TW201634519A - Semiconducting mixtures - Google Patents

Abstract

The invention relates to novel semiconducting mixtures comprising a conjugated polymer and a substituted fullerene, to their use in organic electronic (OE) devices, especially organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising these mixtures.

Description

Semiconductor mixture

The present invention relates to a novel semiconductor mixture comprising a conjugated polymer and a substituted fullerene, and to an organic electronic (OE) device, in particular an organic photovoltaic (OPV) device and an organic photodetector (OPD), And OE, OPV and OPD devices comprising the mixtures.

The photoactivated layer in an organic photovoltaic (OPV) or organic photodetector (OPD) device is composed of at least two of the following components: a p-type semiconductor (or electron donor) as a first component, such as a polymer. , an oligomer or a defined molecular unit, and an n-type semiconductor (or electron acceptor) as a second component such as a fullerene derivative, a substituted fullerene, a graphene, a metal oxide or a quantum dot. In recent years, the stability of OPV devices has been studied. The interactions that occur during OPV operation are complex, which creates a path for many OPV devices to deteriorate.

One promising type of OPV device is a bulk heterojunction (BHJ) OPV in which p-type and n-type semiconductors are mixed to form a blend. The p-type and n-type semiconductors in the BHJ OPV device should be selected so that they can be generated The effective charge and the formation of a well formed and stable block heterojunction.

However, the properties of donor-acceptor blends that have hitherto been useful for BHJ OPV devices, such as solubility, photostability, power conversion efficiency, and thermal stability, limit their wide range of commercial applications.

Therefore, there is still a need for an improved combination of p-type and n-type semiconductors suitable for use in OPV devices, particularly BHJ OPV devices, and exhibits good structural and film-forming properties, exhibiting good electronic properties (especially charge carriers). Mobility), good processability, high solubility in organic solvents, and high light and thermal stability.

It is an object of the present invention to provide a combination of p-type and n-type semiconductors that provides one or more of the above advantageous properties. Another object of the present invention is to extend the pool of p-type/n-type semiconductors available to experts. The expert will immediately understand the other objects of the present invention from the following detailed description.

The inventors of the present invention have found that one or more of the above objects can be achieved by providing a semiconductor mixture as disclosed and claimed below.

The present invention relates to a mixture comprising a conjugated polymer comprising one or more units of formula 1 and one or more units of formula 2

And a substituted fullerene of formula F Wherein each group is independently or independently of each occurrence and has the following meaning R ^13-18 H, a straight or branched alkyl group having 1 to 30 C atoms, wherein one or more CH ₂ groups The group may be O-, -S-, -C(O)-, -C(S)-, -C(O)-O-, -OC(O) in such a manner that the O and/or S atoms are not directly connected to each other. )-, -NR ⁰ -, -SiR ⁰ R ⁰⁰ -, -CF ₂ -, -CHR ⁰ =CR ⁰⁰ -, -CY ¹ =CY ² - or -C≡C-, and one or more of them H The atomic system is optionally replaced by F, Cl, or CN, and C _n is a fullerene composed of n carbon atoms, and the inside thereof randomly captures one or more atoms, o An integer of 1 or a non-integer of >1, R ¹ has an alkyl group of 7 to 20 C atoms, which is straight or branched, and wherein one or more CH ₂ groups may be O and/or S atoms are not mutually The direct connection is optionally via -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, - NR ⁰ -, -C(=O)-NR ⁰ -, -NR ⁰ -C(=O)-, -SiR ⁰ R ⁰⁰ -, -CF ₂ -, -CR ⁰ =CR ⁰⁰ -, -CR ⁰ = N-, -N=N- or -C≡C-substitution, and/or wherein one or more of the H atoms are optionally substituted by F, Cl, or CN, and Ar is selected from the aryl or hetero-formula of formula C1 to C9 An aryl group optionally substituted by one or more identical or different groups L

LF, Cl, -CN, or alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or alkoxycarbonyloxy, each having from 1 to 20 C Atom and optionally fluorinated, R ⁰ , R ⁰⁰ H or an alkyl group having 1 to 12 C atoms, Y ¹ and Y ² H, F, Cl or CN, Ad is attached to the fullerene by any connectivity An adduct of C _n , or a combination of adducts, m 0, An integer of 1, or a non-integer of >0.

The invention further relates to a mixture as described above and below which additionally comprises one or more selected from the group consisting of semiconductors, charge transport, hole transport, electron transport, hole blocking, electron blocking, conducting, light guiding, photoactive and luminescent properties. A compound of one or more compounds.

