JP5155852B2 - Aryl-ethylene substituted aromatic compounds and their use as organic semiconductors - Google Patents

Description

  The present disclosure relates to a new class of aryl-ethylene substituted aromatic compounds. The present disclosure also relates to the use of these compounds in electronic devices and methods for making these devices.

  Organic materials are widely used in electronic devices such as organic thin film transistors (OTFTs), organic light emitting diodes (OLEDs), photovoltaic diodes, and liquid crystal displays. OTFTs are of particular interest for use in low cost integrated circuit (IC) technology suitable for applications such as smart cards, electronic tags, displays and memory devices. In OTFT, the semiconductor layer is made of an organic semiconductor material containing a conjugated polymer and an oligomer. Many organic materials having the electronic properties necessary for electronic device applications have been synthesized.

  Organic compounds that have been studied for use as semiconductors include conjugated polymers such as regioregular poly (3-alkylthiophene), polyfluorene-bithiophene copolymers, polycyclic aromatic amines and polythiophene derivatives, pentacene, tetracene and their derivatives. And conjugated oligomers such as oligothiophene, fluorene-thiophene oligomer, and phenylthiophene polysomer.

Unfortunately, the performance of most of the organic semiconductor compounds described above is either low charge mobility (about 0.1 cm ² / Vs) or unstable. For example, pentacene has a high mobility (about 0.1-2 cm ² / Vs), but also has a relatively low band gap (2.2 eV) and a high HOMO (highest occupied molecular orbital) energy level. Easily oxidized. Furthermore, since pentacene compounds often exhibit high oxygen and humidity sensitivity, a high on / off ratio can only be obtained in an inert atmosphere. As a result of these features, device stability is poor, making pentacene compounds unsuitable for practical electronic circuit applications. On the other hand, compounds such as oligofluorene, oligofluorene-thiophene, phenylene-thiophene and conjugated polyfluorene-thiophene polymers show improved stability but are not used in highly efficient electronic devices due to their low mobility . Accordingly, there remains a need for a class of organic compounds that have high mobility and high on / off ratios and are stable to heat, light and air.

  There is also a need for organic compounds that can be easily incorporated into electronic devices such as OLEDs using commercially available manufacturing methods. In other aspects of the OLED, a short device lifetime is a commercial defect. Organic triarylamine compounds such as NPD and derivatives thereof are widely used as hole transport materials. The low charge mobility of these triarylamine compounds and the low glass transition temperature of the hole transport material are believed to limit the stability of the OLED. For this reason, new materials with high hole charge mobility and thermal stability are needed for OLEDs.

US Pat. No. 6,621,098 US Patent Application Publication No. 2004/0254297 US Patent Application Publication No. 2004/029133 PCT Publication Application International Publication No. 02/02714 Pamphlet US Patent Application Publication No. 2001/0019782 EP11991612 International Publication No. 02/15645 Pamphlet EP 1191614 US Pat. No. 6,303,238 International Publication No. 00/70655 Pamphlet International Publication No. 01/41512 Pamphlet US Pat. No. 6,452,207 Literature (Miyaura, N, Suzuki, A., Chem. Rev. (1995), 95 (7), 2457-83) Scheme 5, Lightfoot, A.M. P. Maw, G .; Thirsk, C.I. Tiddle, S .; J. et al. R. , Whiting, A. Tetrahedron Lett. (2003), 44 (41), 7645-7648 Darses, S .; Genet, J .; P. Eur. J. et al. of Org. Chem. (2003), (22), 4313-4327 Herrmann, W.H. A. Reisinger, C.I. P. Hater P. "C-C coupling reaction (Heck, Still, Suzuki, etc.), water-phase organometallic catalyst (C-C coupling reactions (Heck, Stille, Suzuki, etc.). ), 511-523 Huo, S.A. Negishi, E .; , Palladium-catalyzed alkenyl-aryl, aryl-alkenyl and alkenyl-alkenyl coupling reactions Organopalladium Chemistry for Organic Synthesis (2002), 1, 335-408 of Organic Synthesis Littke, A.R. F. Fu, G. C. Angew. Chem. Int. Ed. (2002), 41 (22), 4176-4211 Farina, V.M. The latest synthesis and catalysis (Adv. Synthesis & Catalysis) (2004), 346 (13-15), 1553-1582. Braese, S.M. De Meijere, A .; , Double and multiple Heck reactions Organopalladium Chemistry for Organic Synthesis of Organic Synthesis (2002), 1: 1179-1208 Itami, K .; Ushiogi, Y. et al. Nokami, T .; Ohashi, Y .; Yoshida, J. et al. Org. Lett. (2004), 6 (21), 3695-3698. Reetz, M.C. T.A. , De Vries, J.A. G. Chem. Commun. (2004), (14) 1559-1563) Scheme 6 and Kerins, F. O'Shea, D.C. F. , J .; Org. Chem. 2002, 67, 4968-4971 S. M.M. By Sze, Physics of Semiconductor Devices, 2nd edition, John Wiley and Sons, New York (1981) Peter Van Zant, Microchip Fabrication, 4th edition, McGraw-Hill, New York (2000) S. M.M. Physics of Semiconductor Devices, 2nd edition by Sze, John Wiley and Sons, New York (1981), p. 492 “Flexible light-emitting diodes from solid conducting polymer” Nature, 357, 477, 479 (June 11, 1992) Kirk Osmer Encyclopedia of Chemical Technology, 4th edition, volume 18, pages 837, 860, 1996, Y.C. Wang Bradley et al., Synth. Met. (2001), 116 (1-3), 379-383 and Campbell et al., Phys. Rev. B, Volume 65 085210 Hodge, P.A. , Power, G.M. A. Rabjohns, M .; A. Chem. Commun. 1997, 73 Ficker et al. Appl. Phys. 94, 2638 (2003)

  Formula 1:

A compound represented by
Where
Ar is an arylene group,
Ar ′ and Ar ″ are independently selected from aryl groups;
R ^{1 to} R ⁴ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R Independently selected from the group consisting of ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
m and n are integers each independently having a value of 0 to 5, and m + n ≠ 0.

  In one embodiment, Ar is the following group:

And selected from the group consisting of these,
Where
Q is selected from the group consisting of S, Se, Te, O and NR ⁰ ;
q and r are integers each independently having a value of 0 to 5,
s is an integer having a value of 1 to 5,
R ⁰ is independently selected from the group consisting of hydrogen, alkyl and aryl;
R ^{5 to} R ¹⁰ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R Independently selected from the group consisting of ₂ and CN;
R is as described above,
In the formula, any two adjacent groups R ^{5 to} R ¹⁰ can be combined to form a ring.

  Synthetic methods for the preparation of compounds of Formula 1 are also provided.

  Also provided are hole transport compounds represented by Formula 1 and hole transport layers comprising these compounds.

  An electron transport compound represented by Formula 1 and an electron transport layer including these compounds are also provided.

  Buffer layers containing these compounds are also provided.

  An electronic device comprising an organic thin film transistor (OTFT) comprising a compound represented by Formula 1 is also provided. A method of manufacturing these electronic devices is also provided.

  A display device comprising the compound represented by Formula 1 is also provided.

  Also provided are organic light-emitting diodes, photoconductors, memory cells, current limiters, field effect diodes, Schottky diodes, photovoltaic cells, photodetectors, rectifiers, transistors, thermistors and pn junctions comprising the compound represented by Formula 1. Is done.

  For a better understanding of the concepts presented herein, embodiments are illustrated in the accompanying drawings.

  Those skilled in the art will appreciate that the objects of the drawings are illustrated for simplicity and clarity and are not necessarily to scale. For example, in order to better understand the embodiments, some dimensions of the objects in the drawings are exaggerated relative to other objects.

  A new class of substituted arylethylene aromatic compounds and methods for the synthesis of these compounds are provided. The use of these and other substituted arylethylene aromatic compounds in organic semiconductor devices is disclosed.

  Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans will appreciate other aspects and embodiments without departing from the scope of the invention.

  Other features and advantages of one or more embodiments will be apparent from the following detailed description and from the claims. In the best mode for carrying out the invention, the definitions and explanations of terms are first given, followed by aryl-ethylene aromatic compounds, general preparation methods, semiconductor devices and finally examples.

(1. Definition and explanation of terms)
Before addressing details of embodiments described below, some terms are defined or explained.

  As used herein, the term “aromatic” refers to an unsaturated cyclic organic compound or a group having a continuous conjugation with a delocalized π electron. The aromatic group may have one or more rings, each having 2n + 2π electrons. The term includes groups having one or more heteroatoms having π electrons in the ring. In one embodiment, the heteroatom is selected from the group consisting of N, O and S.

  As used herein, the term “acene” refers to a hydrocarbon parent component that contains two or more ortho-fused benzene rings in a linear configuration. “Acene” includes naphthalene (two ortho-fused benzene rings) and anthracene (three ortho-fused benzene rings). A system of four or more fused benzene rings is named with a numeric prefix and ends with “-acene” after indicating the number of benzene rings.

  The term “alkyl” used as part of another term or independently refers to a saturated hydrocarbon group. Examples of the alkyl group include n-butyl, n-pentyl, n-heptyl, iso-butyl, t-butyl and iso-pentyl. This term also includes heteroalkyl. In one embodiment, the alkyl group has 1-20 carbon atoms. In one embodiment, the alkyl group is a fluoroalkyl group.

  The term “alkyl ether” refers to an alkyl group substituted with O and having one or more carbon atoms attached through oxygen.

  The term “etheralkyl” refers to an alkyl group substituted with O and having one or more carbon atoms attached through the carbon.

  The term “alkenyl” used as part of another term or independently refers to a hydrocarbon group having one or more double bonds between adjacent carbon atoms of the group. Examples of alkenyl groups include vinyl, allyl, butenyl, pentenyl and heptenyl. This term includes heteroalkenyl groups. In one embodiment, the alkenyl group has 1-20 carbon atoms.

  The term “alkynyl” used as part of another term or used independently refers to a hydrocarbon group having one or more triple bonds between adjacent carbon atoms of the group. Alkynyl groups include ethynyl, propynyl, butynyl, hexynyl and heptynyl. This term includes heteroalkyl groups. In one embodiment, the alkynyl group has 1-20 carbon atoms.

  The term “aryl” used as part of another term or used independently refers to an aromatic group having one point of attachment. The term “arylene” refers to an aromatic group having two points of attachment. In one embodiment, the aryl group has 4 to 30 carbon atoms.

The term “silyl” as part of another term or used independently refers to the group —SiR ₃ . Wherein R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino.

  The term “thioalkyl” used as part of another term or independently refers to the group —SR. Wherein R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl and alkynyl.

  The prefix “hetero” indicates that one or more carbons have been replaced with a different atom. In one embodiment, the heteroatom is selected from the group consisting of N, O and S.

  The prefix “fluoro” indicates that one or more hydrogens have been replaced with fluorine. The term includes partially and fully fluorinated materials.

  Any of the above groups may be linear or branched. Examples of linear alkyl, alkenyl and alkynyl include n-butyl, n-pentyl, n-heptyl, n-octyl, n-butenyl, n-pentenyl, n-heptenyl and n-heptynyl. Examples of branched alkyl, alkenyl and alkylnyl include iso-butyl, t-butyl, iso-pentyl, neo-pentyl, isopentenyl and neo-pentenyl.

  Any of the above groups may be substituted or unsubstituted. The term “substituted” refers to a mono- or poly-substituted group with the same or different substituents. Suitable substituents include cyano group, nitro group, ester group, ether group, halogen, hydroxy, alkyl group, aryl group and alkoxy group. In one embodiment, the substituent includes an ether group and a fluorine substituent.

  As used herein, the term “charge transport” refers to a layer, material, member or structure such that the layer, material, member or structure is relatively efficient and has a low loss of charge. It means promoting the movement of such charges through the thickness of the member or structure. “Electron transport” refers to negative charge transport, and “hole transport” refers to positive charge transport.

