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  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
  • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
  • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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  • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
  • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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  • H10K85/211—Fullerenes, e.g. C60
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  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• the present invention relates to copolymers comprising one or more benzo- dithiophene (repeating) unit(s) of the class benzo[1 ,2-b;4,3-b']dithiophene and/or benzo[1 ,2-b;3,4-b']dithiophene, and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor.
• the polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties.
• v and w each are from the range 4 to 1000, especially 4 to 200, very especially 5 to 100, the weight ratio v:w preferably ranging from 1 :20 to 20:1 ;
• A is a benzodithiophene repeating unit of the formula II or III
• Gi , G2, G3, G 4 and G5 may be the same or different and are selected from hydrogen, halogen such as F, C1 -C25alkyl, O- and/or S-interrupted C2-C25alkyl, C1 -C25alkoxy, C3-C12cycloalkyl, C2-C25alkenyl, C2-C25alkynyl, C4-C25aryl, C5-C25alkylaryl or C5- C25aralkyl, each of which is unsubstituted or substituted by one or more halogen, hy- droxy, nitro, -CN, or C6-C18aryl, and any alkyl of 2 or more carbon atoms may be interrupted by -0-, -COO-, -OCO-, -S-;
• halogen such as F, C1 -C25alkyl, O- and/or S-interrupted C2-C25alkyl, C1 -
• R1 and R2 may be the same or different and are selected from hydrogen, a C1 - C1 OOalkyl group, -COOR103, a C1 -C1 OOalkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, -CN, or C6-C18aryl groups and/or interrupted by -0-, -COO-, -OCO-, or -S-; a C7-C100arylalkyl group, a carbamoyl group, C5-C12cycloalkyl, which can be substituted one to three times with C1 -C8alkyl and/or C1 -C8alkoxy, a C6-C24aryl group, in particular phenyl or 1 - or 2 naphthyl which can be substituted one to three times with C1 -C8alkyl, C1 -C8thioalkoxy, and/or C1 - C8alkoxy
• R103 is C1 -C50alkyl, especially C4-C25alkyl
• one of X3 and X4 is N and the other is CR99,
• R99, R104 and R104' are independently of each other hydrogen, halogen, especially F, or a C1 -C25alkyl group, especially a C4-C25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C7 C25arylalkyl, or a C1 -C25alkoxy group, R105 and R105' independently of each other hydrogen, halogen, C1 -C25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7- C25arylalkyl, or C1 -C18alkoxy,
• R107 is H; C6-C18aryl; C6-C18aryl which is substituted by C1 -C18alkyl, or C1 - C18alkoxy; C1 -C18alkyl; or C2-C18alkyl which is interrupted by -0-,
• p 0, 1 , 2, or 3;
• R 3 and R 3 are independently of each other hydrogen, halogen, CrC 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or CrC 25 alkoxy;
• R 4 and R 4 are independently of each other hydrogen, halogen, CrC 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or CrC 25 alkoxy;
• X 1 and X 2 are independently of each other -0-, -S-, -NR 8 -, -Si(R 11 )(R 11' )-, -C(R 7 )(R 7' )-, -
• X 5 is -O-, or -NR 8 -;
• R 5 and R 5 are independently of each other hydrogen, halogen, CrC 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 6 -C 24 aryl, which may optionally be substituted one to three times with CrC 8 alkyl and/or CrC 8 alkoxy; C 7 -C 25 arylalkyl, CN, or d-C 25 alkoxy; or
• R 5 and R 5 together form a ring
• R 6 is H, CrCi 8 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, Ci-Ci 8 perfluoroalkyl, C 6 -C 24 aryl, which may optionally be substituted one to three times with CrC 8 alkyl and/or CrC 8 alkoxy; C 2 -C 2 oheteroaryl, which may optionally be substituted one to three times with Ci-C 8 alkyl and/or Ci-C 8 alkoxy; or CN, R 7 and R 7' are independently of each other hydrogen, Ci-C3salkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; or C7-C25arylalkyl, R 8 and R 8' are independently of each other hydrogen, C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; or Ci-dsalkyl, especially d-
• R 11 and R 11' are independently of each other Ci-dsalkyl group, C7-C25arylalkyl, or a phenyl group, which optionally can be substituted one to three times with d-Csalkyl and/or Ci-Csalkoxy.
