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EP1344261A2 - Organic semiconductor, production method therefor and the use thereof - Google Patents

Organic semiconductor, production method therefor and the use thereof

Info

Publication number
EP1344261A2
EP1344261A2 EP01995611A EP01995611A EP1344261A2 EP 1344261 A2 EP1344261 A2 EP 1344261A2 EP 01995611 A EP01995611 A EP 01995611A EP 01995611 A EP01995611 A EP 01995611A EP 1344261 A2 EP1344261 A2 EP 1344261A2
Authority
EP
European Patent Office
Prior art keywords
pav
polyarylene vinylene
monomer units
monomers
regular
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01995611A
Other languages
German (de)
French (fr)
Inventor
Mark Giles
Henning Rost
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PolyIC GmbH and Co KG
Original Assignee
Merck Patent GmbH
Siemens AG
PolyIC GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH, Siemens AG, PolyIC GmbH and Co KG filed Critical Merck Patent GmbH
Publication of EP1344261A2 publication Critical patent/EP1344261A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof

Definitions

  • the invention relates to a new class of organic semiconductors with high regioregularity.
  • organic semiconducting material is used which, on the one hand, can be easily applied and processed as a film and, on the other hand, shows high charge carrier mobility.
  • the 3-alkyl substituents of thiophene can be incorporated into a polymer chain with two different orientations: on the one hand there is the head-to-tail connection (head-tail, HT) and on the other hand the head-to-head connection (head- head, HH).
  • regioregular means that only one of the link types (HH or HT) is realized.
  • a high degree of regional regularity also leads to good mobility of the charge carriers.
  • the highest mobilities that have been measured in such films so far are about 0.015-0.045 c 2 / Vs (Z.Bao, A.Dodabalapur and AJLovinger. "Soluble and processible regioregular poly (3-hexylthiophene) for thin film field-effect transistor applications with high mobility * Appl. Phys. Lett. 69 (26): 4108-10, 1996).
  • the commercially available 3-alkyl-substituted thiophenes have a regio-regularity of approx. 98% and therefore not a perfect order. In order to achieve a higher charge carrier mobility in the polymer, however, the aim is to have a regioregularity of 100%.
  • the object of the invention is therefore to provide an organic material which has a high degree of regional regularity, to specify a manufacturing process for the production of this material and finally to indicate preferred uses of the material.
  • Ar stands for an aryl group with 4 to 14 C atoms and (R) means that Ar can have one or more substituents R, which can be the same or different, and a phenyl or phenyloxy group or a straight-chain or branched or cyclic alkyl - Or alkoxy group with 1 to
  • a ⁇ means a single charged anion, where the PAV has a regioregularity of more than 98%, in particular 99% or more, preferably 99.5% or more particularly preferably 100% in the chain linkage.
  • the invention furthermore relates to a process for producing a polyarylene vinylene (PAV) with high charge carrier mobility, in particular from 10 -4 cm 2 / Vs or higher, preferably 10 "3 cm 2 / Vs or higher, particularly preferably 10 ⁇ 2 cm 2 / Vs or higher, in which an AB elimination achieves more than 98%, in particular 100%, regioregular linking of the monomers.
  • B is one of the groups -CHPPh 3 ] + C1 " , -CH 2 P0 (OEt) 2 or (-CH 3 ), which react regio-regularly with one another as part of a cross-linking condensation reaction.
  • the invention also relates to various uses of the semiconducting material, for example for organic light-emitting diodes, photocells, field emission displays or sensors, and an integrated circuit based on organic materials.
  • a method is preferably used which leads to a regio-regular HT (head-tail) linkage of the monomers.
  • the polymers generally have between 2 and 15,000 monomer units, preferably 10 to 7500, particularly preferably 100 to 5000 and very preferably between 250 and 2000 monomer units, which are linked to 98% or more in a regionally regular manner. These values are preferably chosen so that the rheological and mechanical behavior of the polymers and the films produced from them is optimized.
  • the formation of the polymer from the same or different monomer units depends on the need and can by Addition of various monomer units can be controlled during manufacture. This then results in copolymers, that is to say polymers which are composed of at least two different monomer units.