  As used herein, "including", "including", "containing", "containing", "having", "having" or variations thereof are meant to include, but not be limited to It is intended to cover. For example, a process, method, article or device that includes a list of components is not necessarily limited to only those components, but also includes other components that are not explicitly specified or are specific to such processes, methods, articles or devices. . Further, on the contrary, unless explicitly stated otherwise, “or” refers to an inclusive “or” and not an exclusive “or”. For example, the condition A or B satisfies any one of the following. A is true (or present), B is false (or does not exist), A is false (or does not exist), B is true (or exists), both A and B are true Is (or exists).

  Also, “one” or “some” is used to describe the components and components described herein. This is done for convenience only and gives a general sense of the scope of the invention. This description should be understood to include one or at least one and the singular also includes the plural unless it is clearly meant to be inconsistent.

  The group numbers corresponding to the columns of the periodic table of elements use the “New Notation” rule in the CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001).

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned herein are hereby incorporated by reference in their entirety unless otherwise specified. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

  Many details regarding specific materials, processing operations, and circuits, to the extent not described herein, are conventional, text and other sources of organic light emitting diode display, photodetector, photovoltaic and semiconductor component industries. It is in.

(2. Aryl-ethylene aromatic compound)
Formula 1:

A compound represented by
Where
Ar is an arylene group,
Ar ′ and Ar ″ are independently selected from aryl groups;
R ^{1 to} R ⁴ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R Independently selected from the group consisting of ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
m and n are integers each independently having a value of 0 to 5, and m + n ≠ 0.

  In one embodiment, Ar, Ar ′ and Ar ″ are selected from the group consisting of an aromatic group having at least two fused rings and an aromatic group having at least two rings joined by a single bond. In embodiments, Ar is selected from the group consisting of an aromatic group having at least two fused rings and an aromatic group having at least two rings joined by a single bond, hi one embodiment, Ar is an acene group is there.

In one embodiment, R ^{1 to} R ⁴ are H. In one embodiment, m and n are not both zero. In one embodiment, m = n = 1.

  In one embodiment, Ar is

And selected from the group consisting of these,
Where
Q is selected from the group consisting of S, Se, Te, O or NR ⁰ ;
q and r are integers each independently having a value of 0 to 5,
s is an integer having a value of 1 to 5,
R ⁰ is selected from the group consisting of hydrogen, alkyl and aryl;
R ^{5 to} R ¹⁰ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R Independently selected from the group consisting of ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
In the formula, any two adjacent groups R ^{5 to} R ¹⁰ can be combined to form a ring.

  In one embodiment, Ar is

Selected from the group consisting of
Where
Q, q, r, s, R ⁰ , R ⁵ and R ⁶ are as described above.

  In one embodiment, for any of the above Ar groups, r is at least 1 and s is at least 2. In one embodiment, q is 0, 1, 2 or 3, r is 1, 2 or 3, and s is 2 or 3. In one embodiment, Ar is selected from tetracene and pentacene.

  In one embodiment, Ar is 2,6-naphthalene, substituted 2,6-naphthalene, 2,6-anthracene, substituted 2,6-anthracene, 2,7-fluorene, provided that there is no diarylamino substituent. It has at least one group selected from the group consisting of substituted 2,7-fluorene, 3,6-carbazole, substituted 3,6-carbazole, and combinations thereof. In one embodiment, the substituents are independently selected from the group consisting of alkyl, alkoxy, alkyl ether, ether alkyl, thioalkyl, silyl, and combinations thereof. In the present specification, the numbers indicate the point of attachment of the group, and follow the rules in the CRC and Handbook of Chemistry and Physics, 81st Edition (2000-2001).

  In one embodiment, Ar ′ and Ar ″ are independently selected from substituted aryl groups provided that there are no diarylamino substituents. In one embodiment, there are no amino substituents. In one embodiment, Ar 'And Ar ″ are independently selected from substituted aryl groups, wherein the substituents are independent from the group consisting of alkyl, aryl, alkylaryl, alkoxy, alkyl ether, ether alkyl, fluoro, thioalkyl, silyl, and combinations thereof. Selected.

  While not wishing to be bound by theory, it is believed that the specific geometric properties of these compounds correlate with performance in electronic devices. In one embodiment, compounds of formula 1 having a flat symmetric chemical structure are used in OTFTs. Such a structure is an extended conjugated system with a number of possible extension resonance structures, such as the two resonance structures of 2,6-bis- (2-naphthalen-2-yl-vinyl) -anthracene shown below. Can be formed.

  The resonance structure of aryl-ethyleneacene can be converted to the quinoid state when exposed to an electric field, as exemplified herein for 2,6-bis- (2-naphthalen-2-yl-vinyl) -naphthalene. It is also considered.

This is expected to be high mobility. In fact, when a compound of the formula 1 is used like an active semiconductor of OTFT, a mobility exceeding 1 cm ² / V is obtained. Since the band gap of these semiconductors is relatively large (about 2.3 to 3.5 eV), the compounds are also extremely stable materials. Such high mobility semiconductors can also be used as charge transport materials or host materials in OLEDs.

  The compound of Formula 1 exhibits high mobility and a high on / off ratio and is suitable for use in the manufacture of semiconductor devices. These compounds have high thermal stability and are not affected by light or air. Therefore, the semiconductor device does not need to be manufactured in an inert atmosphere. When these compounds are used, an electronic device can be produced at a low substrate temperature. Furthermore, these compounds have good film forming ability.

In one embodiment, for the aryl-ethylene compound used in OTFT, R ^{1 to} R ⁴ are independently H, F, or CN. The arylethylene acene compound used in OTFT preferably has a trans structure with respect to the full-duplex C═C bond and maximizes the conjugate of the unsaturated system.

In one embodiment, arylethylene acene compounds intended for use in OTFTs also have a flat symmetric molecular structure. “Flat” means that the twist angle between the intermediate ring and the trans-C═C double bond connecting segment is 0 ° to 10 °, preferably 0 °. The “twisted” molecular structure has a twist angle greater than 10 °. The twist of the acene group is mainly controlled by the steric interaction of the substituents of the acene ring. Compounds having relatively bulky neighboring groups, R ^{6 to} R ¹⁰ , tend to twist more than compounds in which all of R ^{6 to} R ¹⁰ are H, F or CN. In the “symmetric” molecule, the aryl-ethylene substituents are identical, ie Ar ′ = Ar ″, R ¹ = R ⁴ and R ² = R ^3. Compound A is a suitable material for use as a semiconductor in OTFT It is.

  Examples of the compound represented by Formula 1 include the following.

  In one embodiment, the compound of formula 1 may be polymerized to form longer oligomers or polymers. In one embodiment, the compound of formula 1 may be copolymerized with one or more different compounds of formula 1 and / or one or more different monomers that do not have formula 1. In one embodiment, the compound represented by Formula 1 may have a crosslinkable group. These compounds can be applied to form a layer and then cross-linked to improve durability and solvent resistance.

(3. General preparation of compounds of formula 1)
The compound represented by Formula 1 can be prepared by a conjugated cross-coupling reaction of a substituted boronic acid (or ester) with a dihaloarylene compound. Such a reaction is commonly referred to as “Suzuki coupling” and is illustrated in Scheme 1.

  As shown in Scheme 2, a “Heck coupling reaction” in which a substituted aryl-ethylene is reacted with a dihaloarylene compound in the presence of a Pd (II) catalyst and a phosphine can also be used. Hal-Ar-Hal is as described above in Scheme 1.

  Variations on these synthetic procedures as shown in Schemes 3 and 4 can also be used.

  In schemes 3 and 4, Ar 'is as described above.

  The Suzuki coupling reaction is well known in organic chemistry and is described in Non-Patent Document 1.

  Boric acid or ester reagents can be synthesized according to literature methods (see Non-Patent Document 2).

  The reagent is not limited to the above substituted boronic acids or esters. Any Suzuki coupling reagent used as an organic boron coupling reagent, such as potassium trifluoro (organo) borate, can be used. (Non-Patent Document 3). The reaction conditions, catalyst, solvent, phase transfer agent and reaction medium can also be varied. (Non-Patent Document 4).

  The Heck coupling reaction is also well established in organic chemistry and is described in the literature (Non-patent document 5, Non-patent document 6, Non-patent document 7, Non-patent document 8, Non-patent document 9, Non-patent document 10. Non-patent document 11. Non-patent document 12).

  Aryl-ethylene or substituted styrene reagents can be synthesized according to literature methods (see Non-Patent Document 13).

(4. Semiconductor devices)
A semiconductor device is described in Non-Patent Document 14. Such devices include rectifiers, transistors (many types including pnp, npn and thin film transistors), current limiters, thermistors, pn junctions, field effect diodes, Schottky diodes. Etc. A semiconductor device can be manufactured or manufactured by a known method (Non-patent Document 15). In each semiconductor device, the semiconductor material is combined with one or more metals or insulators to form the device. Common to all semiconductor devices is the presence of one or more semiconductor materials. The compound represented by Formula 1 can be used as a semiconductor material in a semiconductor device.

  In one embodiment, the semiconductor device includes at least one charge transport layer comprising a compound represented by Formula 1.

((I) Thin film transistor)
A particularly useful type of transistor device, a thin film transistor (TFT), generally comprises a gate electrode, a gate dielectric on the gate electrode, a source and drain electrode in proximity to the gate dielectric, and a source electrode in close proximity to the gate dielectric. And a semiconductor layer adjacent to the drain electrode (see, for example, Non-Patent Document 16 above). These components can be assembled in various configurations. Specifically, an organic thin film transistor (OTFT) has an organic semiconductor layer.

  In general, the substrate supports the OTFT during manufacturing, testing and / or use. The substrate can optionally provide an electrical function to the OTFT. Useful substrate materials include organic and inorganic materials. For example, the substrate may be an inorganic glass, a ceramic foil, a polymer material (for example, acrylic, epoxy, polyamide, polycarbonate, polyimide, polyketone, poly (oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4- Phenylene), poly (ether ether ketone) or PEEK), polynorbornene, polyphenylene oxide, poly (ethylene naphthalene dicarboxylate) (PEN), poly (ethylene terephthalate) (PET), poly (phenylene sulfide) (PPS)). The substrate can also include a filled polymeric material (eg, fiber reinforced plastic (FRP)) or a coated metal foil.

  The gate electrode can be any useful conductive material. For example, the gate electrode can include doped silicon or metal (eg, aluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum or titanium). For example, a conductive polymer such as polyaniline or poly (3,4-ethylenedioxythiophene) / poly (styrene sulfonate) (PEDOT: PSS) can also be used. In addition, alloys of these materials, combinations thereof, and multilayers thereof can also be used. In a certain OTFT, a single material functions as a gate electrode function and a substrate. For example, doped silicon can function as a gate electrode and support an OTFT.

  The gate dielectric typically covers the gate electrode. The gate dielectric electrically insulates the gate electrode from the rest of the OTFT device. Useful materials for the gate dielectric include inorganic insulating materials such as strontate, tantalate, titanate, zirconate, aluminum oxide, silicon oxide, tantalum oxide, titanium oxide, silicon nitride, barium titanate, barium strontium titanate, Barium zirconate titanate, zinc selenide and zinc sulfide). In addition, alloys of these materials, combinations thereof, and multilayers thereof can also be used for the gate dielectric.

  The source and drain electrodes are separated from the gate electrode by a gate dielectric, and the organic semiconductor layer can be above or below the source and drain electrodes. The source and drain electrodes can be made of a sufficiently conductive material (for example, a material such as aluminum, barium, calcium, chromium, gold, silver, nickel, palladium, platinum, titanium, or an alloy thereof). . Conductive polymers such as polyaniline, PEDOT: PSS, and combinations and multilayers thereof can also be used as source and drain electrodes. As is known in the art, some of these materials are suitable for use with n-type semiconductor materials and others, and others are suitable for use with p-type semiconductor materials.