• copolymers of the formula I, Gi, G2, G3, G 4 and G5 independently are selected from hydrogen, fluoro, C1 -C25alkyl, O- and/or S-interrupted C2-C25alkyl, C1 - C25alkoxy, C3-C12cycloalkyl, C2-C25alkenyl, C2-C25alkynyl, phenyl, naphthyl, C1 - C12alkylphenyl, phenyl-C1 -C12alkyl, each of which is unsubstituted or substituted by one or more fluoro, -CN, phenyl, naphthyl;
• R1 and R2 may be the same or different and are selected from Ci-Ciooalkyl, C5- Ci2cycloalkyl, which can be substituted one to three times with d-Csalkyl and/or Ci- Csalkoxy, phenyl or 1 - or 2-naphthyl which can be substituted one to three times with Ci-C 8 alkyl and/or Ci-C 8 alkoxy, or -CR 101 R 102 -(CH 2 )u-A 3 , wherein R 101 and R 102 stand for hydrogen or d-dalkyl, A 3 stands for phenyl or 1 - or 2-naphthyl each of which can be substituted one to three times with Ci-Csalkyl and/or Ci-Csalkoxy, and u stands for 0, 1 , 2, or 3. Also preferred are copolymers of the formula I, wherein
• R103 is C1 -C25alkyl
• one of X3 and X4 is N and the other is CR99,
• R99, R104 and R104' are independently of each other hydrogen, F, or a C1 -C25alkyl group, especially a C4-C25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C7-C25phenylalkyl, C1 -C12alkoxy,
• R105 and R105' independently of each other hydrogen, fluoro, C1 -C25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7-C25phenylalkyl, or C1 -C18alkoxy,
• R107 is H; phenyl or naphthyl which is optionally substituted by C1 -C18alkyl or C1 - C18alkoxy; C1 -C18alkyl; or C2-C18alkyl which is interrupted by -0-;
• Gi, G2, G3, G 4 and G5 independently are selected from hydrogen, fluoro, Ci-C25alkyl; and especially are hydrogen;
• R 1 and R 2 are Ci-dsalkyl, especially a Cs-dsalkyl group, and
• each R 104 and R 104' independently is selected from H, Ci-dsalkyl.
• Examples are materials or devices, where in the copolymer oiety COM is selected from repeating units of the formulae
• copolymers conforming to the formula XI I or XI I I are copolymers conforming to the formula XI I or XI I I
• n ranges from 4 to 300, especially from 10 to 200.
• the copolymers are preferably of a molecular weight range (weight average as determined by GPC; Mw) from 5000 to about 200000, especially from about 10000 to about 120000, for example 50000 to 100000, in order to obtain a material combining optimum semiconductor and solubility properties (Mw of 10000 stands for 10000 Dalton, which is 10 kg/mol).
• the number average molecular weight Mn is preferably in the range of from 10.000 to 100.000 g/mol.
• copolymers of formula I are novel compounds, preferred species and classes among them are as defined for the materials and devices of the invention described above.
• 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 unsubsti- tuted thiophene, without being restricted thereto.
• Chain termination is often effected by monofunctional monomers, i.e. formula I terminates on both ends often, for example, with hydrogen, phenyl or Ci-C2salkyl.
• the units A and COM in formula I may be distributed statistically or in blocks; preferred are regular copolymers of the type ...A-COM-A- COM-A-COM... etc.; similarly, several divalent aromatic units forming one unit COM may be distributed in a regular manner; a preferred class of copolymers contains units
• Any alkyl group such as R 1 and R 2 as a CrC 36 alkyl group, or R104 or R104' as d- C 25 alkyl, include, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, iso- butyl, tert.
• the groups R 1 and R 2 can be represented by formula
• Chiral side chains such as R 1 and R 2 , can either be homochiral, or racemic, or have opposite chirality, which can influence the morphology of the compounds of formula I in the solid state.
• Alkenyl refers to a straight-chain or branched alkyl group having one or more carbon- carbon double bonds. Examples are ethenyl, propenyl, butenyl, pentenyl, hexenyl, bu- tadienyl, pentadienyl, hexadienyl groups. The one or more carbon-carbon double bonds can be internal (such as in 2-butene) or terminal (such as in 1 -butene). In various embodiments, an alkenyl group can have 2 to 20 carbon atoms. In some embodiments, alkenyl groups can be substituted as disclosed herein. An alkenyl group is gen- erally not substituted with another alkenyl group, an alkyl group, or an alkynyl group.
• Alkynyl refers to a straight-chain or branched alkyl group having one or more triple carbon-carbon bonds. Examples include ethynyl, propynyl, butynyl, pentynyl. The one or more triple carbon-carbon bonds can be internal (such as in 2-butyne) or terminal (such as in 1 -butyne). In various embodiments, an alkynyl group can have 2 to 20 carbon atoms. In some embodiments, alkynyl groups can be substituted as disclosed herein. An alkynyl group is generally not substituted with another alkynyl group, an alkyl group, or an alkenyl group.