  • R, R can be identical or different and represent phenyl or a phenaloxy group or a straight-chain, branched or cyclic alkyl or alkoxy group with 1 to 25 C atoms, one or more non-adjacent CH 2 groups being represented by -0-, - S-, -CO-, -COO-, -OCO-, -NR 1 -, -NR 2 R 3 ) + A ⁇ , -O-COO-, -NR ⁇ CO-NR 1 - or -CONR 4 can be replaced and one or more H atoms can be replaced by F, CN, CI, Br, J or an aryl group having 4 to 14 C atoms, which can be substituted by one or more non-aromatic radicals R; in which R X , R 2 , R 3 , R 4 are the same or different and stand for aliphatic or aromatic hydrocarbon radicals with 1 to 25 carbon atoms or also H.
  • a 3-alkyl-substituted thiophene is particularly preferably used as the Ar, a pol (3-alkyl-2,5-thienylene-vinylene) (PTV) being formed by the carbonyl olefinization method.
  • PTV pol (3-alkyl-2,5-thienylene-vinylene)
  • an alkyl or alkoxy group having 6 to 24 carbon atoms is preferably used.
  • the polymers are preferably used as organic semiconductors, particularly preferably as a functional layer e.g. an integrated circuit, an organic diode, a photocell, field emission display or a sensor.
  • a functional layer e.g. an integrated circuit, an organic diode, a photocell, field emission display or a sensor.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Thin Film Transistor (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to a novel class of organic semiconductor with a high charge carrier mobility by means of high regio-regularity. Said regio-regularity is produced by the production of the polymer, starting from an AB elimination of the monomers.

Description

Beschreibungdescription
Organischer Halbleiter, Herstellungsverfahren dazu und VerwendungenOrganic semiconductor, manufacturing process therefor and uses
Die Erfindung betrifft eine neue Klasse organischer Halbleiter mit hoher Regioregularitat.The invention relates to a new class of organic semiconductors with high regioregularity.
Zur Herstellung eines organischen Dünnfilm-Transistors oder eines organischen Feld-Effekt-Transistors (OFET) nimmt man organisches halbleitendes Material, das sich zum einen leicht als Film aufbringen und verarbeiten lässt und zum anderen eine hohe Ladungsträgerbeweglichkeit zeigt.To produce an organic thin-film transistor or an organic field-effect transistor (OFET), organic semiconducting material is used which, on the one hand, can be easily applied and processed as a film and, on the other hand, shows high charge carrier mobility.
Bekannt ist ein organisches Material, das bereits eine zufriedenstellend hohe Ladungsträgerbeweglichkeit von 0 22cm2/Vs besitzt, das Poly (2, 5-thienylenvinylen) „PTN* . Dieses Material kann allerdings nur über einen aufwendigen Precursor-Prozess hergestellt werden und ist selbst unlös- lieh, unschmelzbar und damit nicht verarbeitbar. Dieses Material ist also teuer und zur Herstellung von Dünnschichtfilmen nicht geeignet. Es muss in situ auf dem Substrat hergestellt werden.An organic material that already has a satisfactorily high charge carrier mobility of 0 22 cm 2 / Vs is known, the poly (2, 5-thienylenevinylene) “PTN *. However, this material can only be produced using a complex precursor process and is itself unsolvable, infusible and therefore cannot be processed. This material is therefore expensive and is not suitable for the production of thin-film films. It must be made in situ on the substrate.
Deshalb wurden schon früh Versuche gestartet andere Polythi- ophene mit gleicher Ladungsträgerbeweglichkeit aber besserer Verarbeitbarkeit herzustellen (A.Assadi, C.Svensson, M. Willander and O.Inganäs „Field effect mobility of poly (3-hexyl- thiopheneP Appl. Phys . Lett. 53(3):195-7, 1988). Insbesonde- re zeigten die 3-Alkylsubstituierten Thiophene eine bessere Verarbeitbarkeit .Therefore, early attempts were made to produce other polythiophenes with the same charge carrier mobility but better processability (A.Assadi, C.Svensson, M. Willander and O.Inganäs "Field effect mobility of poly (3-hexylthiopheneP Appl. Phys. Lett 53 (3): 195-7, 1988. In particular, the 3-alkyl-substituted thiophenes showed better processability.