  Thin film electrodes (eg, gate electrode, source electrode and drain electrode) can be provided by several means including physical vapor deposition (eg, thermal evaporation or sputtering) and ink jet printing. The patterning of these electrodes can be performed by a known method such as shadow mask, additive photolithography, subtractive photolithography, printing, microcontact printing, or pattern coating.

  1A and 1B are schematic diagrams of a bottom contact mode and a top contact mode of an OTFT, respectively. The OTFT typically includes a substrate, such as an n-type silicon wafer 102. The wafer functions as the gate electrode of the TFT device. A silicon dioxide dielectric layer 104 is typically thermally grown on the gate electrode.

  For bottom-contact mode OTFTs (FIG. 1A), the electrodes 106 and 108 forming the source and drain channels can each be fabricated on silicon dioxide using a photolithographic process. A semiconductor layer 110 is deposited on the surfaces of the electrodes 106, 108 and 104.

  For top-contact mode OTFT (FIG. 1B), layer 110 is deposited on layer 104 prior to fabrication of electrodes 106 and 108. FIG. 1B is a schematic diagram of an OTFT, showing the relative position of the active layer of such a device in top contact mode.

  FIG. 1C is a schematic diagram of an OTFT, showing the relative position of the active layer of such a device in top contact bottom contact mode.

  FIG. 1D is a schematic diagram of an OTFT, showing the relative position of the active layer of such a device in a bottom contact mode with a top gate.

  The semiconductor layer 110 can include one or more compounds represented by Formula 1. Layer 110 may be deposited by various techniques known in the industry such as thermal evaporation, chemical vapor deposition, thermal transfer, ink jet printing, and screen printing. Useful dispersion thin film coating techniques for deposition include spin coating, doctor blade coating and drop casting.

  For top contact mode OTFT (FIG. 1B), layer 110 is deposited on layer 104 prior to fabrication of electrodes 106 and 108.

  The semiconductor compounds described herein can also be used in other OTFT device structures, such as gate top device configurations. Such a device structure is described in US Patent Publication (Patent Document 1).

  In some cases, the substrate 100 can be a plastic polymer material, an inorganic insulator, or a metal substrate. The gate electrode 102 can be coated on the substrate by various coating methods such as spin coating, bar coating and doctor blade coating, or printing methods such as thermal laser printing, ink jet printing and screen printing.

The characteristics of the OTFT device shown herein can function as follows.
The linear region (V _g ≦ V _sd ) mobility is calculated according to the equation μ _lin = (L / WC _i V _sd ) (dI _d / dV _g ) (Equation 1). Where I _d is the drain current, V _g is the gate voltage, V _sd is the source-drain voltage, L is the channel length, W is the channel width, and C _i is the gate dielectric. It is the capacitance per unit area. C _i is the unit F / cm ² and is calculated according to the formula C _i = (ε ₀ ε / t) (10 ⁻⁴ ) (Formula 2). In the equation, ε is a transmittance constant, ε is a dielectric constant, and t is a dielectric thickness.

Saturation region (V _g > = V _sd ) mobility is

Calculated according to

The threshold voltage V _t is measured in the saturation region. Plot the square root of I _d against V _g . V _t can be obtained by linear extrapolation from the steepest portion of the curve to the x-axis.

The on / off ratio is the ratio of the current I _{DS at} the lowest V _GS to the current I _DS at the highest V _GS under the highest applied drain voltage V _DS .

(B. Display device)
FIG. 2 is a schematic diagram of the display device 200. The anode 202 and the cathode 204 are electrically connected to a power source 206. The power source 206 is preferably a current source. The buffer layer 208 is in contact with the anode 202. The buffer layer 208 is not limited to these in organic electronic devices, but includes planarization of underlying layers, charge transport and / or charge injection properties, scavenging of impurities such as oxygen or metal ions, and organic electrons. It may have one or more functions, including other aspects that promote or improve the performance of the device. The hole transport layer 210 is in contact with the buffer layer 208 from one side and the organic semiconductor layer 212 on the other side. The hole transport layer 210 facilitates the passage of holes from the hole injection layer 208 to the organic semiconductor layer 212.

  Similarly, the electron injection layer 214 is in contact with the cathode 204. The electron injection layer 214 facilitates injection of electrons from the cathode 204 into the display device 200. The electron transport layer 216 exists in contact with the hole injection layer 214 from one side and the organic semiconductor layer 212 on the other side. The electron transport layer 216 facilitates the passage of electrons from the electron injection layer 214 to the organic semiconductor layer 212. In one embodiment, the organic semiconductor layer includes a photoactive material. The term “photoactive” refers to emitting light when activated by an applied voltage (such as in a light emitting diode or chemical cell), or in response to radiant energy, with or without applying a bias voltage. Refers to the material that produces the signal (such as in a photodetector).

  In some embodiments, one of the hole injection layer 208 and the hole transport layer 210 is omitted. In some embodiments, one of the electron injection layer 214 and the electron transport layer 216 is omitted.

  When current is applied to anode 202 and cathode 204, electrons and holes are injected into device 200. These electrons and holes combine in the organic semiconductor layer 212 and emit photons due to the electroluminescent properties of the compounds present in the organic semiconductor layer 212. Layer 212 is also referred to as a “light emitting layer”.

  In one embodiment, the light emitting layer 212 includes one or more compounds represented by Formula 1. In one embodiment, the compound of Formula 1 is present in layer 212 as a host for the photoactive material. In one embodiment, the compound of Formula 1 in layer 212 does not have an amino substituent.

  In one embodiment, the electron transport layer 214 includes one or more compounds represented by Formula 1. In one embodiment, the electron transport layer 214 includes one or more compounds of Formula 1 in combination with other known charge transport materials (such as Alq3 derivatives). The term “electron transport or transport of electrons” does not include such layers, materials, members or structures, even if the light emitting or photosensitive layer, material, member or structure has electron transport properties.

  In one embodiment, the hole transport layer 210 includes one or more compounds represented by Formula 1. In one embodiment, the compound of formula 1 is present in the host hole transport material of layer 210. Examples of the host material include, but are not limited to, polythiophene, polypyrrole, polyaniline, and polyvinyl carbazole. In one embodiment, the hole transport layer 210 includes one or more compounds of Formula 1 in combination with other known charge transport materials (such as NPD derivatives). The term “hole transport or hole transport” includes such layers, materials, members or structures, even if the light emitting or photosensitive layer, material, member or structure has hole transport properties. I can't.

  In one embodiment, the buffer layer 208 includes one or more compounds represented by Formula 1. In one embodiment, the compound of Formula 1 in the buffer layer 208 does not have an amino substituent.

In one embodiment, the hole transport layer 210 includes one or more compounds of Formula 1 without an amino substituent.

  In one embodiment, the hole transport layer 210 includes one or more compounds represented by Formula 1.

  Wherein Ar is the following group:

And combinations thereof,
Where
Q is selected from the group consisting of S, Se, Te, O and NR ⁰ ;
q and r are integers each independently having a value of 0 to 5,
s is an integer having a value of 1 to 5,
R ⁰ is selected from the group consisting of hydrogen, alkyl and aryl;
R ^{5 to} R ¹⁰ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R Independently selected from the group consisting of ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl and alkynyl;
In which any two neighboring groups R ^{5 to} R ¹⁰ can be taken together to form a ring;
In addition, there are no diarylamino groups.

In one embodiment, the substituents or substituents R and R ¹ -R ¹⁰ are independently selected from the group consisting of alkyl, aryl, thioalkyl, silyl, alkylaryl, alkoxy, alkyl ether, ether alkyl, fluorine, and combinations thereof. Is done.

In one embodiment, m = n = 1, and R ^{1 to} R ¹⁰ are all selected from the group consisting of hydrogen, fluorine, a chain alkyl group, an aryl group, and an aryl group substituted with a chain alkyl group. . In one embodiment, the alkyl group has 1-10 carbon atoms. In one embodiment, Ar is an acene group.

  In one embodiment, the hole transport layer 210 includes one or more compounds selected from the group consisting of Compound 1, Compound 3, Compound 48, Compound 49, and Compound 50.

  The other layers of the device can be made of any material that has been found useful for such layers in view of the function to be provided by such layers.

  The anode 202 can be made of a material containing or including, for example, a metal, mixed metal, alloy, metal oxide, or mixed metal oxide. The anode may comprise a conductive polymer, polymer blend or polymer mixture. Suitable metals include Group 11 metals, Group 4, 5, and 6 metals, and Group 8-10 transition metals. When the anode is to transmit light, a mixed metal oxide of Group 12, 13, and 14 metals such as indium tin oxide is usually used. The anode may also include an organic material, particularly a conductive polymer such as polyaniline. Exemplary materials are described, for example, in (Non-Patent Document 17). At least one of the anode and cathode must be at least partially transparent so that the generated light can be observed.

  The buffer layer may contain, for example, hole transport materials as summarized in (Non-patent Document 18). Any of the hole transporting “small” molecules, oligomers and polymers may be used. The hole transport molecule is not limited to these, but is 4,4 ′, 4 ″ -tris (N, N-diphenyl-amino) -triphenylamino (TDATA), 4,4 ′, 4 ″- Tris (N-3-methylphenyl-N-phenyl-amino) -triphenylamine (MTDATA), N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl ] -4,4'-diamino (TPD), 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC), N, N'-bis (4-methylphenyl) -N, N'- Bis (4-ethylphenyl)-[1,1 ′-(3,3′-dimethyl) biphenyl] -4,4′-diamino (ETPD), tetrakis- (3-methylphenyl) -N, N, N ′ , N'-2,5-fe Range amine (PDA), α-phenyl-4-N, N-diphenylaminostyrene (TPS), p- (diethylamino) benzaldehyde diphenylhydrazone (DEH), triphenylamine (TPA), bis [4- (N, N -Diethylamino) -2-methylphenyl] (4-methylphenyl) methane (MPMP), 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP) ), 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB), N, N, N ′, N′-tetrakis (4-methylphenyl)-(1,1′-biphenyl)- 4,4′-diamine (TTB), N, N′-bis (naphthalen-1-yl) -N, N′-bis- (F Examples include porphyrin compounds such as (enyl) benzidine (α-NPB), 4,4′-N, N′-dicarbazolyl-biphenyl (CBP) and copper phthalocyanine. Useful hole transport polymers include, but are not limited to, polyvinyl carbazole, (phenylmethyl) polysilane, polythiophene, polypyrrole and polyaniline. The hole transport polymer may be a complex of a conductive polymer and a colloid-forming polymer acid as disclosed in US Patent Publication (Patent Document 2) and US Patent Publication (Patent Document 3). Conductive polymers are useful as one class. As described above, the hole transport polymer can be obtained by doping the hole transport portion into a polymer such as polystyrene or polycarbonate.

  Any organic electroluminescent (“EL”) material can be used as the photoactive material in the emissive layer 212. Such materials include, but are not limited to, fluorescent dyes, small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. Examples of fluorescent dyes include, but are not limited to, pyrene, perylene, rubrene, derivatives thereof, and mixtures thereof. Metal complexes include, but are not limited to, metal chelated oxinoid compounds such as tris (8-hydroxyquinolate) aluminum (Alq3), cyclometalate iridium and platinum electroluminescent compounds such as Petrov. (Petrov) et al. (Patent Document 4) complexes of iridium and phenylpyridine, phenylquinoline or phenylpyrimidine ligand, and, for example, US Patent Publication (Patent Document 5), (Patent Document 6). , (Patent Document 7) and (Patent Document 8), and organometallic complexes described in (Patent Document 8) and mixtures thereof. An electroluminescent emitting layer comprising a charge-carrying host material and a metal complex has been described by Thompson et al. In U.S. Pat. No. 6,057,049 and Burrows and Thompson in U.S. Pat. Patent Document 11). Examples of the conjugated polymer include, but are not limited to, poly (phenylene vinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof, and mixtures thereof. .