The invention further relates to a semiconductor, charge transport, conductive, photoconductive, photoactivated, thermoelectric or luminescent material comprising or consisting of a mixture as described above and below.

The invention further relates to the use of a mixture as described above and below, in an organic electronic (OE) device, or a component in the OE device, or in a combination comprising the OE device or the component, as a semiconductor, Charge transport, conduction, light guide, photoactivation, thermoelectric or luminescent materials.

The invention further relates to a blend comprising a mixture as described above and below, additionally comprising one or more solvents, preferably selected from organic solvents, very preferably selected from chlorine-free organic solvents, preferably selected from halogen-free organic Solvent.

The invention further relates to an OE device, or a component thereof, or a combination thereof, which is prepared using a composition as described above and below.

The invention further relates to an OE device, or a component thereof, or a combination comprising the same, comprising a mixture or semiconductor, charge transfer as described above and below Transmission, conduction, light guide, photoactivation or luminescent materials.

The OE device is preferably an optical, optoelectronic, electronic, photoactivated, electroluminescent or photoluminescent device.

OE devices include, but are not limited to, organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting diodes (OLEDs), organic light emitting transistors (OLETs), organic photovoltaic devices (OPVs), Organic Photodetector (OPD), Organic Solar Cell, Dye Sensitized Solar Cell (DSSC), Perovskite Based Solar Cell, Laser Diode, Schottky Diode, Photoconductor, Photodetector Or thermoelectric device.

Preferred OE devices are OFETs, OTFTs, OPVs, OPDs, and OLEDs, particularly bulk heterojunction (BHJ) OPVs or inverted BHJ OPVs.

Further preferred is a mixture as described above and below for use as a dye for DSSC or perovskite based solar cells comprising a mixture as described above and below.

The components of the above OE device include, but are not limited to, a charge injection layer, a charge transport layer, an intermediate layer, a planarization layer, an antistatic film, a polymer electrolyte film (PEM), a conductive substrate, and a conductive pattern.

Combinations comprising such OE devices or components include, but are not limited to, integrated circuits (ICs), radio frequency identification (RFID) tags or security tags or security devices therewith, flat panel displays or backlights thereof, electrophotographic devices, An electrophotographic recording device, an organic memory device, a sensor device, a biosensor, and a biochip.

Furthermore, the mixture of the invention can be used in batteries and for detection and identification. An electrode material in a component or device of a DNA sequence.

The invention further relates to a bulk heterojunction (BHJ) comprising or formed from a mixture as described above and below, and a BHJ OPV device or an inverted BHJ OPV device comprising the bulk heterojunction.

Terms and definitions

As used herein, any of the formulas (e.g., "Formula 1") are understood to include any particular sub-formula of the formula as shown below.

As used herein, the term "fullerene" is understood to mean a compound consisting of an even number of carbon atoms formed to have a 6-membered ring and a 5-membered ring (generally having 12 5-membered rings and the rest) A cage-shaped fused ring on the surface of a 6-membered ring), optionally one or more atoms are trapped inside. The surface of the fullerene may also contain a hetero atom such as B or N.

As used herein, the term "embedded fullerenes" is understood to mean a fullerene having one or more atoms trapped inside.

As used herein, the term "metal fullerene" is understood to mean an in-line fullerene in which the atomic system trapped inside is selected from a metal atom.

As used herein, the term "carbon-based fullerene" is understood to mean a fullerene in which no atoms are trapped inside and the surface consists solely of carbon atoms.

As used herein, the term "polymer" is understood to mean a relatively high molecular weight molecule whose structure essentially comprises a plurality of repeating units which are actually or conceptually derived from relatively low molecular weight molecules ( Pure Appl. Chem. , 1996, 68 , 2291). The term "oligomer" is understood to mean a molecule of intermediate relative molecular weight, the structure of which essentially comprises a small number of units which are actually or conceptually derived from relatively low molecular weight molecules ( Pure Appl. Chem. , 1996, 68 , 2291). ). In the preferred meaning of the terms as used herein, a polymer is understood to mean having >1, ie at least 2 repeating units, preferably A compound of 5 repeating units, and an oligomer is understood to mean a compound having >1 and <10, preferably <5 repeating units.

