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• • C—CHEMISTRY; METALLURGY
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  • 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
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  • 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
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C08G61/124—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 nitrogen atom in the ring
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  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• • 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
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/151—Copolymers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K99/00—Subject matter not provided for in other groups of this subclass
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/14—Macromolecular compounds
  • C09K2211/1441—Heterocyclic
  • C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/14—Macromolecular compounds
  • C09K2211/1441—Heterocyclic
  • C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms
• • 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]
  • H10K10/462—Insulated gate field-effect transistors [IGFETs]
  • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
• • 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]
  • H10K50/14—Carrier transporting layers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• the present invention relates to benzothiadiazole-cyclopentadithiophene copolymers, to a process for their preparation and to their use as semiconductors or charge transport materials.
• FET field-effect transistor
• OFTs organic thin-film transis- tors
• organic semiconductors in OTFTs has some advantages over the inorganic semiconductors used to date. They can be processed in any form, from the fiber to the film, exhibit a high mechanical flexibility, can be produced at low cost and have a low weight.
• the significant advantage is, however, the possibility of producing the entire semiconductor component by deposition of the layers from solution on a polymer substrate at atmospheric pressure, for example by printing techniques, such that inexpensively producible FETs are obtained.
• the performance of the electronic devices depends essentially on the mobility of the charge carriers in the semiconductor material and the ratio between the current in the on- state and the off-state (on/off ratio).
• An ideal semiconductor therefore has a minimum conductivity in the switched-off state and a maximum charge carrier mobility in the switched-on state (mobility above 10 "3 cm 2 V " V 1 on/off ratio above 10 2 ).
• the semiconductor material has to be relatively stable to oxidation, i.e. has to have a sufficiently high ionization potential, since its oxidative degradation reduces the performance of the component.
• EP 1510535 A1 describes polythieno(2,3-b)thiophenes, which have a mobility of 3 ⁇ 10 "3 or
• WO2006/094645 A1 describes polymers, which have one or more selenophene-2,5-diyl and one or more thiophene-2,5-diyl groups, while WO 2006/131185 discloses polythieno(3,4-d)thiazoles, and US 2005/0082525 A1 discloses benzo(1 ,2-b,4,5-b')dithiophenes.
• R is n-hexadecyl or 3,7-dimethyloctyl
• the advantage of the benzothiadiazol-cyclopentadithiophene copolymer of the present invention is a significantly increased charge carrier mobility in a field effect transistor due to an improved, higher molecular weight in combination with a high purity of the material.
• the number average molecular weight M n is preferably in the range of from 40 to 60 kg/mol. In one particular embodiment, M n is in the range of from 65 to 70 kg/mol.
• R is n-hexadecyl or 3,7-dimethyloctyl .
• Mobility or “mobility” refers to a measure of the velocity with which charge carriers induced by an external stimulus such as an electric field, for example, holes (or units of positive charge) in the case of a p-type semiconducting material and electrons in the case of an n-type semiconducting material, move through the material under the influence of an elec- trie field.
• an electric field for example, holes (or units of positive charge) in the case of a p-type semiconducting material and electrons in the case of an n-type semiconducting material, move through the material under the influence of an elec- trie field.
• the present invention further provides for the use of the copolymers according to the present invention as semiconductors or charge transport materials, especially in optical, elec- trooptical or electronic components, as thin-film transistors, especially in flat visual display units, or for radiofrequency identification tags (RFID tags) or in semiconductor components for organic light-emitting diodes (OLEDs), such as electroluminescent displays or backlighting for liquid-crystalline displays, for photovoltaic components or in sensors, as electrode material in batteries, as optical waveguides, for electrophotography applications such as electrophotographic recording.
• semiconductors or charge transport materials especially in optical, elec- trooptical or electronic components, as thin-film transistors, especially in flat visual display units, or for radiofrequency identification tags (RFID tags) or in semiconductor components for organic light-emitting diodes (OLEDs), such as electroluminescent displays or backlighting for liquid-crystalline displays, for photovoltaic components or in sensors, as electrode material in batteries, as optical waveguides, for electrophotography applications such as electrophotographic recording
• the present invention further provides optical, electrooptical or electronic components comprising the polymer according to the present invention.
• Such components may be, for example, FETs, integrated circuits (ICs), TFTs, OLEDs or alignment layers.