• Cycloalkyl refers to a non-aromatic carbocyclic group including cyclized alkyl, alkenyl, and alkynyl groups.
• a preferred cycloalkyl group can have 3 to 10 carbon atoms.
• a cycloalkyl group can be monocyclic (e.g., cyclohexyl) or polycyclic (e.g., containing fused, bridged, and/or spiro ring systems), where the carbon atoms are located inside or outside of the ring system. Any suitable ring position of the cycloalkyl group can be covalently linked to the defined chemical structure.
• cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornyl, norpinyl, norcaryl, ada- mantyl, and spiro[4.5]decanyl groups, as well as their homologs, isomers, and the like. Cycloalkyl groups can be substituted as disclosed herein.
• Aryl refers to an aromatic monocyclic hydrocarbon ring system or a polycyclic ring system in which two or more aromatic hydrocarbon rings are fused (i.e., having a bond in common with) together or at least one aromatic monocyclic hydrocarbon ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings.
• An aryl group can have from 6 to 14 carbon atoms in its ring system, which can include multiple fused rings.
• Preferred aryl groups having only aromatic carbocyclic ring(s) include phenyl, 1 - naphthyl (bicyclic), 2-naphthyl (bicyclic), anthracenyl (tricyclic), phenanthrenyl (tricyclic).
• Preferred polycyclic ring systems in which at least one aromatic carbocyclic ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings include, among others, benzo derivatives of cyclopentane (i.e., an indanyl group, which is a 5,6-bicyclic cycloalkyl/aromatic ring system), cyclohexane (i.e., a tetrahydronaphthyl group, which is a 6,6-bicyclic cycloalkyl/aromatic ring system), imidazoline (i.e., a benzimidazolinyl group, which is a 5,6-bicyclic cycloheteroalkyl/aromatic ring system), and pyran (i.e., a chromenyl group, which is a 6,6-bicyclic cycloheteroalkyl/aromatic ring system).
• aryl groups include benzodioxanyl, benzodioxolyl, chromanyl, indolinyl groups, and the like.
• aryl groups can be substituted as disclosed herein.
• an aryl group can have one or more halogen substituents, and can be referred to as a "haloaryl" group.
• Perhaloaryl groups i.e., aryl groups where all of the hydrogen atoms are replaced with halogen atoms (e.g., - C6F5), are included within the definition of "haloaryl.”
• an aryl group is substituted with another aryl group and can be referred to as a biaryl group. Each of the aryl groups in the biaryl group can be substituted or unsubstituted.
• Heteroaryl refers to an aromatic monocyclic or polycydic ring system containing at least one ring heteroatom.
• the heteroatom is preferably selected from oxygen (O), nitrogen (N), sulfur (S), silicon (Si), and selenium (Se) or a polycydic ring system with- out being restricted thereto.
• Polycydic heteroaryl groups include two or more heteroaryl rings fused together and monocyclic heteroaryl rings fused to one or more aromatic carbocyclic rings, non-aromatic carbocyclic rings, and/or non-aromatic cycloheteroalkyi rings.
• a heteroaryl group can have from 5 to 14 ring atoms and contain 1 -5 ring het- eroatoms.
• R 104 or R 104' is particularly preferred H or, especially one of R 104 or R 104' , prefereably linear or branched C6-C20 alkyl, e.g. n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecy, n-heptadecyl, n- octadecy, n-nonadecyl, n-isosyl, 1 -methylpentyl, 1-methylhexyl, 2-methylpentyl, 2- ethylhexyl, and 2,7-dimethyloctyl.
• C6-C20 alkyl e.g.
• 2,6-dimethyloctyl I- ethylhexyl, l-methylhexyl, 2-ethylpentyl, 2-methylhexyl, n-decyl, n-dodecyl, n- tetradecyl, and 2-ethylhexyl, most preferred is n-dodecyl.
• 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 electric 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 electric field.
• the group can be arranged in
• COM is derived from a group of formula , it is preferably a repeating unit of formula
• R 3' , R 5 , R 5 , R 7 , R 7' , R 8 , R 8' , R 11 and R 11' are as defined above and
• R 9 is Ci-C 25 alkyl, which may optionally be interrupted by one or more oxygen or sul- phur atoms, Ci-C 25 perfluoroalkyl, CrC 25 alkoxy, or CN.
• Groups of formula Xd, Xe, Xf, Xg, Xh and Xk are preferred, groups of formula Xd, Xe, Xh and Xk are most preferred.
• the present invention thus includes a semiconductor device comprising a copolymer (I) as defined above.