Also, as used herein, the term "polymer" is understood to mean a molecule comprising a backbone (also referred to as the "backbone") of one or more different types of repeating units (the smallest constituent unit of a molecule) and includes The terms "oligomer", "copolymer", "homopolymer" and the like are known. In addition, it is to be understood that the term polymer, in addition to the polymer itself, also includes residues from the initiators, catalysts, and other components that accompany the synthesis of the polymer, wherein such residues are understood to be uncovalently incorporated into the polymer. in. In addition, the residues and other elements, although normally removed during the post-polymerization purification process, are typically mixed or co-mixed with the polymer such that they are between the polymer or between the solvent or dispersion medium. The transfer is usually kept with the polymer.

As used herein, in the formula showing a polymer or repeating unit, the asterisk (*) is understood to mean a chemical linkage to an adjacent unit or to a terminal group in the polymer backbone. In a ring, such as a benzene or thiophene ring, an asterisk (*) is understood to mean a C atom fused to an adjacent ring.

As used herein, the terms "repeating unit" and "monomeric unit" are used interchangeably and are understood to mean a constituent repeating unit (CRU), which is the smallest constituent unit whose repetition constitutes a regular macromolecule, regular Oligomer molecules, regular blocks or regular chains ( Pure Appl. Chem. , 1996, 68 , 2291). As used herein, the term "unit" is understood to mean that it may itself be a repeating unit or may form, together with other units, a structural unit that constitutes a repeating unit.

As used herein, "end group" is understood to mean a group that terminates the polymer backbone. The phrase "end position in the backbone" is understood to mean a divalent unit or repeating unit that is attached to the end group on one side and to another repeat unit on the other side. The terminal groups include a capping group or a reactive group attached to a monomer forming a polymer backbone that does not participate in the polymerization reaction, such as a group having the meaning of R ³³ or R ³⁴ as defined below.

As used herein, the term "blocking group" is understood to mean a group attached to or substituted for a terminal group of the polymer backbone. The capping group can be introduced into the polymer by a capping method. Blocking can be accomplished, for example, by the end group of the polymer backbone with a monofunctional compound ("blocking agent") (eg, an alkyl or aryl halide, an alkylstannane or an arylstannane, or an alkyl borate). Or aryl borate) reaction. The blocking agent can be added, for example, after the polymerization reaction. Alternatively, the blocking agent can be added to the reaction mixture on site before or during the polymerization. The addition of a blocking agent on the spot can also be used to terminate the polymerization and thus control the molecular weight of the forming polymer. Typical capping groups are, for example, H, phenyl and lower alkyl.

As used herein, the term "small molecule" is understood to mean a monomeric compound that is generally free of reactive groups that are reactive to form a polymer, and which is intended to be used in monomeric form. In contrast, unless otherwise stated, the term "monomer" is understood to mean the reaction with one or more reactive polymers. A monomeric compound having a functional group.

As used herein, the terms "donor" or "supply" and "acceptor" or "accept" are understood to mean an electron donor or an electron acceptor, respectively. "Electron donor" is understood to mean a chemical entity that supplies electrons to another compound or group of atoms of another compound. "Electron acceptor" is understood to mean a chemical entity that accepts electrons transferred from another compound or another group of atoms of the compound. See also International Union of Pure and Applied Chemistry, Compendium of Chemical Technology, Gold Book, version 2.3.2, August 19, 2012, pages 477 and 480.

As used herein, the term "n-type" or "n-type semiconductor" is understood to mean a conductive semiconductor having a density exceeding the mobile hole density, and the term "p-type" or "p-type semiconductor" is understood to mean Refers to a mobile semiconductor with a density exceeding the conduction electron density (see also J. Thewlis, Concise Dictionary of Physics , Pergamon Press, Oxford, 1973).

As used herein, the term "dissociative group" is understood to mean an atom or group that is separated from an atom in a residue or major portion of a molecule that is considered to be involved in a specified reaction (which may or may not be charged) (see also Pure Appl. Chem., 1994, 66, 1134).

As used herein, the term "conjugated" is understood to mean a compound which predominantly contains a C atom having sp ² -mixed (or optionally also sp blended) and wherein such C atoms can also be replaced by a hetero atom (eg polymer). In the simplest case, this is for example a compound having alternating CC single and double (or triple) bonds, but also compounds having aromatic units such as 1,4-phenylene. The term "mainly" is understood in this respect to mean that a compound having a naturally (spontaneously) generated defect that may cause a conjugate interruption or a defect included in the design is still considered to be a conjugated compound.