  In one embodiment of the device, the photoactive material can be an organometallic complex. In other embodiments, the photoactive material is a cyclometallate complex of iridium or platinum. Other useful photoactive materials may be used. Complexes of iridium and phenylpyridine, phenylquinoline or phenylpyrimidine ligands are disclosed as electroluminescent compounds in Petrov et al. Other organometallic complexes are described in, for example, US Patent Publication (Patent Literature 5), (Patent Literature 6), (Patent Literature 7), and (Patent Literature 8). An electroluminescent device having an active layer of polyvinylcarbazole (PVK) doped with a metal complex of iridium is described in Burrows and Thompson (US Pat. Yes. An electroluminescent emission layer containing a charge transporting host material and a phosphorescent platinum complex is described in US Pat.

Electron transport materials for layer 218 are not limited to these, but include bis (2-methyl-8-quinolinolate) (para-phenyl-phenolate) aluminum (III) (BAIQ) and tris (8-hydroxyquino). Rate) aluminum (Alq ₃ ), azole compounds such as 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD), 3- (4- Biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ) and 1,3,5-tri (phenyl-2-benzimidazole) benzene (TPBI), quinoxaline Derivatives such as 2,3-bis (4-fluorophenyl) quinoxaline, phenanthroline derivatives such as 9,10-di E sulfonyl phenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA), as well as mixtures of these.

Cathode layer 204 may be deposited as a line or as a film. The cathode can be a metal or non-metal having a lower work function than the anode. Exemplary materials for the cathode can include Group 1 alkali metals, particularly lithium, Group 2 (alkaline earth) metals, Group 12 metals, including rare earth elements and lanthanoids, actinides. . Materials such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof can be used. Li containing and other compounds such as LiF and Li ₂ O may be deposited between the organic layer and the cathode layer as the electron injection layer 214 to reduce the operating voltage of the system.

  Although not shown, it is contemplated that device 200 may include additional layers. Other layers known in the industry may be used. Further, any of the above-described layers may include two or more sublayers or form a layered structure. Alternatively, some or all of the anode layer 202, the hole transport layer 210, the electron transport layer 218, the electron injection layer 214, the cathode layer 204, and other layers may be treated, particularly surface treated to provide charge transport. Efficiency or other physical properties of the device may be increased. The choice of material for each component layer is preferably intended to provide a device with high device efficiency, taking into account device operating life considerations, manufacturing time and complex factors and other considerations recognized by those skilled in the art. It is preferable to make a balance with this. Determining the best component, component configuration, and composite identification would be stylized by those skilled in the art.

  In one embodiment, the different layers have a thickness in the following range. Anode 202, 500-5000５, in one embodiment 1000-2000Å, buffer layer 208 and hole transport layer 210, 50-2000 そ れ ぞ れ, respectively, in one embodiment 200-1000Å, photoactive layer 212, 10-2000Å, one In embodiments, 100-1000 soot, layers 216 and 214, 50-2000 soot, in one embodiment 100-1000 soot, cathode 204, 200-10000 soot, in one embodiment 300-5000 soot. The location of the electron-hole recombination region in the device and the emission spectrum of the device can affect the relative thickness of each layer. Thus, the thickness of the electron-transport layer should be selected so that the electron-hole recombination region becomes the light-emitting layer. The desired ratio of layer thickness depends on the exact nature of the material used. The different layers can be formed by known deposition methods including liquid deposition, vapor deposition and thermal transfer. In one embodiment, the device is manufactured by liquid deposition of a buffer layer, a hole transport layer and a photoactive layer, and by evaporation of an electron transport layer, an electron injection layer and a cathode.

  While detailed embodiments of the present invention have been illustrated and described, it is clear that the present disclosure is not limited to these embodiments. Many modifications, changes, variations, substitutions and equivalents will be apparent to those skilled in the art without departing from the spirit and scope of the invention as set forth in the claims.

  The invention is further illustrated by the following examples. These examples illustrate preferred embodiments of the present invention, but are considered to be illustrative only.

(Overview)
Thermogravimetric analysis (TGA) was performed on a TA Instruments Q550 TGA system ™ with a heating rate of 10 ° C./min and a nitrogen flow rate of 60 cm ³ / min.

Cyclic voltammetry (CV), EG & G Parc model 273A (trademark) potentiostat, with 3 electrode batteries in a solution of Bu ₄ NBF ₄ (0.1 M) in acetonitrile at a scan rate of 50 mV / s. / Carried out with a galvanostat system.

The semiconductor film was coated on a disk Pt electrode (0.050 cm ² ) by vacuum sublimation. A Pt wire was used as the counter electrode, and an Ag / AgNO ₃ (0.01M) electrode was used as the reference electrode. Prior to each series of measurements, the cells were deoxygenated with argon. Organic semiconductor was added to the electrolyte solution (0.2 mg / mL). A Pt wire was used as the counter electrode, and an Ag wire electrode was used as the reference electrode. The electrode potential was calibrated with a saturated calomel electrode (SCE) by measuring the ferrocene / ferrocenium pair in this system (0.15 V vs. SCE). The band gap was derived from the difference between the onset potentials.

  The synthesis results were confirmed by mass spectrometry, nmr analysis and / or x-ray crystal structure.

  The x-ray data were taken with a CAD-4 diffractometer with copper Kα radiation and the structure was solved using a series of NRCVAX ™ programs.

  Nuclear magnetic resonance (NMR) spectra were taken on a Bruker ™ 500 MHz spectrometer. All chemical shifts were recorded relative to tetramethylsilane (TMS) at 0.0 ppm unless otherwise noted. 2,6-Dibromoanthracene was synthesized according to the method of (Non-patent Document 20).

  Unless otherwise noted, other reagents were purchased from Aldrich and used without purification.

Example 1
(Synthesis of 2,6-distyryl-anthracene (compound 1))

  2,6-Dibromoanthracene (5.20 g, 15.48 mmol) and 2-styryl- [1,3,2] -dioxaborinane (8.73 g, 46.43 mmol, Sigma-Aldrich Chemical Company) in toluene (200 ml) To a mixture of (Sigma-Aldrich Chemical Co.), Milwaukee, WI, 2M sodium carbonate (8.20 g, 77.36 mmol) dissolved in water (38.7 ml) was added, followed by Phase Transfer Agent Aliquat® 336 (3.10 g, 7.74 mmol, Sigma-Aldrich Chemical Co.) was added. The mixture was bubbled with nitrogen for 15 minutes before tetrakis (triphenylphosphine) palladium (0) (358.5 mg, 2% mol, Sigma-Aldrich Chemical Co.) was added. The mixture was heated to 90 ° C. for 3 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol (600 ml). The precipitate was filtered and washed with water, dilute acid (5% HCl), water, methanol and 3 times with acetone to remove starting material and mono-substituted by-products. The crude product was purified by sublimation (twice) in a 3 zone furnace to give 2.71 g (46%) of a yellow solid.

(Example 2)
(Synthesis of 2,6-bis [2-4-pentyl-phenyl) -vinyl] -anthracene (Compound 2))

2,6-Dibromoanthracene (2.688 g, 8.0 mmol) and trans-2- (4-fluoro-phenyl) vinyl-boronic acid (3.983 g, 24.0 mmol, Sigma-Aldrich) in toluene (120 ml) to a mixture of Chemical Co. (Sigma-Aldrich Chemical Co.)) , 2M Na 2 CO 3 sodium carbonate dissolved in water (20 ml) (4.24 g, was added 40 mmol), followed by phase transfer agent Arikueto (Aliquat ) (R) 336 (1.6 g, 4 mmol, Sigma-Aldrich Chemical Co.) was added. The mixture was bubbled with nitrogen for 15 minutes before tetrakis (triphenylphosphine) palladium (0) (185.3 mg, 2% mol, Sigma-Aldrich Chemical Co.) was added. The mixture was heated to 90 ° C. for 3 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol (300 ml). The yellow precipitate was filtered and washed with water, dilute acid (5% HCl), water, methanol and 3 times with acetone to remove starting material and mono-substituted by-product. The crude product was purified by sublimation in a three zone furnace to give a bright yellow solid.

(Example 3)
(Synthesis of 2,6-bis [2-4-pentyl-phenyl) -vinyl] anthracene (Compound 3))

  2,6-Dibromoanthracene (5.20 g, 15.48 mmol) and 2- [2- (4-pentylphenyl) vinyl] -4,4,5,5-tetramethyl-1,3 in toluene (200 ml) , 2-dioxaborolane (14.67 g, 46.42 mmol, Sigma-Aldrich Chemical Co.) in 2M sodium carbonate (8.20 g, 77) dissolved in water (38.7 ml). .36 mmol) was added followed by phase transfer agent Aliquat® 336 (3.10 g, 7.74 mmol, Sigma-Aldrich Chemical Co.). . The mixture was bubbled with nitrogen for 15 minutes before tetrakis (triphenylphosphine) palladium (0) (358.5 mg, 2% mol, Sigma-Aldrich Chemical Co.) was added. The mixture was heated to 90 ° C. for 3 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol (600 ml). The precipitate was filtered and washed with water, dilute acid (5% HCl), water, methanol and 3 times with acetone to remove starting material and mono-substituted by-products. The crude product was purified twice by sublimation in a three zone furnace to give 2.00 g (25%) of a bright yellow solid.

Example 4
(Synthesis of 2,6-bis (2-naphthalen-2-yl-vinyl) anthracene (Compound 4))

  2,6-dibromoanthracene (3.36 g, 10.0 mmol) and 2-vinylnaphthalene (4.63 g, 30.0 mmol, Sigma-Aldrich Chemical Co.) in anhydrous DMF (150 ml). ), Triphenylphosphine (0.13 g, 0.50 mmol, Sigma-Aldrich Chemical Co.) and tributylamine (11.9 ml, 50.0 mmol, Sigma-Aldrich Chemical Co.). (Sigma-Aldrich Chemical Co.)) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, palladium acetate (112.0 mg, 0.5 mmol, Sigma-Aldrich Chemical Co.) was added. The mixture was heated to 130 ° C. for 18 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol (500 ml). The precipitate was filtered and washed with methanol, acetone and then chloroform. The crude product was purified twice by sublimation in a 3-zone furnace to give a yellow solid.

(Example 5)
(Determination of OTFT device characteristics)
This example summarizes the results obtained for OTFT device characterization with a W / L ratio (W is channel width, L is channel length) of 10.

  The OTFT device was fabricated in a similar manner as described with respect to FIG. 1B. Thereafter, the performance of each OTFT device was evaluated using an Agilent 4155C ™ semiconductor parameter analyzer interfaced with a probe station (Semiconductor Parameter Analyzer).

  In Example 5e, a conductive polymer layer of polyaniline (PANI) and dispersed carbon nanotubes (PANI / NT) were applied as a patterned gate electrode, the polyaniline-carbon nanotube (PANI / NT) composition as a donor, and Mylar Thermal transfer printing was performed using a CREO-Trendsetter TML printer using a (Mylar) ® RS8 receiver sheet. A dielectric layer of latex RS35 was laminated or thermal transfer printed to the patterned gate. Source and drain patterns, using polyaniline-carbon nanotube (PANI / NT) composition as a donor, and Mylar® RS8 receiver sheet, using a CREO-Trendsetter TML printer Printed. The semiconductor of composition 1 was thermally evaporated on the source and drain electrodes through a shadow mask.

  Measurements were performed at ambient conditions. No special measures were taken to control temperature or eliminate light or air.

  The results obtained from the evaluation of OTFT devices are summarized in the table. These results show that OTFT devices containing the compound of Formula 1 have high mobility and high on / off ratio.