• the polymers according to the present invention are suitable particularly as semiconductors, since they show high mobilities required for this purpose.
• the polymers may be end-capped by several groups as known from the prior art.
• Preferred end groups are H, substituted or unsubstituted phenyl or substituted or unsubstituted thio- phene, without being restricted thereto.
• copolymers according to the present invention can be prepared by methods which are already known. Preferred synthesis routes are described hereinafter.
• copolymers of the invention can preferably be prepared from 2,1 ,3-benzothiadiazole- 4,7-bis(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl) (BTZ) and 2,6-dibromo-4,4- dihexadecyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene (CDT).
• BTZ 2,1 ,3-benzothiadiazole- 4,7-bis(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)
• CDT 2,6-dibromo-4,4- dihexadecyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene
• the monomer 2,6-dibromo-4,4-dihexadecyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene can be prepared by the method described in P. Coppo et al., Macromolecules 2003, 36, 2705 - 271 1 , using the following reaction scheme:
• R is n-hexadecyl or 3,7-dimethyloctyl .
• the comonomer 2,1 ,3-benzothiadiazole-4,7-bis(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl) (BTZ) can be prepared from 4,7-dibromo-2,1 ,3-benzothiadiazole as described in Zhang et al., J. Am. Chem. Soc. 2007, 129(12), 3472-3473.
• the BTZ/CDT copolymer can be synthesized via a cross-coupling polymerisation reaction, such as Stille or Suzuki reaction, in which an aryl dihalide is reacted with an organotin compound or a boronic diester/acid in the presence of a base and a small amount of metal catalyst such as tetrakis(triphenylphosphino)palladium(0).
• a cross-coupling polymerisation reaction such as Stille or Suzuki reaction
• an aryl dihalide is reacted with an organotin compound or a boronic diester/acid in the presence of a base and a small amount of metal catalyst such as tetrakis(triphenylphosphino)palladium(0).
• a cross-coupling polymerisation reaction such as Stille or Suzuki reaction
• an aryl dihalide is reacted with an organotin compound or a boronic diester/acid in the presence of a base and a small amount
• the BTZ monomer which was previously obtained as a pink solid (Zhang et al., J. Am. Chem. Soc. 2007, 129(12), 3472-3473) is subjected to multiple recrystallizations to yield colourless crystals with a purity >99% determined by GC.
• the molecular weight can be reproducibly obtained by adjusting the concentration of the 1 :1 monomer mixture.
• the optimum, total concentration of the monomers in the reaction solution to yield a number average molecular weight of 50-60 kg/mol is about 60 wt%.
• the invention comprises both the oxidized and the reduced forms of the polymers according to the present invention. Either a deficiency or an excess of electrons leads to the formation of a delocalized ion which has a high conductivity. This can be done by doping with customary dopants. Dopants and doping processes are common knowledge and are known, for example, from EP-A 0 528 662, US 5198153 or WO 96/21659. Suitable doping processes comprise, for example, doping with a doping gas, electrochemical doping in a solution comprising the dopant, by thermal diffusion and by ion implantation of the dopant into the semiconductor material.
• halogens e.g. I 2 , Cl 2 , Br 2 , ICI, ICI 3 , IBr and IF
• Lewis acids e.g. PF 5 , AsF 5 , SbF 5 , BF 3 , BCI 3 , SbCI 5 , BBr 3 and SO 3
• inorganic acids e.g. HF, HCI, HNO 3 , H 2 SO 4 , HCIO 4 , FSO 3 H and CISO 3 H
• organic acids or amino acids e.g.
• FeCI 3 FeOCI, Fe(CIO 4 ) 3 , Fe(4-CH 3 C 6 H 4 SO 3 ) 3 , TiCI 4 , ZrCI 4 , HfCI 4 , NbF 5 , NbCI 5 , TaCI 5 , MoF 5 , MoCI 5 , WF 5 , WCI 6 , UF 6 and LnCI 3 (where Ln is a lanthanoid)), anions (e.g.
• the conductive form of the copolymers according to the present invention can be used as an organic conductor, for example charge injection layers and ITO planarizing layers in organic light-emitting diodes (OLEDs), flat screens and touch screens, antistatic films, printed circuits and capacitors, without being restricted thereto.