As used herein, unless otherwise indicated, means a number average molecular weight molecular weight M _n or weight average molecular weight M _W, which is based glue penetration by chromatography (GPC) relative to polystyrene standards in a solvent Eluant (Measured in tetrahydrofuran, chloroform (TCM, chloroform), chlorobenzene or 1,2,4-trichlorobenzene). Unless otherwise stated, 1,2,4-trichlorobenzene was used as a solvent. Degree of polymerization (also referred to as the total number of repeating units) n is understood to mean number average degree of polymerization _n = M n / M is given of the _U, where M _n of the number average molecular weight, M _U and a single repeat unit of For molecular weight, see JMG Cowie, Polymers: Chemistry & Physics of Modern Materials, Blackie, Glasgow, 1991.

As used herein, the term "carbyl" is understood to mean any monovalent or multivalent organic moiety comprising at least one carbon atom and free of any non-carbon atom (eg -C≡C-), Or optionally combining at least one non-carbon atom (such as B, N, O, S, P, Si, Se, As, Te or Ge) (e.g., carbonyl, etc.).

As used herein, the term "hydrocarbyl" is understood to mean additionally containing one or more H atoms and optionally containing one or more heteroatoms (eg B, N, O, S, P, Si, Se, As, The carbon base of Te or Ge).

As used herein, the term "heteroatom" is understood to mean an atom of an organic compound that is not an H or C atom, and is preferably understood to mean B, N, O, S, P, Si, Se. , As, Te or Ge.

A carbon group or a hydrocarbon group containing a chain of 3 or more C atoms may be linear, Branched and/or annular, and may comprise a spiro link and/or a fused ring.

Preferred carbon-based and hydrocarbyl groups include alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl and alkoxycarbonyloxy groups, each of which is optionally substituted and has 1 to 40, preferably 1 to 25, very preferably 1 to 18 C atoms, and optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 C atoms, and An alkylaryloxy group, an arylcarbonyl group, an aryloxycarbonyl group, an arylcarbonyloxy group and an aryloxycarbonyloxy group, each of which is optionally substituted and has 6 to 40, preferably 7 to 40, C atoms, of which all The groups optionally contain one or more heteroatoms, preferably selected from the group consisting of B, N, O, S, P, Si, Se, As, Te and Ge.

Other preferred carbyl and hydrocarbyl groups include, for example: C ₁ -C ₄₀ alkyl, C ₁ -C ₄₀ fluoroalkyl, C ₁ -C ₄₀ alkoxy or oxaalkyl, C ₂ -C ₄₀ alkenyl , C ₂ -C ₄₀ alkynyl, C ₃ -C ₄₀ allyl, C ₄ -C ₄₀ alkyldienyl, C ₄ -C ₄₀ polyalkenyl, C ₂ -C ₄₀ keto, C ₂ -C ₄₀ ester group, C ₆ -C ₁₈ aryl group, C ₆ -C ₄₀ alkaryl group, C ₆ -C ₄₀ aralkyl group, C ₄ -C ₄₀ cycloalkyl group, C ₄ -C ₄₀ cycloalkenyl group and the like. Preferred among the above groups are C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ fluoroalkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ ally A C ₄ -C ₂₀ alkyldienyl group, a C ₂ -C ₂₀ ketone group, a C ₂ -C ₂₀ ester group, a C ₆ -C ₁₂ aryl group, and a C ₄ -C ₂₀ polyalkenyl group.

Also included are combinations of a group having a carbon atom and a group having a hetero atom, such as an alkynyl group, preferably an alkynyl group substituted with a decyl group (preferably a trialkyl decyl group), preferably an ethynyl group.

The carbon group or hydrocarbon group may be a non-cyclic group or a cyclic group. Carbon or hydrocarbon In the case where the group is an acyclic group, it may be a straight chain or a branched chain. In the case where the carbon group or the hydrocarbon group is a cyclic group, it may be a non-aromatic carbocyclic or heterocyclic group or an aryl or heteroaryl group.