• the copolymer of the invention usually forms a major active con- stituent of one or more semiconducting layers in said device, which is, for example, an organic photovoltaic (PV) device or solar cell, a photodiode, or an organic field effect transistor, or a device containing a photodiode and/or an organic field effect transistor.
• PV organic photovoltaic
• 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, electrooptical or electronic components, as thin-film transistors, especially in flat visual display units, or for radiofrequency identification tags (RFID tags) or in semicon- ductor 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 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, electronic 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 applications.
• 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.
• Suitable solvents or solvent mixtures comprise, for example, alkanes, aromatics, especially their fluorinated derivatives.
• 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 poly- mers, 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 selection is common knowledge and is described, for example, in Synthetic Materials, 1 1 1 1 -1 12 (2000), 31 34 or J. Appl. Phys., 88 (2000) 7124-7128.
• printing includes a noncontact process such as inkjet printing, micro- dispensing and the like, and a contact process such as screen-printing, gravure printing, offset printing, flexographic printing, lithographic printing, pad printing, microcontact printing and the like.
• Other solution processing techniques include, for example, spin coating, drop-casting, zone casting, dip coating, blade coating, or spraying.
• Various articles of manufacture including electronic devices, optical devices, and optoelectronic devices, such as field effect transistors (e.g., thin film transistors), photovol- taics, organic light emitting diodes (OLEDs), complementary metal oxide semiconductors (CMOSs), complementary inverters, D flip-flops, rectifiers, and ring oscillators, that make use of the compounds disclosed herein also are within the scope of the present teachings as are methods of making the same.
• field effect transistors e.g., thin film transistors
• OLEDs organic light emitting diodes
• CMOSs complementary metal oxide semiconductors
• complementary inverters e.g., D flip-flops, rectifiers, and ring oscillators
• the present teachings therefore, further provide methods of preparing a semiconductor material.
• the methods can include preparing a composition that includes one or more compounds disclosed herein dissolved or dispersed in a liquid medium such as solvent or a mixture of solvents, depositing the composition on a substrate to provide a semiconductor material precursor, and processing (e.g. heating) the semiconductor precursor to provide a semiconductor material (e.g. a thin film semiconductor) that includes a compound disclosed herein.
• the liquid medium is an organic solvent, an inorganic solvent such as water, or combinations thereof.
• the composition can further include one or more additives independently selected from detergents, dispersants, binding agents, compatiblizing agents, curing agents, initiators, humectants, antifoaming agents, wetting agents, pH modifiers, bio- cides, and bacteriostats.
• additives independently selected from detergents, dispersants, binding agents, compatiblizing agents, curing agents, initiators, humectants, antifoaming agents, wetting agents, pH modifiers, bio- cides, and bacteriostats.
• surfactants and/or other polymers e.g., polystyrene, polyethylene, poly-alpha-methylstyrene, polyisobutene, polypropylene, polymethylmethacrylate, and the like can be included as a dispersant, a binding agent, a compatiblizing agent, and/or an antifoaming agent.
• the depositing step can be carried out by printing, including inkjet printing and various contact printing techniques (e.g., screen-printing, gravure printing, offset printing, pad printing, lithographic printing, flexographic printing, and microcontact printing).
• the depositing step can be carried out by spin coating, drop-casting, zone- casting, dip coating, blade coating, or spraying.
• the present teachings further provide articles of manufacture such as the various devices described herein that include a composite having a semiconductor material of the present teachings and a substrate component and/or a dielectric component.
• the sub- strate component can be selected from doped silicon, an indium tin oxide (ITO), ITO- coated glass, ITO-coated polyimide or other plastics, aluminum or other metals alone or coated on a polymer or other substrate, a doped polythiophene, and the like.
• the dielectric component can be prepared from inorganic dielectric materials such as various oxides (e.g., Si02, AI203, Hf02), organic dielectric materials such as various poly- meric materials (e.g., polycarbonate, polyester, polystyrene, polyhaloethylene, poly- acrylate), and self-assembled superlattice/self-assembled nanodielectric (SAS/SAND) materials (e.g., described in Yoon, M-H. et al., PNAS, 102 (13): 4678-4682 (2005), the entire disclosure of which is incorporated by reference herein), as well as hybrid organic/inorganic dielectric materials (e.g., described in U.S. Patent Application Serial No.
• inorganic dielectric materials such as various oxides (e.g., Si02, AI203, Hf02)
• organic dielectric materials such as various poly- meric materials (e.g., polycarbonate, polyester, polystyrene, polyhaloethylene, poly- acrylate
• the dielectric component can include the crosslinked polymer blends described in U.S. Patent Application Serial Nos. 1 1/315,076, 60/816,952, and 60/861 ,308, the entire disclosure of each of which is incorporated by reference herein.