Die 3-Alkyl-Substituenten des Thiophens können in eine Polymer-Kette mit zwei verschiedenen Orientierungen eingebaut werden: Zum einen gibt es die Kopf-Schwanz-Verknüpfung (head- tail, HT) und zum anderen die Kopf-Kopf-Verknüpfung (head- head, HH) . Regioregular heißt in diesem Zusammenhang, dass nur eine der Verknüpfungsarten (HH oder HT) realisiert wird. Eine hohe Regioregularitat bewirkt auch eine gute Ladungsträgerbeweglichkeit. Die höchsten Beweglichkeiten, die in solchen Filmen bislang gemessen wurden betragen ca. 0,015- 0,045 c 2/Vs (Z.Bao, A.Dodabalapur and A.J.Lovinger. „Soluble and processible regioregular poly (3-hexylthiophene) for thin film field-effect transistor applications with high mobility* Appl. Phys. Lett. 69 (26) : 4108-10, 1996).The 3-alkyl substituents of thiophene can be incorporated into a polymer chain with two different orientations: on the one hand there is the head-to-tail connection (head-tail, HT) and on the other hand the head-to-head connection (head- head, HH). In this context, regioregular means that only one of the link types (HH or HT) is realized. A high degree of regional regularity also leads to good mobility of the charge carriers. The highest mobilities that have been measured in such films so far are about 0.015-0.045 c 2 / Vs (Z.Bao, A.Dodabalapur and AJLovinger. "Soluble and processible regioregular poly (3-hexylthiophene) for thin film field-effect transistor applications with high mobility * Appl. Phys. Lett. 69 (26): 4108-10, 1996).
Die kommerziell erhältlichen 3-Alkyl-substituierten Thiophene besitzen eine Regioregularitat von ca 98 % und damit keine perfekte Ordnung. Zur Erzielung einer höheren Ladungsträger- beweglichkeit im Polymer wird jedoch angestrebt, dass eine Regioregularitat von 100% gegeben ist.The commercially available 3-alkyl-substituted thiophenes have a regio-regularity of approx. 98% and therefore not a perfect order. In order to achieve a higher charge carrier mobility in the polymer, however, the aim is to have a regioregularity of 100%.
Aufgabe der Erfindung ist es daher, ein organisches Material zur Verfügung zu stellen, das hohe Regioregularitat hat, ein Herstellungsverfahren zur Produktion dieses Materials anzugeben und schließlich noch bevorzugte Verwendungen des Ma- terials anzugeben.The object of the invention is therefore to provide an organic material which has a high degree of regional regularity, to specify a manufacturing process for the production of this material and finally to indicate preferred uses of the material.
Gegenstand der Erfindung ist ein Polyarylenvinylen (PAV) der allgemeinen Formel I - (Ar (R) -CH=CH) n- in derThe invention relates to a polyarylene vinylene (PAV) of the general formula I - (Ar (R) -CH = CH) n - in the
Ar für eine Arylgruppe mit 4 bis 14 C-Atomen steht und (R) bedeutet, dass Ar einen oder mehrere Substituenten R haben kann, die gleich oder verschieden sein können und eine Phenyl- oder Phenyloxygruppe oder eine geradkettige oder ver- zweigte oder cyclische Alkyl- oder Alkoxygruppe mit 1 bisAr stands for an aryl group with 4 to 14 C atoms and (R) means that Ar can have one or more substituents R, which can be the same or different, and a phenyl or phenyloxy group or a straight-chain or branched or cyclic alkyl - Or alkoxy group with 1 to
25 C-Atomen darstellen, wobei ein oder mehrere nicht benachbarte CH2-Gruppen durch -0-, -S-, -CO-, -COO-, -OC0-, -NR1-, -NR2R3)+A", -0-COO-, -NR^CO-NR1- oder -CONR4 ersetzt sein können und wobei ein oder mehrere H-Atome durch F, CN, Cl, Br, J oder eine Arylgruppe mit 4 bis 14 C-Atome ersetzt sein können, die durch einen oder mehrere, nicht aromatische Reste R substituiert sein kann; wobei R1 /R2,R3 R4 gleich oder verschieden sind und für aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 25 C-Atomen oder auch H stehen und25 carbon atoms, one or more non-adjacent CH 2 groups by -0-, -S-, -CO-, -COO-, -OC0-, -NR 1 -, -NR 2 R 3 ) + A " , -0-COO-, -NR ^ CO-NR 1 - or -CONR 4 can be replaced and wherein one or more H atoms by F, CN, Cl, Br, J or an aryl group with 4 to 14 C- Atoms can be replaced, which can be substituted by one or more, non-aromatic radicals R; R 1 / R 2 , R 3 R 4 are identical or different and stand for aliphatic or aromatic hydrocarbon radicals with 1 to 25 C atoms or also H and
A~ ein einfach geladenes Anion bedeutet, wobei das PAV eine Regioregularitat von mehr als 98 %, insbesondere 99 % oder mehr, bevorzugt 99,5 % oder mehr besonders bevorzugt 100 % in der Kettenverknüpfung hat.A ~ means a single charged anion, where the PAV has a regioregularity of more than 98%, in particular 99% or more, preferably 99.5% or more particularly preferably 100% in the chain linkage.
