the transistor is relative to the potential of the source electrode. For p-type gate materials where a negative potential is applied to the gate, positive charge carriers (holes) accumulate on the opposite side of the semiconductor gate dielectric. (A positive voltage is applied to the n-channel FET.) Here, it is called the storage mode. Capacitance C per unit area of gate dielectric_iDetermines the amount of charge it brings. Negative potential V_DSWhen adding to the drain, the accumulated carriers are source-drain current I_DSGeometric factors such as the shape, size and distance of the drain and source electrodes, which depend primarily on the density of accumulated carriers and, importantly, the mobility of the source-drain channels, affect the current. Typical ranges of gate and drain voltages were read during device investigation. The source and drain currents are described by equation 1.<maths num="2"><img file="JP5089986B2_D0076.tif" /></maths>In the formula, V_OIs the offset voltage and I_ΩIs a resistance current independent of the gate voltage and is due to the finite permittivity of the material. Other parameters are described above.

A transistor sample was attached to the sample holder for electrical measurement. Microprobe connections were made using Karl Suss PH100 miniature probe-heads at the gate, drain and source electrodes. These were connected to a Hewlett-Packard 4155B parameter analyzer. Set the drain voltage to -5V, read the gate voltage from + 20 to -60V, and return to + 20V in 1V steps. | V_G|&gt; | V_DS| When accumulating, the source-drain current is V_GIt changes linearly with. Therefore, the field effect mobility is I according to equation 2._DSAgainst V_G It can be calculated from the gradient (S) of.<maths num="3"><img file="JP5089986B2_D0077.tif" /></maths>

All field-effect mobilities cited below were calculated using this regime (unless otherwise stated). When the field effect mobility changes with the gate voltage, the value is | V in storage mode._G|&gt; | V_DSIt takes the highest level value in the regime that becomes |. The values listed in Table 4 are the average of several devices (manufactured on the same substrate), and the sample size relative to the number of devices tested is also listed in Table 4. Figure 1 shows an example of the current-voltage and mobility-voltage characteristics of Example 12. Forward and backward scans depict low device current hysteresis. The results show good charge mobility of OFET devices when using binders in the tested organic semiconductor materials. When no binder is used, the mobility measured with devices coated on the same substrate varies considerably. This result is reflected in the wide standard deviation (a% of the mean) of the mobility values of the OFETs applied to the same substrate.

<u style="single">Table 4-Mobility value performance of OFETs in semiconductor formulations manufactured with or without binder material</u><tables num="19"><img file="JP5089986B2_D0078.tif" /></tables>

The results in Table 4 show the results for OFET devices.<u style="single">Prescription</u>It is shown that there is a substantial improvement in mobility value and the uniformity of OFET when a (polymerization) binder is used. The improvement in homogeneity is indicated by a small standard deviation (Std.dev.) Of the mobility results as a percentage of the mean values in the examples with binders (Examples 12 and 14). This is in contrast to Examples 13 and 15 without the binder, which show a wide standard deviation (ratio of mean values).

<u style="single">Examples 16-26-Mobility values of OFETs manufactured using different polymerization binders</u> OFETs were prepared using the methods described in Examples 12-15, except that different polymerization binders were used.<u style="single">Table 5-Mobility values of OFETs manufactured using different polymerization binders</u>

<tables num="20"><img file="JP5089986B2_D0079.tif" /></tables>

Topas® 8007 --ex. Ticona (straight olefin and cycloolefin (norbornene) copolymer), (Examples 16 and 17); PS (1M)-Polystyrene Mw = 1,000,000 Aldrich Catalog No. 48,080-0, (Example 18); p-4-MS-Poly-4-methylstyrene Aldrich Catalog No. 18,227-3, (Example 19) PS-co-αMS-Polystyrene-co-alpha-methylstyrene Aldrich Catalog No. 45,721-3, (Example 20); Poly (vinyl cinnamate) Aldrich No: 18,264-8, (Example 21) PMMA-Polymethylmethacrylate Mn = 797, (Example 22) PVP-Poly-4-Vinylphenol Aldrich Catalog No. 43,622-4, (Comparative Example 23); PVA-Polyvinyl alcohol Aldrich Catalog No. 36,316-2, (Comparative Example 24); Poly (4-vinylbiphenyl) Aldrich Catalog No. 18,254-0, (Example 25);^a Polymer Handbook (3rd edition) Wiley and Sons (1989).^{b b} Manufacturer data^c Obtained by measuring the capacitance and the thickness of the binder membrane between the two metal electrodes, the relationship ε = Cd / E₀A (in the formula, C is capacitance, d is film thickness, E₀Calculates the dielectric constant ε using the permittivity of free space and A indicates the area of the capacitor).^d Ficker et al., J. Appl. Phys. 2003 94 (4), 2638.^e Stutzman et al. Science 2003, 299, 1881. The results in Table 5 show that binders with a dielectric constant value greater than 3.3 significantly reduce the mobility value of the OFET device. Therefore, a preferred polymerization binder is a polymerization binder having a dielectric constant value of less than 3.3.

<u style="single">Example 27 ~ 28</u> OFETs were produced using the methods described in Examples 12 to 15 above, except that the polymerization binder used was not an insulating binder but a semiconductor material. The results are shown in Table 6.<u style="single">Table 6-Mobility values of OFETs manufactured using semiconductor binders</u><tables num="21"><img file="JP5089986B2_D0080.tif" /></tables>

In Table 6, poly (9-vinylcarbazole) is available from Aldrich Catalog No .: 18,260-5 (Example 27). ^* -See Schaffert RM IBM Journal of Res. And Devel. Vol 15 No1, p79 (1971) c --Same as Table 5 PTAA1-Triarylamine of formula 18<chemistry num="57"><img file="JP5089986B2_D0081.tif" /></chemistry>In the formula, n = 10.7 and Mn = 3100 (Adv. Funct. Mater. 2003, 13, No. 3. p199-204) The results in Table 6 show that semiconductor binders may also be used to obtain devices of the invention that exhibit good mobility values.

<u style="single">Example 29 ~ 31</u> OFETs were remanufactured using the methods described in Examples 12-15 above. However, in Examples 29-31, the ratio of OSC material to binder was varied. Example 12 is also included in the comparison.<u style="single">Table 7-Mobility values of OFETs manufactured by varying the amount of binder to OSC material</u><tables num="22"><img file="JP5089986B2_D0082.tif" /></tables> The above results show that good mobility values are obtained with OFET devices even when the OSC material and binder are in a 50:50 ratio.

<u style="single">Example 32-35-Mobility value of OFETs manufactured by changing the solid content</u><u style="single">Prescription</u>OFETs were remanufactured using the methods described in Examples 12-15 above, except that the solids content of<u style="single">Table 8-Changes in solid content of coating liquid used for OFET manufacturing</u><tables num="23"><img file="JP5089986B2_D0083.tif" /></tables>

<figref num="1">It is a figure which shows the example of the current-voltage and mobility-voltage characteristic of Example 12.</figref>