In another device fabrication, an organic thin film field effect transistor (OTFT) device is topped with a 200 nm thermal oxide that acts as a dielectric layer with a capacitance per unit area of 1.73 × 10 ⁻⁸ F / cm ^2. And on a heavily doped n-type Si wafer with heavily doped n-type Si etched as a back contact (gate electrode). The wafer was subsequently cleaned by washing with acetone, isopropanol and deionized water, blown dry with N ₂ gas, and cleaned in oxygen plasma for 6 minutes. Next, the cleaned wafer substrate is immersed in a 0.1M solution of OcTS in toluene at 60 ° C. for 15 minutes to form a self-assembled monolayer (SAM) of octyltrichlorosilane (OcTS) on the wafer SiO ₂ surface. Processed. After rinsing with toluene and blow drying with N ₂ gas, the substrate was annealed at 150 ° C. for 5 minutes to crosslink the SAM layer (the contact angle of the OcTS treated surface is about 88 ° to 91 °). A semiconductor layer was deposited on the processing dielectric surface through a shadow mask (the area of the 40 shadows to define the active layer was approximately 1000 × 1000 μm each). The organic semiconductor was deposited at a rate of 1-2 liters / s under a pressure of about 2.0 × 10 ⁻⁶ torr to a final thickness of 400 liters as required by a quartz crystal monitor. The film thickness was corrected by a palpated surface profile measuring device. The substrate temperature during deposition was controlled by heating or cooling the copper block on which the substrate was mounted. Gold electrodes were deposited after semiconductor deposition by using a shadow mask with a W / L of about 10/1. The mask defines eight sets of source-drain pairs, each with a channel width W of 400, 600, 800, 1000 μm, and eight different channel lengths L corresponding to 40, 60, 80, and 100 μm, respectively. It was. Electrical properties were obtained at room temperature in the air using an Agilent 4155C semiconductor parameter analyzer. Mobility and threshold voltage were extracted from standard TFT analysis. The on / off ratio was obtained from the current I _DS to V _GS = + 10 V and the current I _DS when V _GS = −40V. All data in Table 1 were obtained by randomly measuring eight separate TFTs and determining the average value. The standard deviation was in the range of 5-10%.

μ ^sat : saturation mobility, μ ^lin : linear mobility, on / off ^sat : drain-source current on (grain-source voltage is −60 V) and off in the saturation region when maximum gate voltage is applied (−60 V) Drain-source voltage is 0) current ratio, on / off ^lin : drain-source current on (grain-source voltage is -60 V) and off (drain-source voltage in a linear region when maximum gate voltage is applied (-5 V) 0) current ratio, V _t ^sat : threshold voltage in saturation region, V _t ^lin : threshold voltage in linear region, SubThrSW ^sat : subthreshold coefficient in saturation region, SubThrSW ^lin : subthreshold coefficient in linear region, NA = invalid.

(Example 6)
(Stability test of OTFT manufactured using Compound 1 and Compound 36)
The device was tested according to the procedure described above and the data was analyzed as described in (Non-Patent Document 21). A device using compound 36 (5n) was operated continuously with a constant drain-source voltage of -40V and an AC gate-source voltage of + 40V to -40V. It was found that the semiconductor material was stable in the device and the device performance was the same as the initial test results. The device was operated continuously for at least 24 hours during the test. In contrast, it produced using pentacene as semiconductor layers, device tested under the same conditions after the continuous operation of only 2 hours, 0.1 cm from the charge mobility (0.4 cm 2 / ^{Vs 2} It showed a significant loss in / reduced to Vs) and on / off ratio (reduced from the initial I6.5 × 10 ⁴ to about 10 ^1).

In other tests, device (5c) was constructed as described above using Compound 1 in the semiconductor layer, and mobility and on / off ratios were measured periodically over a period of 10 months. The performance was substantially stable over that period. The mobility varied from 0.85 to 1.09 cm ² / volt-second. The on / off ratio varied from 1.7 × 10 ⁶ to 8.6 × 10 ⁶ . The mobility was calculated by the method described in US Patent Publication (Patent Document 12) (Column 9, lines 55-63). In all cases, the devices show on / off ratios greater than 10 ⁶ and constant useful mobility during storage for Compound 1 devices, demonstrating that these devices are very stable in air. ing.

However, under similar control conditions, pentacene devices exposed to air showed a significant decrease in charge mobility. The charge mobility decreased from an initial value of 0.4 cm ² / Vs to 0.1 cm ² / Vs after storing for 2 months, and continued to decrease to 0.03 cm ² / Vs after storing for another 2 months. The on / off ratio decreased significantly in the first 2 months and then further significantly. The oxidation instability of this reference semiconductor material was confirmed.

(Example 7)
(Synthesis of 2,7-bis [2- (4-cyclohexyl-phenyl) -vinyl] anthracene (Compound 44))

  To a mixture of 2,6-dibromoanthracene (3.36 g, 10.00 mmol) and 4-cyclohexylstyrene (7.45 g, 40.00 mmol) in DMF (200 ml, anhydrous) was added sodium acetate (3.73 g, 45 0.000 mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, trans-di-m-acetatobis [2- (di-o-tolylphosphino) benzyl] dipalladium (II) (19.1 mg, 0.2 mol%) was added. The mixture was heated at 135 ° C. (oil bath) for 2 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol. The precipitate was filtered and washed with methanol and acetone. The crude product was purified by sublimation in a three-zone furnace, yielding 0.3 g (5.5%) of a yellow solid.

(Example 8)
(Synthesis of 2,7-bis [2- (4-methoxy-phenyl) -vinyl] anthracene (Compound 51))

  To a mixture of 2,6-dibromoanthracene (2.45 g, 7.29 mmol) and 4-vinylanisole (4.03 g, 29.14 mmol) in DMF (90 ml, anhydrous) was added sodium acetate (2.69 g, 32 .79 mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, trans-di-m-acetatobis [2- (di-o-tolylphosphino) benzyl] dipalladium (II) (13.9 mg, 0.2 mol%) was added. The mixture was heated at 135 ° C. (oil bath) for 2 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol. The precipitate was filtered and washed with methanol and acetone. The crude product was purified by sublimation in a 3-zone furnace, yielding 0.66 g (20%) of a yellow solid.

    Example 9

(A. Synthesis of 4- (2- (2-ethoxyethoxy) ethoxystyrene)
To a solution of 4-acetoxystyrene monomer (22.54 g, 0.14 mol), 2- (2-ethoxyethoxy) -ethyl bromide (27.39 g, 0.14 mol) in 200 ml of acetone, NaOH (16. 68 g, 0.42 mol) and water (10 ml) were added. The mixture was refluxed for 2 days. After cooling, the reaction mixture was extracted with ethyl ether. The organic layer was dried over MgSO ₄ , filtered and concentrated. Column purification (hexane / ethyl ether: 8/1 to 2/1) gave 21.82 g (66%) of product.

(B. Synthesis of 2,7-bis [2- (4- (2- (2-ethoxyethoxy) ethoxy) -phenyl) -vinyl] anthracene (Compound 52))
To a mixture of 2,6-dibromoanthracene (2.79 g, 8.30 mmol) and 4- (2- (2-ethoxyethoxy) ethoxystyrene (7.86 g, 33.26 mmol) in DMF (100 ml, anhydrous) Sodium acetate (3.07 g, 37.42 mmol) was added, the mixture was bubbled with nitrogen for 15 minutes, and then trans-di-m-acetatobis [2- (di-o-tolylphosphino) benzyl] dipalladium. (II) (15.9 mg, 0.2 mol%) was added and the mixture was heated at 135 ° C. (oil bath) for 2 days under a nitrogen atmosphere The reaction mixture was cooled to room temperature and poured into methanol. The precipitate was filtered and washed with methanol and acetone The crude product was purified by sublimation in a 3-zone furnace to give a yellow solid.

(Example 10)
(Synthesis of Compound 16)

  To a mixture of 2-vinylanthracene (4.68 g, 22.91 mmol) and 1,4-diiodobenzene (2.55 g, 7.64 mmol) in DMF (100 ml, anhydrous) was added sodium acetate (2.82 g, 34.37 mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, trans-di-m-acetatobis [2- (di-o-tolylphosphino) benzyl] dipalladium (II) (14.6 mg, 0.2 mol%) was added. The mixture was heated at 135 ° C. (oil bath) for 2 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol. The precipitate was filtered and washed with water, methanol and acetone. The crude product was purified by sublimation in a 3-zone furnace to give 1.28 g (35%) of an orange solid.

(Example 11)
(Synthesis of Compound 53)

  To a mixture of 2-vinylanthracene (4.68 g, 22.91 mmol) and 2,6-dibromonaphthalene (2.21 g, 7.64 mmol) in DMF (100 ml, anhydrous) was added sodium acetate (2.82 g, 34). .37 mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, trans-di-m-acetatobis [2- (di-o-tolylphosphino) benzyl] dipalladium (II) (14.6 mg, 0.2 mol%) was added. The mixture was heated at 135 ° C. (oil bath) for 2 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol. The precipitate was filtered and washed with water, methanol and acetone. The crude product was purified by sublimation in a three-zone furnace, yielding 0.086 g (2%) of an orange solid.

(Example 12)
(Synthesis of Compound 9)

  To a mixture of 2-vinylanthracene (4.48 g, 21.93 mmol) and 2,6-dibromoanthracene (2.57 g, 7.64 mmol) in DMF (100 ml, anhydrous) was added sodium acetate (2.82 g, 34 .37 mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, trans-di-m-acetatobis [2- (di-o-tolylphosphino) benzyl] dipalladium (II) (14.6 mg, 0.2 mol%) was added. The mixture was heated at 135 ° C. (oil bath) for 2 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol. The precipitate was filtered and washed with water, methanol and acetone. The crude product was purified by sublimation in a three zone furnace to give an orange solid.

(Example 13)
(Synthesis of 2,6-bis [2- (4-pentylphenyl) -vinyl] naphthalene (Compound 49))

  2,6-Dibromonaphthalene (2.29 g, 8.00 mmol) and 2- [2- (4-pentylphenyl) vinyl] -4,4,5,5-tetramethyl-1,3 in toluene (120 ml) , 2-dioxaborolane (7.59 g, 24.00 mmol) was added 2M sodium carbonate (4.24 g, 40.00 mmol dissolved in 20.0 ml water) followed by phase transfer agent aliquotate. (Aliquat) 336 (1.60 g, 4.00 mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, tetrakis (triphenylphosphine) palladium (0) (185.3 mg, 2 mol%) was added. The mixture was heated at 90 ° C. (oil bath) for 3 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol (300 ml). The yellow precipitate was filtered and washed with dilute acid (5% HCl), water, methanol and then acetone. The crude product was purified by sublimation in a three zone furnace to give 2.55 g (67%) of a pale yellow solid.

(Example 14)
(Synthesis of 2,7-bis [2- (4-pentyl-phenyl) -vinyl] -9H-fluorene (Compound 50))

  2,7-Dibromofluorene (2.67 g, 8.00 mmol) and 2- [2- (4-pentylphenyl) vinyl] -4,4,5,5-tetramethyl-1,3 in toluene (120 ml) , 2-dioxaborolane (7.59 g, 24.00 mmol) was added 2M sodium carbonate (4.24 g, 40.00 mmol dissolved in 20.0 ml water) followed by phase transfer agent aliquotate. (Aliquat) 336 (1.60 g, 4.00 mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, tetrakis (triphenylphosphine) palladium (0) (185.3 mg, 2 mol%) was added. The mixture was heated at 90 ° C. (oil bath) for 3 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol (300 ml). The yellow precipitate was filtered and washed with dilute acid (5% HCl), water, methanol and then acetone. The crude product was purified by sublimation in a three zone furnace to give 2.59 g (63%) of a yellow solid.