Weiterhin ist Gegenstand der Erfindung ein Verfahren zur Her- Stellung eines Polyarylenvinylen (PAV) mit hoher Ladungsträgerbeweglichkeit, insbesondere von 10-4 cm2/Vs oder höher, bevorzugt 10"3 cm2/Vs oder höher, besonders bevorzugt 10~2 cm2/Vs oder höher, bei dem über eine AB-Eliminierung eine mehr als 98%, insbesondere 100 % regioregulare Verknüpfung der Monome- ren erzielt wird. Insbesondere steht für A eine Formaldehydgruppe -CH=0 und für B eine der Gruppen -CHPPh3] +C1", -CH2P0(OEt)2 oder (-CH3) , die im Rahmen einer Vernetzungskon- densationsreaktion regioregular miteinander abreagieren. Schließlich sind noch verschiedene Verwendungen des halblei- tenden Materials beispielsweise für organische Leuchtdioden, Photozellen, Feldemissionsanzeigen oder Sensoren, und eine integrierte Schaltung auf Basis organischen Materials Gegenstand der Erfindung.The invention furthermore relates to a process for producing a polyarylene vinylene (PAV) with high charge carrier mobility, in particular from 10 -4 cm 2 / Vs or higher, preferably 10 "3 cm 2 / Vs or higher, particularly preferably 10 ~ 2 cm 2 / Vs or higher, in which an AB elimination achieves more than 98%, in particular 100%, regioregular linking of the monomers. In particular, A is a formaldehyde group -CH = 0 and B is one of the groups -CHPPh 3 ] + C1 " , -CH 2 P0 (OEt) 2 or (-CH 3 ), which react regio-regularly with one another as part of a cross-linking condensation reaction. Finally, the invention also relates to various uses of the semiconducting material, for example for organic light-emitting diodes, photocells, field emission displays or sensors, and an integrated circuit based on organic materials.
Bevorzugt wird ein Verfahren angewendet, dass zu einer regio- regularen HT (head-tail) Verknüpfung der Monomeren führt.A method is preferably used which leads to a regio-regular HT (head-tail) linkage of the monomers.
Die Polymere weisen im allgemeinen zwischen 2 und 15000 Monomereinheiten, vorzugsweise 10 bis 7500 besonders bevorzugt 100 bis 5000 und ganz bevorzugt zwischen 250 und 2000 Monomereinheiten auf, die zu 98% oder mehr regioregular verknüpft sind. Diese Werte werden vorzugsweise so gewählt, dass das rheologische und mechanische Verhalten der Polymere und der daraus hergestellten Filme optimiert ist.The polymers generally have between 2 and 15,000 monomer units, preferably 10 to 7500, particularly preferably 100 to 5000 and very preferably between 250 and 2000 monomer units, which are linked to 98% or more in a regionally regular manner. These values are preferably chosen so that the rheological and mechanical behavior of the polymers and the films produced from them is optimized.
Die Bildung des Polymers aus gleichen oder ungleichen Monomereinheiten richtet sich je nach Bedarf und kann durch die Zugabe verschiedener Monomereinheiten während der Herstellung gesteuert werden. So entstehen dann Copolymere, das heißt Polymere, die zumindest aus zwei verschiedenen Monomereinheiten aufgebaut sind.The formation of the polymer from the same or different monomer units depends on the need and can by Addition of various monomer units can be controlled during manufacture. This then results in copolymers, that is to say polymers which are composed of at least two different monomer units.