The non-aromatic carbocyclic groups as mentioned above and hereinafter are saturated or unsaturated and preferably have 4 to 30 ring C atoms. The non-aromatic heterocyclic group as mentioned above and hereinafter preferably has 4 to 30 ring C atoms, wherein one or more C ring atoms are optionally passed through a hetero atom (preferably selected from N, O, The S, Si and Se) are replaced or replaced by a -S(O)- or -S(O) ₂ - group. The non-aromatic carbocyclic and heterocyclic groups are monocyclic or polycyclic, and may also contain a fused ring, preferably containing 1, 2, 3 or 4 fused or non-fused rings and optionally passing one or more a group L substituted, wherein L is selected from the group consisting of halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=O)NR ⁰ R ⁰⁰ , -C(=O)X ⁰ , -C(=O)R ⁰ , -NH ₂ , -NR ⁰ R ⁰⁰ , -SH, -SR ⁰ , -SO ₃ H, -SO ₂ R ⁰ , -OH, -NO ₂ , -CF ₃ , -SF ₅ , optionally substituted indenyl, or optionally substituted and optionally including one or more heteroatoms having from 1 to 40 C atoms, preferably from 1 to 40 C atoms, optionally fluorinated to have 1 to 20 C atom alkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or alkoxycarbonyloxy, X ⁰ is halogen, preferably F, Cl or Br, and R ⁰ and R ⁰⁰ have the meanings given above and below, and preferably represent H or an alkyl group having 1 to 12 C atoms.

Preferred substituents L are selected from halogen (preferably F), or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl and fluoro having 1 to 12 C atoms. Alkoxy, or having 2 to 12 C atoms Alkenyl or alkynyl.

Preferred non-aromatic carbocyclic or heterocyclic groups are tetrahydrofuran, indoline, piper, pyrrolidine, piperidine, cyclopentane, cyclohexane, cycloheptane, cyclopentanone, cyclohexanone, dihydrogen. Furan-2-one, tetrahydro-pepirone-2-one and oxepane-2-one.

The aryl group as defined in the context preferably has 4 to 30 ring C atoms, is monocyclic or polycyclic, and may also contain a fused ring, preferably containing 1, 2, 3 or 4 fused rings or non- A fused ring, and optionally substituted with one or more groups L as defined above and below.

A heteroaryl group as referred to above, preferably having 4 to 30 ring C atoms, wherein one or more of the ring C atoms are replaced by a hetero atom, preferably selected from the group consisting of N, O, S, Si and Se. , is monocyclic or polycyclic, and may also contain a fused ring, preferably containing 1, 2, 3 or 4 fused or non-fused rings, and optionally one or more groups as defined by the context. Group L replaced.

As used herein, "extended aryl" is understood to mean a divalent aryl group, and "heteroaryl" is understood to mean a divalent heteroaryl group, including aryl and heteroaryl as given above and below. All the preferred meanings of the base.

Preferred aryl and heteroaryl are phenyl (in addition, one or more CH groups may be substituted by N), naphthalene, thiophene, selenophene, thienothiophene, dithienothiophene, anthracene and The azoles, all of which may be unsubstituted, are mono- or poly-substituted as defined above. A very preferred ring system is selected from the group consisting of pyrrole (preferably N-pyrrole), furan, pyridine (preferably 2-pyridine or 3-pyridine), pyrimidine, hydrazine. Pyr , triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, iso Azole, Azole, Diazole, thiophene (preferably 2-thiophene), selenophene (preferably 2-selenophene), thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, furan[ 3,2-b]furan, furo[2,3-b]furan,seleno[3,2-b]selenophene,seleno[2,3-b]selenophene, thieno[3, 2-b] selenophene, thieno[3,2-b]furan, hydrazine, isoindole, benzo[b]furan, benzo[b]thiophene, benzo[1,2-b;4, 5-b']dithiophene, benzo[2,1-b;3,4-b']dithiophene, quinoline, 2-methylquinoline, isoquinoline, quinolin Porphyrin, quinazoline, benzotriazole, benzimidazole, benzothiazole, benzisothiazole, benzopyrene Azole, benzo Diazole, benzo Oxazole, benzothiadiazole, 4H-cyclopenta[2,1-b;3,4-b']dithiophene, 7H-3,4-dithia-7-indole-cyclopenta[a]pentyl Terpenes, all of which may be unsubstituted, monosubstituted or polysubstituted as defined above. Other examples of aryl and heteroaryl groups are selected from the groups shown below.

The alkyl or alkoxy group (i.e., wherein the terminal CH ₂ group is replaced by -O-) may be a straight or branched chain group. It is preferably a straight chain having 2, 3, 4, 5, 6, 7, 8, 12 or 16 C atoms, and thus is preferably, for example, ethyl, propyl, butyl, pentyl, hexyl, g. Base, octyl, dodecyl or hexadecanyl, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy or dodecyloxy, for example, Is methyl, fluorenyl, fluorenyl, undecyl, thirteen, tetradecyl, decyl, decyloxy, decyloxy, undecyloxy, tridecyloxy or tetradecyloxy base.