• the composite also can include one or more electrical contacts.
• Suitable materials for the source, drain, and gate electrodes include metals (e.g., Au, Al, Ni, Cu), transparent conducting oxides (e.g., ITO, IZO, ZITO, GZO, GIO, GITO), and conducting polymers (e.g., poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), polyani- line (PANI), polypyrrole (PPy)).
• PDOT:PSS poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
• PANI polyani- line
• Py polypyrrole
• One or more of the composites described herein can be embodied within various organic electronic, optical, and optoelectronic devices such as organic thin film transistors (OTFTs), specifically, organic field effect transistors
• OFETs optical electrowetting-on-dielectric sensors
• capacitors unipolar circuits
• complementary circuits e.g., inverter circuits
• Other articles of manufacture in which materials of the present teachings are useful are photovoltaics or solar cells.
• Components of the present teachings can exhibit broad optical absorption and/or a very positively shifted reduction potential, making them desirable for such applications.
• the substances described herein can be used as a p-type semiconductor in a photovoltaic design, which includes an adjacent n- type semiconducting material that forms a p-n junction.
• the compounds can be in the form of a thin film semiconductor, which can be deposited on a substrate to form a composite.
• Another aspect of the present teachings relates to methods of fabricating an organic field effect transistor that incorporates a semiconductor material of the pre-sent teachings.
• the semiconductor materials of the present teachings can be used to fabricate various types of organic field effect transistors including top-gate top-contact capacitor structures, top-gate bottom-contact capacitor structures, bottom-gate top-contact capacitor structures, and bottom-gate bottom-contact capacitor structures.
• An OFET can include a dielectric layer, a semiconductor layer, a gate contact, a substrate, source and drain contacts
• OTFT devices can be fabricated with the present compounds on doped silicon substrates, using Si02 as the dielectric, in top-contact geometries.
• the active semiconducting layer which incorporates at least a material of the present teachings can be deposited at room temperature or at an elevated temperature.
• the active semiconducting layer which in- corporates at least a compound of the present teachings can be applied by spin- coating or printing as described herein.
• metallic contacts can be patterned on top of the films using shadow masks.
• polymers (I), more specifically described above as copolymers of the formula (I), are novel compounds and thus another embodiment of the present invention.
• Preferred embodiments of this class are (co)polymers es described for the present organic semiconductor material, layer or components.
• Monomers may be obtained according to methods known in the art. For example, benzo[1 ,2-b;4,3-b']dithiophene can be made photochemically. For this reason, 2-carbonylthiophene may be reductively coupled in a McMurry reaction to yield E-dithienylethene. This molecule may be dibrominated by lithiation and treatment with tetrabromomethane. The dibromo intermediate thus obtained may be stored under argon at low temperatures. Benzo[1 ,2-b;4,5-b']dithiophene may be obtained on UV irradiation, e.g.
• Irradiation time is preferably from hours (e.g. 1 or 2 hours) up to several days (e.g. 1 t d in the following scheme:
• Benzo[1 ,2-b;3,4-b']dithiophene may be obtained in a similar manner from the required dithienylethene via photochemical cyclodehydrogenation.
• the required non-symmetric dithienylethene may be obtained in 3 steps from thiophene by chloromethylation with formaldehyde (i) preferably in presence of a protonic acid (e.g. in concentrated hydrochloric acid whith additional HCI gas saturation).
• the chloromethylated intermediate may be collected by distillation.
• Triethylphosphite reacts with it (ii; Arbusov reaction) to give the phosphonate; best results are obtained when both reagents are heated, e.g.
• a strong base like an alcoholate (e.g. potassium tert-butylate as base) to yield the E- dithienylethene in high selectivity.
• Photochemical cyclodehydrogenation is performed following the procedure given above for the isomeric benzodithiophene.
• the monomers thus obtained may be subjected to copolymerization as such, or may be reacted with further comonomers COM before conversion into the copolymer chain.
• monomers for an oxidative polymerization may be obtained in a Stille coupling from the above dibromobenzodithiophenes.
• the dibromo compounds may be reacted with the mono-stannated comonomer to obtain an aggregated unit.
• the dibromo monomer may be reacted with 2-trialkylstannylthiophene, which may be substituted by R 104 , such as 2-tributylstannyl-3-dodecylthiophene, with the aid of a catalyst.
• 2-trialkylstannylthiophene which may be substituted by R 104 , such as 2-tributylstannyl-3-dodecylthiophene
• An example is the reaction in presence of a catalytic amount of Pd(PPh3)4 in a solvent such as DMF, e.g. with heating to 30-120°C.