Bevorzugt sind MonomereinheitenMonomer units are preferred
in der Ar folgende Bedeutung annimmt:in which Ar assumes the following meaning:
ArAr
wobei in which
R, R gleich oder verschieden sein können und Phenyl- oder eine Phenaloxygruppe oder eine geradkettige, verzweigte oder cyclische Alkyl- oder Alkoxygruppe mit 1 bis 25 C-Atomen darstellen, wobei ein oder mehrere nicht benachbarte CH2-Gruppen durch -0-, -S-, -CO-, -COO-, -OCO-, -NR1-, -NR2R3)+A~, -O-COO-, -NR^CO-NR1- oder -CONR4 ersetzt sein können und wobei ein oder mehrere H-Atome durch F, CN, CI, Br, J oder eine Arylgruppe mit 4 bis 14 C-Atomen, die durch einen oder mehrere, nicht aromatische Reste R substituiert sein kann, ersetzt sein können; wobei RX,R2,R3,R4 gleich oder verschieden sind und für aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 25 C-Atomen oder auch H stehen.R, R can be identical or different and represent phenyl or a phenaloxy group or a straight-chain, branched or cyclic alkyl or alkoxy group with 1 to 25 C atoms, one or more non-adjacent CH 2 groups being represented by -0-, - S-, -CO-, -COO-, -OCO-, -NR 1 -, -NR 2 R 3 ) + A ~ , -O-COO-, -NR ^ CO-NR 1 - or -CONR 4 can be replaced and one or more H atoms can be replaced by F, CN, CI, Br, J or an aryl group having 4 to 14 C atoms, which can be substituted by one or more non-aromatic radicals R; in which R X , R 2 , R 3 , R 4 are the same or different and stand for aliphatic or aromatic hydrocarbon radicals with 1 to 25 carbon atoms or also H.
Besonders bevorzugt wird als Ar ein 3-Alkyl-substituiertes Thiophen eingesetzt, wobei durch die Methode der Carbonylole- finierung ein Pol (3-alkyl-2, 5-thienylen-vinylene) (PTV) entsteht.A 3-alkyl-substituted thiophene is particularly preferably used as the Ar, a pol (3-alkyl-2,5-thienylene-vinylene) (PTV) being formed by the carbonyl olefinization method.
Bevorzugt wird als R eine Alkyl- oder Alkoxygruppe mit 6 bis 24 C-Atomen eingesetzt.As R, an alkyl or alkoxy group having 6 to 24 carbon atoms is preferably used.
Im folgenden wird das Verfahren zur mehr als 98 % regioregu- laren Verknüpfung durch die Methode der Carbonylolefinierung anhand eines Beispiels näher erläutert: In the following, the procedure for more than 98% regional regulation linking by the method of carbonyl olefinization is explained in more detail using an example:
Synthesemöglichkeit I:Synthesis option I:
CCI4 PPhßCCI4 PPhß
smeer smeer
WittigWittig
100% regioregular Poly(3-alkyl-2,5-thienylen-vinylene) (PTV) 100% regioregular poly (3-alkyl-2,5-thienylene-vinylene) (PTV)
Synthesemöglichkeit II:Synthesis option II:
100% regioregular Poly(3-alkyl-2,5-thienylen-vinylene) (PTV)100% regioregular poly (3-alkyl-2,5-thienylene-vinylene) (PTV)
wobei R die oben angegebene Bedeutung hat.where R has the meaning given above.
Die Polymere werden bevorzugt als organische Halbleiter eingesetzt, insbesondere bevorzugt als Funktionsschicht z.B. einer integrierten Schaltung, einer organischen Diode, einer Photozelle, Feldemissionsanzeige oder einem Sensor. The polymers are preferably used as organic semiconductors, particularly preferably as a functional layer e.g. an integrated circuit, an organic diode, a photocell, field emission display or a sensor.

Claims

Patentansprüche claims
1. Polyarylenvinylen (PAV) der allgemeinen Formel I -(Ar(R)-CH=CH)n- in der1. Polyarylene vinylene (PAV) of the general formula I - (Ar (R) -CH = CH) n - in the
Ar für eine Arylgruppe mit 4 bis 14 C-Atomen steht und (R) bedeutet, dass Ar einen oder mehrere Substituenten R haben kann, die gleich oder verschieden sein können und eine Phenyl- oder Phenyloxygruppe oder eine geradkettige oder ver- zweigte oder cyclische Alkyl- oder Alkoxygruppe mit 1 bis 25 C-Atomen darstellen, wobei ein oder mehrere nicht benachbarte CH2-Gruppen durch -0-, -S-, -CO-, -COO-, -OCO-, -NR1-, (-NR2R3)+A", -O-COO-, -NR^CO-NR1- oder -CONR4 ersetzt sein können und wobei ein oder mehrere H-Atome durch F, CN, CI, Br, J oder eine Arylgruppe mit 4 bis 14 C-Atoπte ersetzt sein können, die durch einen oder mehrere, nicht aromatische Reste R substituiert sein kann; wobeiAr stands for an aryl group with 4 to 14 C atoms and (R) means that Ar can have one or more substituents R, which can be the same or different, and a phenyl or phenyloxy group or a straight-chain or branched or cyclic alkyl - Or represent alkoxy group with 1 to 25 carbon atoms, one or more non-adjacent CH 2 groups being represented by -0-, -S-, -CO-, -COO-, -OCO-, -NR 1 -, (- NR 2 R 3 ) + A " , -O-COO-, -NR ^ CO-NR 1 - or -CONR 4 can be replaced and where one or more H atoms by F, CN, CI, Br, J or one Aryl group can be replaced with 4 to 14 C-Atoπte, which can be substituted by one or more, non-aromatic radicals R;
R^R^R^R4 gleich oder verschieden sind und für aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 25 C-Atomen oder auch H stehen undR ^ R ^ R ^ R 4 are the same or different and stand for aliphatic or aromatic hydrocarbon radicals having 1 to 25 carbon atoms or H and
A" ein einfach geladenes Anion bedeutet, wobei das PAV eine Regioregularitat von mehr als 98 %, in derA "means a single charged anion, where the PAV has a regioregularity of more than 98%, in the
Kettenverknüpfung hat .Has chain linkage.