• OLEDs organic light-emitting diodes
• flat screens and touch screens flat screens and touch screens
• antistatic films printed circuits and capacitors, without being restricted thereto.
• the copolymers according to the present invention can be used to produce optical, elec- tronic and semiconductor materials, especially as charge transport materials in field-effect transistors (FETs), for example as components of integrated circuits (ICs), ID tags or TFTs.
• FETs field-effect transistors
• ICs integrated circuits
• ID tags ID tags
• TFTs TFTs
• OLEDs organic light-emitting diodes
• LCDs liquid-crystal displays
• photovoltaic applications or for sensors for electrophotographic recording and other semiconductor ap- plications.
• copolymers according to the present invention have good solubility, they can be applied to the substrates as solutions. Layers can therefore be applied with inexpensive processes, for example spin-coating or printing.
• Suitable solvents or solvent mixtures comprise, for example, ether, aromatics and espe- cially chlorinated solvents.
• FETs and other components comprising semiconductor materials can be used advantageously in ID tags or security labels in order to indicate authenticity and to prevent forgeries of valuable items such as banknotes, credit cards, identity documents such as ID cards or driving licenses or other documents with pecuniary advantage such as rubber stamps, postage stamps or tickets, etc.
• the polymers according to the present invention can be used in organic light- emitting diodes (OLEDs), for example in displays or as backlighting for liquid-crystal displays (LCDs).
• OLEDs have a multilayer structure.
• a light-emitting layer is generally embedded between one or more electron- and/or hole-transporting layers.
• the electrons or holes can migrate in the direction of the emitting layer, where their recombination to the excitation and subsequent luminescence of the luminophoric compounds in the emitting layer.
• the polymers, materials and layers may, according to their electrical and optical properties, find use in one or more of the transport layers and/or emitting layers.
• the compounds, materials or layers are electroluminescent or have electroluminescent groups or compounds, they are particularly suitable for the emitting layer.
• the BTZ/n-hexadecyl-CDT copolymer was synthesized via a Suzuki coupling reaction, n- hexadecyl-CDT (300 mg, 0.382 mmol) and BTZ (148 mg, 0.382 mmol), K 2 CO 3 (2mL, 2M) and 3 drops of Aliquat 336 were dissolved into X ml. of toluene in a 50 ml. Schlenk flask equipped with a reflux condenser. The solution was then degassed using the freeze/pump/purge method three times, and tetrakis(triphenylphosphine)palladium was added.
• Highly n++ doped Si wafer with a 150 nm SiO 2 layer was used as transistor substrates.
• the SiO 2 dielectric was treated with phenyltriethoxysilane.
• the whole substrate was then immersed in a solution containing 1 mg/ml copolymer (dissolved in chlorobenzene).
• a polymer film was "directionally grown" via this dip-coating method.
• the semiconducting layer can be coated by spincoating a 0.5 wt% solution in chlorobenzene with a thickness of 50 nm. This polymer layer was heated at 200 0 C for 1 h in nitrogen atmosphere and the transistors were finished by evaporating 50 nm gold contacts on top of this layer.
• the charge carrier mobilities were derived from the saturation transfer plot.
• Table 1 Transistor performance for BTZ/n-hexadecyl-CDT copolymer in dependence of molecular weight obtained by spin coating:
• Typical output curves at various gate voltages V G are illustrated in Figure 1.
• the reaction was then cooled to room temperature and an additional 4 ml. of toluene was added.
• the mixture was degassed three times using the freeze/pump/purge method and additional tetrakis(triphenylprosphine)palladium (0.0191 mmol) was added, followed by 3 freeze/pump/purge cycles.
• the reaction was heated to 100 0 C for 48 hours, and then a solution of phenyl boronate ester (0.1 M) in toluene was added and stirred an additional 12 hours, at which time a solution of bromobenzene (0.1 M) in toluene was added.
• Samples were drop-cast from 2 mg/mL in o-Dichlorobenzene on bottom contact FET substrates held at 100°C with 200 nm Si ⁇ 2 functionalized with HMDS.
• the channel lengths and widths are 20 ⁇ m and 1.4 mm respectively.
• the on/off ration is 10 6 ( Figure 4). Processing was conducted in nitrogen atmosphere.

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