• the tin reagent may conveniently be dissolved in THF before adding to the mixture.
• the resulting ag- gregates may be purified, e.g. by chromatography and/or recrystallization (using solvents such as ethyl acetate), before the polymerization reaction in order to avoid defects in the polymer chain.
• Copolymer preparation The copolymers can be synthesized via a cross-coupling po- lymerisation reaction, such as Stille or Suzuki reaction, in which an aryl dihalide is reacted with a organotin corn-pound or a boronic diester/acid in the presence of a base and a small amount of metal catalyst. Typically the reaction is carried out in a solvent or mixture of solvents with a reaction temperature between 20°C and 150°C.
• a cross-coupling po- lymerisation reaction such as Stille or Suzuki reaction, in which an aryl dihalide is reacted with a organotin corn-pound or a boronic diester/acid in the presence of a base and a small amount of metal catalyst.
• the reaction is carried out in a solvent or mixture of solvents with a reaction temperature between 20°C and 150°C.
• Synthesis by Stille polymerization proceeds e.g. with the corresponding bisstannylated benzodithiophene and an appropriate dibrominated comonomer Br-COM-Br such as dialkyl-dibromo-dithiophene, e.g. using a catalyst like Pd2(dba)3 and triphenyl- phosphine in a suitable solvent.
• Preferred solvents are aromatic and/or halogenated hydrocarbons such as benzene, toluene, xylene, as well as mono- or dichlorobenzene.
• oxidative polymerization may be effected by adding a solution of the monomer(s), especially highly concentrated (e.g.
• the polymers may be recovered in conventional manner, e.g. by precipitation in a non-solvent (such as an alcohol like methanol) and/or extraction (e.g. soxhlet extraction with acetone).
• a non-solvent such as an alcohol like methanol
• extraction e.g. soxhlet extraction with acetone.
• the polymerization process is advantageously monitored by analyzing samples via chromatography (e.g. size exclusion chromatography in reference to polystyrene standards); it may be interrupted (e.g. by precipitation as described) in order to improve solubility properties of the material.
• the present invention thus includes a process for the preparation of a polymer of for ⁇
• X 11 A- amount of a diboronic acid or diboronate corresponding to formula -X wherein X 10 is halogen, especially Br, and
• X 11 is independently in each occurrence -B(OH)2, -B(OY 1 )2, , or
• Y 1 is independently in each occurrence a Ci-Cioalkyl group
• Y 2 is independently in each occurrence a C2-Cioalkylene group, such as
• Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 are independently of each other hydrogen or Ci-Cioalkyl subject to the condition that the number of carbon atoms in the alkylene group -CY 3 Y 4 -CY 5 Y 6 - or
• Y 2 being -C(CH 3 )2C(CH 3 )2-, -C(CH 3 )2CH 2 C(CH3)2-, -CH 2 C(CH 3 )2CH2-;
• Y 13 and Y 14 are independently of each other hydrogen or a Ci-Cioalkyl group, in a solvent and in the presence of a catalyst.
• organo tin compound corresponding to formula , wherein
• X 11' is independently in each occurrence -SnR 207 R 208 R 209 , wherein R 207 , R 208 and R 209 are identical or different and are H or d-Cealkyl, or two of the groups R 207 , R 208 and R 209 form a ring and these groups are optionally branched.
• the purity of the monomers i.e. the 5,5'-dihalo-2,2'-dithiophene and the 5,5'- bis(trialkyl)benzo-'thiophene
• the purity of the monomers is in general > 99%.
• a high purity of the 5,5'- bis(trimethylstannyl)benzo-2,2'-dithiophen can be obtained by repeated recrystallisation (preferably at least three time) at low temperature from acetonitrile. This purification yields the monomer in the form of colorless needles.
• the 4,4'-alkyl-5,5'-dibromo-2,2'-dithiophene monomer can be obtained with very high purity by purification by coloumn chromatography (n-hexane, Silica) followed by repeated recrystallisation from ethylacetate.
• the second important factor is the adjustment of the monomer ratio.
• An equimolar mixture yields the desired molecular weight.
• the molecular weight can be reproducibly obtained by adjusting the concentration of the 1 :1 monomer mixture.
• the optimum, total concentration of the monomers is in the range of from 10 to 20 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
• 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. I2, CI2, Br2, ICI, ICI3, IBr and IF
• Lewis acids e.g. PF5, AsF5, SbF5, BF3, BCI3, SbCI5, BBr3 and S03
• inorganic acids e.g.