2t Polyarylenvinylen (PAV) nach Anspruch 1, bei dem zwischen 2 und 15000 Monomereinheiten regioregular verknüpft sind.2 t polyarylene vinylene (PAV) according to claim 1, in which between 2 and 15000 monomer units are linked regionally.
3. Polyarylenvinylen (PAV) nach einem der Ansprüche 1 oder 2, das aus zumindest zwei verschiedenen Monomereinheiten aufge- baut ist.3. polyarylene vinylene (PAV) according to one of claims 1 or 2, which is composed of at least two different monomer units.
4. Verfahren zur Herstellung eines Polyarylenvinylen (PAV) mit hoher Ladungsträgerbeweglichkeit bei dem über eine AB- Eliminierung eine mehr als 98 % regioregulare Verknüpfung der Monomeren erzielt wird, wobei A und B für zwei funktioneile organische Reste an einem Aromaten stehen, die in einer Kondensationsreaktion eine re- gioregulare Verknüpfung der betroffenen Monomeren bewirken.4. Process for the preparation of a polyarylene vinylene (PAV) with high charge carrier mobility, in which a more than 98% regio-regular linkage of the monomers is achieved via AB elimination, where A and B stand for two functional organic residues on an aromatic, which bring about a regionally regular linkage of the monomers concerned in a condensation reaction.
5 Verfahren nach Anspruch 4, wobei A für -CH=0 und B für - CH2PPh3]+X" (X = Halogen) oder -CH2PO(OEt)2 steht, die im Rahmen einer Kondensationsreaktion von Monomeren regioregular miteinander abreagieren.5 The method of claim 4, wherein A stands for -CH = 0 and B for - CH 2 PPh 3 ] + X " (X = halogen) or -CH 2 PO (OEt) 2 , which are regio-regular with one another in the context of a condensation reaction of monomers react.
6. Verfahren nach einem der Ansprüche 4 oder 5, bei dem eine regioregulare HT (head-tail) Verknüpfung der Monomeren entsteht.6. The method according to any one of claims 4 or 5, wherein a regioregular HT (head-tail) linkage of the monomers is formed.
7. Verfahren nach einem der Ansprüche 4 bis 6, bei dem durch Zugabe verschiedener Monomereinheiten während der Herstellung7. The method according to any one of claims 4 to 6, in which by adding different monomer units during manufacture
Copolymere entstehen.Copolymers are created.
8. Polyarylenvinylen hergestellt durch ein Verfahren nach einem der Ansprüche 4 bis 7.8. Polyarylene vinylene produced by a process according to one of claims 4 to 7.
9. Integrierte Schaltung, organische Leuchtdiode, Photozelle, Feldemissionsanzeige oder Sensor enthaltend ein Polyarylenvinylen nach einem der Ansprüche 1 bis 3 oder 8.9. Integrated circuit, organic light-emitting diode, photocell, field emission display or sensor containing a polyarylene vinylene according to one of claims 1 to 3 or 8.
10. Integrierte Schaltung auf der Basis organischen Materials, bei der ein Funktionspolymer ein mehr als 98 % regiore- gulares organisches Polymer aus Monomereinheiten der allgemeinen Formel I ist. 10. Integrated circuit based on organic material, in which a functional polymer is a more than 98% regio-regular organic polymer composed of monomer units of the general formula I.
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