    (Example 15)

(A) 4-Bromo -o- xylene (75.00 g, 0.28 mol) was dissolved in CCl ₄ in 900 ml. Bromine (82.00 ml, 1.60 mol) was gradually added while irradiating with UV light. After the addition, the reaction mixture was irradiated for an additional hour. The reaction mixture was washed twice with water and concentrated on a rotary evaporator. The precipitate was filtered, washed with hexane and dried in a vacuum oven (80.59 g, 57%).

  (B) 4-Bromo-1,2-bis-dibromomethyl-benzene (20.00 g, 0.040 mol), 1,4-naphthoquinone (6.31 g, 0.040 mol) and Nal (in 300 ml DMAc) 68.81 g, 0.46 mol) was refluxed for 18 hours. After cooling, the reaction mixture was poured into water. The precipitate was filtered, washed with MeOH and purified by sublimation to give a yellow solid product (3.67 g, 27%).

(C) A 300 ml flask was charged with Al wire (8.67 g, 0.32 mol), HgCl ₂ (0.17 g, 0.64 mol), cyclohexanol (200 ml) and a catalytic amount of CBr ₄ (0.85 g, 0.0026 mol) was added. The mixture was bubbled with nitrogen for 15 minutes. The reaction was initiated by heating, cooled to slow the reaction and then completed by refluxing for 4 hours. To this solution was added 8-bromo-naphthacene-5,12-dione (12.72 g, 0.032 mol). The mixture was refluxed for 2 days. After cooling slightly, the reaction mixture was poured into MeOH / H ₂ O / concentrated HCl solution (1/1/1, 800 ml). The precipitate was filtered and washed with MeOH / H ₂ O / conc. HCl (1/1/1) and then methanol. The crude product was purified by sublimation in a three-zone furnace to give a pure orange product (8.97 g, 77%).

((D) Synthesis of 2- (4-pentylphenyl) -vinyl] -tetracene (Compound 36))
2-Bromotetracene (3.50 g, 11.39 mmol) and 2- [2- (4-pentylphenyl) vinyl] -4,4,5,5-tetramethyl-1,3,2 in toluene (150 ml) To a mixture of dioxaborolane (4.32 g, 13.67 mmol) was added 2M sodium carbonate (6.04 g, 56.95 mmol dissolved in 28.5 ml water) followed by phase transfer agent aliquot (Aliquat ) (R) 336 (2.28 g, 5.70 mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, tetrakis (triphenylphosphine) palladium (0) (263.0 mg, 2 mol%) was added. The mixture was heated at 90 ° C. (oil bath) for 3 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol. The precipitate was filtered and washed with dilute acid (5% HCl), water, methanol and then acetone. The crude product was purified by sublimation in a 3-zone furnace, yielding 2.91 g (64%) of a red solid.

(Example 16)
(Synthesis of 2- (4-dodecylphenyl) -vinyl] -tetracene (Compound 54))

  To a mixture of 2-bromotetracene (4.91 g, 15.97 mmol) and 4-dodecylstyrene (5.22 g, 19.00 mmol) in DMF (200 ml, anhydrous) was added sodium acetate (1.97 g, 24.00). Mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, trans-di-m-acetatobis [2- (di-o-tolylphosphino) benzyl] dipalladium (II) (15.00 mg, 0.2 mol%) was added. The mixture was heated at 135 ° C. (oil bath) for 2 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature. The precipitate was filtered and washed with water, methanol, chloroform and acetone. The crude product was purified by sublimation in a one-zone furnace, yielding 3.60 g (45%) of a red solid.

(Example 17)
(Synthesis of Compound 42)

  To a mixture of 2-bromotetracene (3.60 g, 11.72 mmol) and p-divinylbenzene (0.51 g, 3.91 mmol) in DMF (80 ml, anhydrous) was added sodium acetate (1.44 g, 17.58 mmol). Mmol) was added. The mixture was bubbled with nitrogen for 15 minutes. Next, trans-di-m-acetatobis [2- (di-o-tolylphosphino) benzyl] dipalladium (II) (7.5 mg, 0.2 mol%) was added. The mixture was heated at 135 ° C. (oil bath) for 2 days under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and poured into methanol. The precipitate was filtered and washed with water, methanol and acetone. The crude product was purified by sublimation in a three-zone furnace to obtain a red solid.

(Example 18)
This example shows the manufacture and device characteristics of an OLED fabricated using an aryl-vinylene aromatic compound for the hole transport layer.

  ITO was used as the anode on the glass substrate. The glass substrate with patterned ITO was cleaned with oxygen plasma for 5 minutes. Immediately after cooling, a buffer material (Buffer-1) was spin coated from the aqueous dispersion onto the ITO surface. After drying, the substrate was transferred to a vacuum deposition chamber and 200 liters of hole transport material was evaporated. Subsequently, a blue light emitting material and a host material were deposited by co-evaporation. An electron transport material was formed by evaporation. The layers were made of 300 Ｚ ZrQ or 100 Ｂ BAlq and 100 Ｚ ZrQ. Thin 6Å lithium fluoride was evaporated on top of the ZrQ layer as an electron injection layer. The mask was changed in vacuum and a 1000 Å layer of Al was deposited by thermal evaporation to form the cathode. The chamber was evacuated with argon and the device was encapsulated with a glass lid, desiccant and UV curable epoxy. Abbreviations used are as follows.

  Buffer-1 refers to an aqueous dispersion of poly (3,4-dioxythiophene) and polymeric fluorinated sulfonic acid. The material was prepared using a procedure similar to that described in Example 3 of US Patent Publication (Patent Document 2).

  BAlq refers to the complex bis (2-methyl-8-hydroxyquinolinato) (4-phenylphenolato) aluminum.

  ZrQ refers to the complex tetrakis (8-hydroxyquinolinato) zirconium.

  The lower NPB refers to N, N'-bis (naphthalen-1-yl) -N, N'-bis- (phenyl) benzidine.

  The materials used for the devices and the device characteristics are shown in Table 2 below.

  Note that not all of the operations described above in the summary or example are required, some of the specific operations may not be necessary, and one or more additional operations may be performed in addition to those described. I want to be. Furthermore, the order of operations listed does not necessarily have to be performed.

  In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

  Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, advantages, advantages, problem resolutions and advantages, advantages or features that provide or make more obvious are not to be construed as essential, necessary or essential requirements of any or all of the claims.

式中、Ａｒは、以下の基：

およびこれらの組み合わせからなる群から選択され、
式中、
Ａｒ’およびＡｒ”は、アリール基からなる群から独立して選択され、
ｍおよびｎは０〜５の値をそれぞれ独立して有する整数であり、ｍ＋ｎ≠０であり、
Ｑは、Ｓ、Ｓｅ、Ｔｅ、ＯおよびＮＲ ^０ からなる群から選択され、
Ｑ ^１ は、Ｓｅ、Ｔｅ、ＯおよびＮＲ ^０ からなる群から選択され、
ｑおよびｒは、０、１、２、３、４および５からなる群から独立して選択され、
ｓは、１〜５の値を有する整数であり、
ｔは、２〜５の値を有する整数であり、
Ｒ ^０ は、水素、アルキルおよびアリールからなる群から選択され、
Ｒ ^１ 〜Ｒ ^１０ は、水素、アルキル、アリール、ハロゲン、ヒドロキシル、アリールオキシ、アルコキシ、アルケニル、アルキニル、アミノ、アルキルチオ、ホスフィノ、シリル、−ＣＯＲ、−ＣＯＯＲ、−ＰＯ _３ Ｒ _２ 、−ＯＰＯ _３ Ｒ _２ およびＣＮからなる群から独立して選択され、
Ｒは、水素、アルキル、アリール、アルケニル、アルキニルおよびアミノからなる群から選択され、
式中、任意の２つの近接基Ｒ ^５ 〜Ｒ ^１０ は一緒になって環を形成することができることを特徴とする有機薄膜トランジスタ。
２．
ｒ≠０およびｓ≠０または１であることを特徴とする前記１．に記載のトランジスタ。
３．
Ａｒは、

およびこれらの組み合わせからなる群から選択され、式中、ｒ≠０であることを特徴とする前記１．に記載のトランジスタ。
４．
前記１．に記載のトランジスタであって、
前記絶縁層、前記ゲート電極、前記半導体層、前記ソース電極および前記ドレイン電極が任意の順序で配置され、ただし、前記ゲート電極および前記半導体層の両方が前記絶縁層と接触しており、前記ソース電極および前記ドレイン電極の両方が前記半導体層と接触しており、前記電極が互いに分離されていることを特徴とするトランジスタ。
５．
前記１．に記載のトランジスタであって、
前記基板が、１つまたは複数の無機ガラス、セラミック箔、アクリル、エポキシ、ポリアミド、ポリカーボネート、ポリイミド、ポリケトン、ポリ（オキシ−１，４−フェニレンオキシ−１，４−フェニレンカルボニル−１，４−フェニレン）、ポリノルボルネン、ポリフェニレンオキシド、ポリ（エチレンナフタレンジカルボキシレート）、ポリ（エチレンテレフタレート）、ポリ（フェニレンスルフィド）、繊維強化プラスチックまたは被覆金属箔を含むことを特徴とするトランジスタ。
６．
前記１．に記載のトランジスタであって、
前記ゲート電極が、ドープされたケイ素、アルミニウム、金、クロム、インジウム錫酸化物、ポリスチレンスルホネートをドープされたポリ（３，４−エチレンジオキシチオフェン）（ＰＳＳ−ＰＥＤＯＴ）、ポリマーバインダーに分散されたカーボンブラックまたはグラファイト、およびポリマーバインダー中のコロイド銀分散液を含むことを特徴とするトランジスタ。
７．
前記１．に記載のトランジスタであって、
前記ソース電極およびドレイン電極が、アルミニウム、バリウム、カルシウム、クロム、金、銀、ニッケル、パラジウム、白金、チタンおよびこれらの合金、カーボンナノチューブ、ポリアニリン、ポリ（３，４−エチレンジオキシチオフェン）／ポリ−（スチレンスルホネート）（ＰＥＤＯＴ：ＰＳＳ）、カーボンナノチューブの導電性ポリマー中の分散液、金属の導電性ポリマー中の分散液、およびこれらの多層を含むことを特徴とするトランジスタ。
８．
前記１．に記載のトランジスタであって、
前記絶縁層が、１つまたは複数の酸化アルミニウム、酸化ケイ素、酸化タンタル、酸化チタン、窒化ケイ素、チタン酸バリウム、チタン酸バリウムストロンチウム、チタン酸ジルコン酸バリウム、セレン化亜鉛、硫化亜鉛、これらの合金、これらの組み合わせおよびこれらの多層、１つまたは複数のポリエステル、ポリカーボネート、ポリ（ビニルフェノール）、ポリイミド、ポリスチレン、ポリ（メタクリレート）、ポリ（アクリレート）、エポキシ樹脂、これらのブレンドおよびこれらの多層を含むことを特徴とするトランジスタ。
９．
前記１．に記載のトランジスタであって、
前記半導体化合物が、化合物１〜６４：