• HF HCI, HN03, H2S04, HCI04, FS03H and CIS03H
• organic acids or amino acids organic acids or amino acids
• transition metal compounds e.g. FeCI3, FeOCI, Fe(CI04)3, Fe(4-CH3C6H4S03)3, TiCI4, ZrCI4, HfCI4, NbF5, NbCI5, TaCI5, MoF5, MoCI5, WF5, WCI6, UF6 and LnCI3 (where Ln is a lanthanoid)
• anions e.g.
• dopants for example, are cations (e.g. H+, Li+, Na+, K+, Rb+ and Cs+), alkali metals (e.g. Li, Na, K, Rb, and Cs), alkaline earth metals (e.g.
• Inert Atmosphere Oxygen or moisture sensitive reactions are carried out in an argon atmosphere (Nonetheless AG). If not mentioned specifically, reactions are degassed by bubbling a stream of argon through the reaction mixture.
• UV reactions are done in a Rayonet RPR-100 with up to eight lamps (20 W each) of either 300 or 350 nm as indicated. The lamps possess a half width wavelength distribution of 40 nm.
• the apparatus is cooled by a 15 W air fan. Quartz glassware is used as reaction vessel, the solution is stirred by a magnetic stir bar.
• Melting Points Melting points are determined on a Buchi hot stage apparatus and are uncorrected.
• Mass Spectrometry Field-desorption mass spectra are obtained on a VG Instruments ZAB 2-SE-FPD spectrometer.
• MALDI-TOF spectrometry is conducted on a Bruker Reflex IITOF spectrometer, utilizing a 337 nm nitrogen laser. If not specifically mentioned, tetracyanoquinodimethane (TCNQ) is used as the matrix substance for solid state prepared samples. Varying thicknesses of the prepared sample on theMALDI target reduced the resolution; therefore only integers of the molecular peaks are given.
• Themost intense peak is compared to the calculated isotope of highest abundance.
• NMR Spectroscopy 1 H-NMR, 13C-NMR, ⁇ , ⁇ -COSY, C.H-COSY and NOESY experiments are recorded in the listed deuterated solvents on a Bruker DPX 250, Bruker AMX 300, Bruker DRX 500 or a Bruker DRX 700 spectrometer.
• Elemental analysis of solid samples is carried out on a Foss Her- aeus Vario EL as a service of the Institute for Organic Chemistry, Johannes Guten- berg-Universitat of Mainz. Liquid compounds or oils are not analyzed because of the difficulties to remove residual solvents and atmospheric gases like C02. Halogen containing molecules evolve hydrohalogenic acids on burning such that for each halogen atom one hydrogen atom escapes the measurement. The theoretical values are corrected accordingly, a note is given when doing so.
• UV-vis Spectroscopy Solution UV-vis spectra are recorded at room temperature on a Perkin-Elmer Lambda 100 spectrophotometer. The molar extinctions are given in the unit m 2 mol "1 which is consistent with the SI standard. Unless otherwise noted, a concentration of 10-5 mol/l is used. Solvents of spectroscopic grade are employed.
• the baseline is corrected by substracting a measurement of the cuvette filled with pure solvent used for the measurement.
• Solution photoluminescence spectra are recorded on a SPEX-Fluorolog II (212) spectrometer.
• Quantum yields of selected compounds are calculated by comparing to the known standard 5,10-diphenylanthracene (three different concentrations). Unless otherwise stated, the measurement is per- formed at room temperature.
• Infrared Spectroscopy is measured on a Nicolet 730 FT-IR spectrometer in the evanscence field of a diamond. The sample is deposited as pristine material on the diamond crystal and pressed on it with a stamp. 64 measurements are recorded for each sample, the background is substracted.
• Cyclic Voltammetry Cyclic volatammetry is measured on a Princeton Applied Research Parstat 2273 instrument with anhydrous solvents under argon atmosphere. Tetrabutylammoniumperchlorate is used as conductive salt at a concentration of 0.1 mol/l. Ferrocen is added as internal standard (1 mM). A platinum working electrode (0.5 mm diameter), a platinum wire as counter electrode, and a silver wire as quasi- reference electrode are used. The peaks are calibrated according to the oxidation peak of ferrocene. Half-step potentials are used for the evaluation.
• Field-Effect Transistors Standard procedure for transistors on silicon substrates: Heav- ily doped silicon wafers with a 200 nm thick thermally grown silicon dioxide layer are used as substrates. Hexamethyldisilazane is deposited out of the gas phase at 120 ° C.
• the semiconductor polymeric film is prepared by spin-coating (3000 rpm, 60 s) a 5 mg/ml 1 ,2-dichlorobenzene solution (roughly 47.5 nm thick).
• the charge carrier mobility is calculated in saturation from the equation
• PET substrates Gold electrodes are evaporated onto an FET foil (roughly
• a solution (2 mg/ml) of the polymer in chlorobenzene is spin-cast at 90 ° C onto the substrate and dried for 30 seconds at 100 ° C.
• the gate contact is made by evaporating a layer of about 50 nm of gold on top by the aid of a shadow mask. Measurements are performed using a Keithley 4200 machine under ambient conditions in the absence of light. Gate-dependent mobility is calculated according to
• Differential Scanning Calorimetry Differential scanning calorimetry (DSC) is measured on a Mettler DSC 30 with heating and cooling rates of 10 K/min. Atomic force microscopy is performed by using a Nanoscope Ilia MultiMode scanning probe microscope; Digital Instruments, Santa Barbara, CA.
• UV light 350 nm, 160 W
• Polymer P5 readily dissolves in toluene, forming a stable solution even at room temperature.
• a microwave tube is charged with 51 .59 mg (0.1 mmol) 5,5'-Bis(trimethylstannyl)- benzo[1 ,2-b;3,4-b']dithiophene (6) and 66.07 (0.1 mmol) 4,4'-didodecyl-5,5'-dibromo- 2,2'-dithiophene (3).
• 5 mg (5 ⁇ ) tetrakis(triphenylphosphine)palla- dium(0), 1 ml anhydrous toluene and 0.1 ml anhydrous DMF are added.
• the tube is sealed and irradiated with 300 W microwaves: 5 minutes at 120 °C, 5 min at 140 °C, and finally 40 min at 170 °C.
• the resulting mixture is dissolved in warm chlorobenzene, precipitated in methanol, and subject to soxhiet extraction with acetone for 12 hours. 63 mg of a red-orange solid are obtained (91 %).
• Example 13 Transistor Characterization Field-effect transistors for the polymer series are fabricated in the standard setup: highly doped silicon wafers with silicon dioxide dielectric are treated with HMDS to protect the hydroxy groups at the interface. The polymers are spin cast from a 5 mg/ml solution in dichlorobenzene to form a 30-50 nm thick film. Top-contact gold electrodes are deposited from the gas phase. The measurements are run in a nitrogen atmosphere with yellow light. Charge carrier mobilities and on-off ratios thus determined are compiled in the below table 2.
• Example 14 Solid morphology
• the materials are extruded as a fiber.
• the two-dimensional diffraction of an X-ray beam reveals both the TT-stacking distance and the packing mode.
• the ⁇ -stacking distance is basically unaffected by the extent of curvature in the polymer. In all cases, a value between 0.37 and 0.38 nm is found. This value is about the same as in polymers with the highest charge-carrier mobility.
• Table 2 Morphology data obtained from fiber X-ray scattering: a. ⁇ -stacking distance; b. lamellar distance; and the performance in field-effect transistors on silicon substrates with a top-contact bottom-gate setup: c. saturation field-effect mobility; d. on-off ratio.
• the solar cell has the following structure: Al electrode/LiF layer/organic layer, including compound of the invention/[poly(3,4-ethylenedioxy-thiophene) (PEDOT):
• poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate The solar cells are made by spin coating a layer of the PEDOT:PSS on a pre-patterned ITO on glass sub- strate. Then a 1 :1 mixture of the compound P4 or P5 (1 % by weight) : [60]PCBM or [70]PCBM (a substituted ⁇ or C70 fullerene) is spin coated (organic layer). LiF and Al are sublimed under high vacuum through a shadow-mask. Solar cell performance
• Example 16 Synthesis snd Application of Polymer 16 a) To a cooled (- 78 °C) solution of 1 .05 g 1 in 20 ml of dry THF is added 4.5 ml butyl lithium (2.5 M in hexane). The resulting solution is stirred for 15 minutes at 0 °C and cooled to - 78°C.
• a solar cell of the following structure is prepared: Al electrode/LiF layer/organic layer, including compound of the invention/[poly(3,4-ethylenedioxy-thiophene) (PEDOT): poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate.
• PEDOT poly(3,4-ethylenedioxy-thiophene)
• PSS poly(styrenesulfonic acid)
• the solar cell is made by spin coating a layer of the PEDOT:PSS on a pre-patterned ITO on glass substrate. Then a 1 :1 .5 mixture of polymer 16 (1 % by weight) : [60]PCBM or [70]PCBM (a substituted C6o or C70 fullerene) is spin coated (organic layer). LiF and Al are sublimed under high vacuum through a shadow-mask.
• Polymer 18 is prepared in analogy the procedure described for the preparation of polymer 16 in example 16.

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