からなる群から選択されることを特徴とするトランジスタ。
１０．
式１：

により表される化合物であって、
式中、Ａｒは、

からなる群から選択され、
式中、
Ａｒ’およびＡｒ”は、アリール基からなる群から独立して選択され、
ｍおよびｎは０〜５の値をそれぞれ独立して有する整数であり、ｍ＋ｎ≠０であり、
Ｑは、Ｓ、Ｓｅ、Ｔｅ、ＯおよびＮＲ ^０ からなる群から選択され、
Ｑ ^１ は、Ｓｅ、Ｔｅ、ＯおよびＮＲ ^０ からなる群から選択され、
ｑおよびｒは０〜５の値をそれぞれ独立して有する整数であり、
ｓは、１〜５の値を有する整数であり、
ｔは、２〜５の値を有する整数であり、
Ｒ ^０ は、水素、アルキルおよびアリールからなる群から選択され、
Ｒ ^１ 〜Ｒ ^１０ は、水素、アルキル、アリール、ハロゲン、ヒドロキシル、アリールオキシ、アルコキシ、アルケニル、アルキニル、アルキルチオ、ホスフィノ、シリル、−ＣＯＲ、−ＣＯＯＲ、−ＰＯ _３ Ｒ _２ 、−ＯＰＯ _３ Ｒ _２ およびＣＮからなる群から独立して選択され、
Ｒは、水素、アルキル、アリール、アルケニルおよびアルキニルからなる群から選択され、
式中、任意の２つの近接基Ｒ ^５ 〜Ｒ ^１０ は一緒になって環を形成することができることを特徴とする化合物。
１１．
アリール−エチレンアセンを調製する方法であって、
式２：

のジボロン化合物を、

からなる群から選択されるジハロアリーレン化合物と、ゼロ価のＰｄ錯体の存在下で反応させて、アリール−エチレンアセン化合物を形成する工程を含み、
式中、
ｍおよびｎは０〜３の値をそれぞれ独立して有する整数であり、
Ｒ’およびＲ”は独立してＨまたはアルキルであり、
Ｈａｌは、Ｃｌ、ＢｒおよびＩからなる群から独立して選択され、
Ａｒ’はアリール基であり、
Ｑは、Ｓ、Ｓｅ、Ｔｅ、ＯまたはＮＲ ^０ からなる群から選択され、
Ｒ ^１ 、Ｒ ^２ およびＲ ^５ 〜Ｒ ^１０ は、水素、アルキル、アリール、ハロゲン、ヒドロキシル、アリールオキシ、アルコキシ、アルケニル、アルキニル、アミノ、アルキルチオ、ホスフィノ、シリル、−ＣＯＲ、−ＣＯＯＲ、−ＰＯ _３ Ｒ _２ 、−ＯＰＯ _３ Ｒ _２ およびＣＮからなる群から独立して選択され、
Ｒは、水素、アルキル、アリール、アルケニル、アルキニルおよびアミノからなる群から選択され、
Ｒ ^０ は水素、アルキルまたはアリールであり、
式中、任意の２つの近接基Ｒ ^５ 〜Ｒ ^１０ は一緒になって環を形成することができることを特徴とするアリール−エチレンアセンを調製する方法。
１２．
アリール−エチレンアセンを調製する方法であって、
式３：

のアリール置換エチレン化合物を、

からなる群から選択されるジハロアリーレン化合物と、ゼロ価のＰｄ錯体の存在下で反応させて、アリール−エチレンアセン化合物を形成する工程を含み、
式中、
ｍおよびｎは０〜３の値をそれぞれ独立して有する整数であり、
Ｒ’およびＲ”は独立してＨまたはアルキルであり、
Ｈａｌは、Ｃｌ、ＢｒおよびＩからなる群から独立して選択され、
Ａｒ’はアリール基であり、
Ｑは、Ｓ、Ｓｅ、Ｔｅ、ＯおよびＮＲ ^０ からなる群から選択され、
Ｒ ^１ 、Ｒ ^２ およびＲ ^５ 〜Ｒ ^１０ は、水素、アルキル、アリール、ハロゲン、ヒドロキシル、アリールオキシ、アルコキシ、アルケニル、アルキニル、アミノ、アルキルチオ、ホスフィノ、シリル、−ＣＯＲ、−ＣＯＯＲ、−ＰＯ _３ Ｒ _２ 、−ＯＰＯ _３ Ｒ _２ およびＣＮからなる群から独立して選択され、
Ｒは、水素、アルキル、アリール、アルケニル、アルキニルおよびアミノからなる群から選択され、
Ｒ ^０ は水素、アルキルまたはアリールであり、
式中、任意の２つの近接基Ｒ ^５ 〜Ｒ ^１０ は一緒になって環を形成することができることを特徴とするアリール−エチレンアセンを調製する方法。
１３．
アリール−エチレンアセンを調製する方法であって、

からなる群から選択されるアセン誘導体を、ハロ−アリール化合物、Ａｒ−Ｈａｌと、ゼロ価のＰｄ錯体の存在下で反応させる工程を含み、
式中、
ｍおよびｎは０〜３の値をそれぞれ独立して有する整数であり、
Ｒ’およびＲ”は独立してＨまたはアルキルであり、
Ｈａｌは、Ｃｌ、ＢｒおよびＩからなる群から独立して選択され、
Ａｒ’はアリール基であり、
Ｑは、Ｓ、Ｓｅ、Ｔｅ、ＯおよびＮＲ ^０ からなる群から選択され、
Ｒ ^１ 、Ｒ ^２ およびＲ ^５ 〜Ｒ ^１０ は、水素、アルキル、アリール、ハロゲン、ヒドロキシル、アリールオキシ、アルコキシ、アルケニル、アルキニル、アミノ、アルキルチオ、ホスフィノ、シリル、−ＣＯＲ、−ＣＯＯＲ、−ＰＯ _３ Ｒ _２ 、−ＯＰＯ _３ Ｒ _２ およびＣＮからなる群から独立して選択され、
Ｒは、水素、アルキル、アリール、アルケニル、アルキニルおよびアミノからなる群から選択され、
Ｒ ^０ は水素、アルキルまたはアリールであり、
式中、任意の２つの近接基Ｒ ^５ 〜Ｒ ^１０ は一緒になって環を形成することができることを特徴とするアリール−エチレンアセンを調製する方法。
１４．
電荷輸送層を含むことを特徴とする有機電子デバイスであって、
該電荷輸送層は
式１：

により表される少なくとも１つの化合物を含み、
Ａｒはアリーレン基であり、
Ａｒ’およびＡｒ”は、アリール基からなる群から独立して選択され、
Ｒ ^１ 〜Ｒ ^４ は、水素、アルキル、アリール、ハロゲン、ヒドロキシル、アリールオキシ、アルコキシ、アルケニル、アルキニル、アミノ、アルキルチオ、ホスフィノ、シリル、−ＣＯＲ、−ＣＯＯＲ、−ＰＯ _３ Ｒ _２ 、−ＯＰＯ _３ Ｒ _２ およびＣＮからなる群から独立して選択され、
Ｒは、水素、アルキル、アリール、アルケニル、アルキニルおよびアミノからなる群から選択され、
ｍおよびｎは０〜５の値をそれぞれ独立して有する整数であり、ｍ＋ｎ≠０であり、
さらに、ジアリールアミノ基がないことを特徴とする有機電子デバイス。
１５．
前記１４．に記載のデバイスであって、
Ａｒが、縮合多環式芳香族基、および単結合により結合した少なくとも２つの環を有する芳香族基からなる群から選択されることを特徴とするデバイス。
１６．
前記１４．に記載のデバイスであって、
Ａｒが、

およびこれらの組み合わせから選択され、
式中、
Ｑは、Ｓ、Ｓｅ、Ｔｅ、ＯまたはＮＲ ^０ からなる群から選択され、
ｑおよびｒは０〜５の値をそれぞれ独立して有する整数であり、
ｓは、１〜５の値を有する整数であり、
Ｒ ^０ は、水素、アルキルおよびアリールからなる群から独立して選択され、
Ｒ ^５ 〜Ｒ ^１０ は、水素、アルキル、アリール、ハロゲン、ヒドロキシル、アリールオキシ、アルコキシ、アルケニル、アルキニル、アミノ、アルキルチオ、ホスフィノ、シリル、−ＣＯＲ、−ＣＯＯＲ、−ＰＯ _３ Ｒ _２ 、−ＯＰＯ _３ Ｒ _２ およびＣＮからなる群から独立して選択され、
Ｒは、水素、アルキル、アリール、アルケニル、アルキニルおよびアミノからなる群から選択され、
式中、任意の２つの近接基Ｒ ^５ 〜Ｒ ^１０ は一緒になって環を形成することができることを特徴とするデバイス。
１７．
前記１４．に記載のデバイスであって、
Ａｒが、２，６−ナフタレン、置換２，６−ナフタレン、２，６−アントラセン、置換２，６−アントラセン、２，６−フルオレン、置換２，６−フルオレン、２，６−カルバゾール、置換２，６−カルバゾールおよびこれらの組み合わせからなる群のうち少なくとも１つから選択されることを特徴とするデバイス。
１８．
前記１４．に記載のデバイスであって、
Ａｒ’およびＡｒ”が、非置換アリール基および置換アリール基より独立して選択され、前記アリール基の置換基が、アルキル、アリール、チオアルキル、シリル、アルキルアリール、アルコキシ、アルキルエーテル、エーテルアルキル、フッ素およびこれらの組み合わせからなる群から独立して選択されることを特徴とするデバイス。
１９．
アノード、カソードおよびその間に配置された光活性層をさらに含むことを特徴とする前記１４．に記載のデバイス。
２０．
前記電荷輸送層が、正孔輸送層であり、前記光活性層とアノードとの間に配置されていることを特徴とする前記１９．に記載のデバイス。
２１.
前記電荷輸送層が、電子輸送層であり、前記光活性層とカノードとの間に配置されていることを特徴とする前記１９．に記載のデバイス。
２２．
アノード、カソードおよびその間に配置された光活性層を含む有機電子デバイスであって、
前記光活性層が、
式１：

により表される少なくとも１つの化合物を含み、
式中、
Ａｒはアリーレン基であり、
Ａｒ’およびＡｒ”は、アリール基からなる群から独立して選択され、
Ｒ ^１ 〜Ｒ ^４ は、水素、アルキル、アリール、ハロゲン、ヒドロキシル、アリールオキシ、アルコキシ、アルケニル、アルキニル、アミノ、アルキルチオ、ホスフィノ、シリル、−ＣＯＲ、−ＣＯＯＲ、−ＰＯ _３ Ｒ _２ 、−ＯＰＯ _３ Ｒ _２ およびＣＮからなる群から独立して選択され、
Ｒは、水素、アルキル、アリール、アルケニル、アルキニルおよびアミノからなる群から選択され、
ｍおよびｎは０〜５の値をそれぞれ独立して有する整数であり、ｍ＋ｎ≠０であり、
さらに、ジアリールアミノ基がないことを特徴とする有機電子デバイス。
For clarity, it is contemplated that certain features described herein in separate embodiments may be provided in combination in a single embodiment. Conversely, various features that are described in a single embodiment for the sake of brevity may also be provided separately or in sub-combinations. Further, values stated in ranges include each value within that range.
The inventions described in this specification are listed below.
1.
A substrate,
An insulating layer;
A gate electrode;
An organic semiconductor layer;
A source electrode;
Drain electrode and
An organic thin film transistor comprising:
The organic semiconductor layer comprises a compound of Formula 1;

Wherein Ar is the following group:

And selected from the group consisting of these,
Where
Ar ′ and Ar ″ are independently selected from the group consisting of aryl groups;
m and n are integers each independently having a value of 0 to 5, m + n ≠ 0,
Q is selected from the group consisting of S, Se, Te, O and NR ⁰ ;
Q ¹ is selected from the group consisting of Se, Te, O and NR ⁰ ;
q and r are independently selected from the group consisting of 0, 1, 2, 3, 4 and 5;
s is an integer having a value of 1 to 5,
t is an integer having a value of 2-5,
R ⁰ is selected from the group consisting of hydrogen, alkyl and aryl;
R ^{1 to} R ¹⁰ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R Independently selected from the group consisting of ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
In the formula, any two adjacent groups R ^{5 to} R ¹⁰ can form a ring together to form an organic thin film transistor.
2.
1. r ≠ 0 and s ≠ 0 or 1. The transistor described in 1.
3.
Ar is

And a combination thereof, wherein r ≠ 0, wherein 1. The transistor described in 1.
4).
1 above. The transistor according to claim 1,
The insulating layer, the gate electrode, the semiconductor layer, the source electrode and the drain electrode are arranged in any order, provided that both the gate electrode and the semiconductor layer are in contact with the insulating layer, and the source A transistor, wherein both the electrode and the drain electrode are in contact with the semiconductor layer, and the electrodes are separated from each other.
5.
1 above. The transistor according to claim 1,
The substrate is one or more inorganic glass, ceramic foil, acrylic, epoxy, polyamide, polycarbonate, polyimide, polyketone, poly (oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) ), Polynorbornene, polyphenylene oxide, poly (ethylene naphthalene dicarboxylate), poly (ethylene terephthalate), poly (phenylene sulfide), fiber reinforced plastic or coated metal foil.
6).
1 above. The transistor according to claim 1,
The gate electrode was dispersed in doped silicon, aluminum, gold, chromium, indium tin oxide, polystyrene sulfonate doped poly (3,4-ethylenedioxythiophene) (PSS-PEDOT), polymer binder A transistor comprising carbon black or graphite and a colloidal silver dispersion in a polymer binder.
7).
1 above. The transistor according to claim 1,
The source and drain electrodes are made of aluminum, barium, calcium, chromium, gold, silver, nickel, palladium, platinum, titanium, and alloys thereof, carbon nanotubes, polyaniline, poly (3,4-ethylenedioxythiophene) / poly A transistor comprising: (styrenesulfonate) (PEDOT: PSS), a dispersion of carbon nanotubes in a conductive polymer, a dispersion of a metal in a conductive polymer, and multilayers thereof.
8).
1 above. The transistor according to claim 1,
The insulating layer is one or more of aluminum oxide, silicon oxide, tantalum oxide, titanium oxide, silicon nitride, barium titanate, barium strontium titanate, barium zirconate titanate, zinc selenide, zinc sulfide, alloys thereof , Combinations thereof and multilayers thereof, including one or more polyesters, polycarbonates, poly (vinylphenols), polyimides, polystyrenes, poly (methacrylates), poly (acrylates), epoxy resins, blends thereof and multilayers thereof A transistor characterized by that.
9.
1 above. The transistor according to claim 1,
The semiconductor compound is compound 1 to 64:

A transistor selected from the group consisting of:
10.
Formula 1:

A compound represented by
Where Ar is

Selected from the group consisting of
Where
Ar ′ and Ar ″ are independently selected from the group consisting of aryl groups;
m and n are integers each independently having a value of 0 to 5, m + n ≠ 0,
Q is selected from the group consisting of S, Se, Te, O and NR ⁰ ;
Q ¹ is selected from the group consisting of Se, Te, O and NR ⁰ ;
q and r are integers each independently having a value of 0 to 5,
s is an integer having a value of 1 to 5,
t is an integer having a value of 2-5,
R ⁰ is selected from the group consisting of hydrogen, alkyl and aryl;
R ^{1 to} R ¹⁰ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R ₂ and Selected independently from the group consisting of CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl and alkynyl;
Wherein any two adjacent groups R ^{5 to} R ¹⁰ can be combined to form a ring.
11.
A process for preparing an aryl-ethyleneacene comprising the steps of:
Formula 2:

Diboron compound

Reacting with a dihaloarylene compound selected from the group consisting of: in the presence of a zero-valent Pd complex to form an aryl-ethyleneacene compound;
Where
m and n are integers each independently having a value of 0 to 3,
R ′ and R ″ are independently H or alkyl;
Hal is independently selected from the group consisting of Cl, Br and I;
Ar ′ is an aryl group,
Q is selected from the group consisting of S, Se, Te, O or NR ⁰ ;
R ¹ , R ² and R ^{5 to} R ¹⁰ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , independently selected from the group consisting of —OPO ₃ R ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
R ⁰ is hydrogen, alkyl or aryl;
A process for preparing an aryl-ethyleneacene, characterized in that any two adjacent groups R ^{5 to} R ¹⁰ can be taken together to form a ring.
12
A process for preparing an aryl-ethyleneacene comprising the steps of:
Formula 3:

An aryl-substituted ethylene compound

Reacting with a dihaloarylene compound selected from the group consisting of: in the presence of a zero-valent Pd complex to form an aryl-ethyleneacene compound;
Where
m and n are integers each independently having a value of 0 to 3,
R ′ and R ″ are independently H or alkyl;
Hal is independently selected from the group consisting of Cl, Br and I;
Ar ′ is an aryl group,
Q is selected from the group consisting of S, Se, Te, O and NR ⁰ ;
R ¹ , R ² and R ^{5 to} R ¹⁰ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , independently selected from the group consisting of —OPO ₃ R ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
R ⁰ is hydrogen, alkyl or aryl;
A process for preparing an aryl-ethyleneacene, characterized in that any two adjacent groups R ^{5 to} R ¹⁰ can be taken together to form a ring.
13.
A process for preparing an aryl-ethyleneacene comprising the steps of:

Reacting an acene derivative selected from the group consisting of a halo-aryl compound, Ar-Hal, in the presence of a zero-valent Pd complex,
Where
m and n are integers each independently having a value of 0 to 3,
R ′ and R ″ are independently H or alkyl;
Hal is independently selected from the group consisting of Cl, Br and I;
Ar ′ is an aryl group,
Q is selected from the group consisting of S, Se, Te, O and NR ⁰ ;
R ¹ , R ² and R ^{5 to} R ¹⁰ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , independently selected from the group consisting of —OPO ₃ R ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
R ⁰ is hydrogen, alkyl or aryl;
A process for preparing an aryl-ethyleneacene, characterized in that any two adjacent groups R ^{5 to} R ¹⁰ can be taken together to form a ring.
14
An organic electronic device comprising a charge transport layer,
The charge transport layer is
Formula 1:

Comprising at least one compound represented by
Ar is an arylene group,
Ar ′ and Ar ″ are independently selected from the group consisting of aryl groups;
R ^{1 to} R ⁴ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R Independently selected from the group consisting of ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
m and n are integers each independently having a value of 0 to 5, m + n ≠ 0,
Furthermore, the organic electronic device characterized by having no diarylamino group.
15.
14. A device as described in
A device wherein Ar is selected from the group consisting of a fused polycyclic aromatic group and an aromatic group having at least two rings joined by a single bond.
16.
14. A device as described in
Ar is

And combinations thereof,
Where
Q is selected from the group consisting of S, Se, Te, O or NR ⁰ ;
q and r are integers each independently having a value of 0 to 5,
s is an integer having a value of 1 to 5,
R ⁰ is independently selected from the group consisting of hydrogen, alkyl and aryl;
R ^{5 to} R ¹⁰ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R Independently selected from the group consisting of ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
Wherein any two neighboring groups R ^{5 to} R ¹⁰ can be taken together to form a ring.
17.
14. A device as described in
Ar is 2,6-naphthalene, substituted 2,6-naphthalene, 2,6-anthracene, substituted 2,6-anthracene, 2,6-fluorene, substituted 2,6-fluorene, 2,6-carbazole, substituted 2 , 6-carbazole and a device selected from the group consisting of combinations thereof.
18.
14. A device as described in
Ar ′ and Ar ″ are independently selected from an unsubstituted aryl group and a substituted aryl group, and the substituent of the aryl group is alkyl, aryl, thioalkyl, silyl, alkylaryl, alkoxy, alkyl ether, ether alkyl, fluorine And a device independently selected from the group consisting of these and combinations thereof.
19.
15. The method according to claim 14, further comprising an anode, a cathode, and a photoactive layer disposed therebetween. Device described in.
20.
18. The charge transport layer is a hole transport layer, and is disposed between the photoactive layer and the anode. Device described in.
21.
18. The charge transport layer is an electron transport layer, and is disposed between the photoactive layer and a canode. Device described in.
22.
An organic electronic device comprising an anode, a cathode and a photoactive layer disposed therebetween,
The photoactive layer is
Formula 1:

Comprising at least one compound represented by
Where
Ar is an arylene group,
Ar ′ and Ar ″ are independently selected from the group consisting of aryl groups;
R ^{1 to} R ⁴ are hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO ₃ R ₂ , —OPO ₃ R Independently selected from the group consisting of ₂ and CN;
R is selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkynyl and amino;
m and n are integers each independently having a value of 0 to 5, m + n ≠ 0,
Furthermore, the organic electronic device characterized by having no diarylamino group.

It is the schematic of the organic thin-film transistor (OTFT) of bottom contact mode. It is the schematic of the OTFT of a top contact mode. FIG. 6 is a schematic diagram of another embodiment of an OTFT. FIG. 6 is a schematic diagram of another embodiment of an OTFT. 1 is a schematic view of a display device.

Claims (7)

A substrate,
An insulating layer;
A gate electrode;
An organic semiconductor layer;
A source electrode;
An organic thin film transistor including a drain electrode,
The organic semiconductor layer has the following compounds 1, 3, 36, 48-50 and 54:
Compound 1

Compound 3

Compound 36

Compound 48

Compound 49

Compound 50

Compound 54

An organic thin film transistor comprising at least one compound selected from the group consisting of: Compound 1, 3, 36, 48-50 or 54 below:
Compound 1

Compound 3

Compound 36

Compound 49

Compound 50

Compound 54

Any of the compounds. A process for preparing an aryl-ethyleneacene comprising the steps of:
Formula 2:

Diboron compound
Dihaloarylene compounds:

And reacting in the presence of a zero-valent Pd complex to form an aryl-ethyleneacene compound,
Where
m is 1 and n is 1 or 2, provided that Ar′- is

In this case, n is 2,
R ′ and R ″ are independently H or alkyl;
Hal is independently selected from the group consisting of Cl, Br and I;
Ar ′ is a phenyl group which may have an alkyl substituent at the p-position,
R ¹ , R ² and R ^{5 to} R ¹⁰ are hydrogen,
A process for the preparation of aryl-ethyleneacenes. A process for preparing an aryl-ethyleneacene comprising the steps of:
Formula 3:

An aryl-substituted ethylene compound

Reacting with a dihaloarylene compound selected from the group consisting of: in the presence of a zero-valent Pd complex to form an aryl-ethyleneacene compound;
Where
n is 1 or 2,
However, Ar-

In this case, n is 2,
R ′ and R ″ are independently H or alkyl;
Hal is independently selected from the group consisting of Cl, Br and I;
Ar is a phenyl group which may have an alkyl substituent in the p-position;
R ¹ , R ² and R ^{5 to} R ¹⁰ are hydrogen,
A process for the preparation of aryl-ethyleneacenes. A process for preparing an aryl-ethyleneacene comprising the steps of:

Or

Reacting an acene derivative selected from the group consisting of a halo-aryl compound, Ar-Hal, in the presence of a zero-valent Pd complex,
Where
m is 1 and n is 1 or 2, provided that Ar- is

In this case, n is 2,
R ′ and R ″ are independently H or alkyl;
Hal is independently selected from the group consisting of Cl, Br and I;
Ar is a phenyl group which may have an alkyl substituent in the p-position;
R ^{1 to} R ¹⁰ are hydrogen,
A process for the preparation of aryl-ethyleneacenes. An organic electronic device comprising a charge transport layer,
The charge transport layer comprises the following compounds 1, 3, 36, 48-50 and 54:
Compound 1

Compound 3

Compound 36

Compound 48

Compound 49

Compound 50

Compound 54

An organic electronic device comprising at least one compound selected from the group consisting of: An organic electronic device comprising an anode, a cathode and a photoactive layer disposed therebetween,
The photoactive layer is
Compounds 1, 3, 36, 48-50 and 54 below:
Compound 1

Compound 3

Compound 36

Compound 48

Compound 49

Compound 50

Compound 54

An organic electronic device comprising at least one compound selected from the group consisting of:

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