The alkenyl group (i.e., wherein one or more CH ₂ groups are replaced by -CH=CH-) may be a straight or branched chain group. It is preferably a linear group having 2 to 10 C atoms, and thus is preferably a vinyl group; a propan-1-, or a prop-2-enyl group; a but-1-, 2- or di-3- Alkenyl; pent-1-, 2-, 3- or pent-4-enyl; hex-1-, 2-, 3-, 4- or hex-5-alkenyl; hept-1-, 2-, 3-, 4-, 5- or hept-6-alkenyl; oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-alkenyl; 壬-1-, 2- , 3-, 4-, 5-, 6-, 7- or 壬-8-alkenyl; 癸-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 癸-9-alkenyl.

Particularly preferred alkenyl group is C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -3E-alkenyl, C ₅ -C ₇ -4-alkenyl, C ₆ -C ₇ -5-alkenyl and C ₇ -6-alkenyl, especially C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -3E-alkenyl and C ₅ -C ₇ --4-alkenyl. Examples of particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl, etc. . Groups having up to 5 C atoms are generally preferred.

An oxaalkyl group, that is, one of the CH ₂ groups is replaced by -O-, for example, preferably a linear 2-oxapropyl group (=methoxymethyl group), 2-oxetane Base (=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl); 2-, 3- or 4-oxapentyl; 2-, 3-, 4- or 5 -oxahexyl; 2-, 3-, 4-, 5- or 6-oxaheptyl; 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl; 2-, 3 -, 4-, 5, 6-, 7- or 8-oxaindole; or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxanonyl.

In an alkyl group in which one CH ₂ group is replaced by -O- and one CH ₂ group is replaced by -C(O)-, these groups are preferably adjacent. Thus, these groups together form a carbonyloxy-C(O)-O- or oxycarbonyl-OC(O)- group. Preferably the group is straight chain and has from 2 to 6 C atoms. Therefore, it is preferably ethoxylated, propyloxy, butyloxy, pentyloxy, hexyloxy, ethoxymethyl, propyloxymethyl, butyloxymethyl, Pentyloxymethyl, 2-ethoxymethoxyethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 3-ethyloxypropyl, 3-propoxypropane Base, 4-ethenyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propyloxycarbonylmethyl, butyl Oxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxy Carbonyl) propyl, 4-(methoxycarbonyl)-butyl.

The alkyl group in which two or more CH ₂ groups are replaced by -O- and/or -C(O)O- may be straight or branched. It is preferably straight chain and has 3 to 12 C atoms. Therefore, it is preferably bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis- Carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-indenyl, 10, 10-bis-carboxy-indenyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)-propyl, 4,4-bis-(methoxycarbonyl)-butyl, 5,5-bis-(methoxycarbonyl)-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl, 7,7-bis- (methoxycarbonyl)-heptyl, 8,8-bis-(methoxycarbonyl)-octyl, bis-(ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl, 3,3-bis-(ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)-butyl, 5,5-bis-(ethoxycarbonyl)-hexyl.

a thioalkyl group, that is, one of the CH ₂ groups is replaced by -S-, preferably a linear methylthio group (-SCH ₃ ), a 1-ethylthio group (-SCH ₂ CH ₃ ), -propylthio (=-SCH ₂ CH ₂ CH ₃ ), 1-(butylthio), 1-(pentylthio), 1-(hexylthio), 1-(heptylthio), 1-( Octylthio), 1-(indolylthio), 1-(indolylthio), 1-(undecylthio) or 1-(dodecylthio), preferably, mixed with sp ² The CH ₂ group adjacent to the vinyl carbon atom is replaced.

The fluoroalkyl group is a perfluoroalkyl group C _i F _2i+1 , wherein i is an integer from 1 to 15, in particular CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ or C ₈ F ₁₇ , very preferably C ₆ F ₁₃ , or partially fluorinated alkyl, preferably having 1 to 15 C atoms, especially 1,1-difluoroalkyl, All of the above are straight or branched.

Preferably "fluoroalkyl" means a partially fluorinated (ie, not perfluorinated) alkyl group.

Alkyl, alkoxy, alkenyl, oxaalkyl, thioalkyl, carbonyl and carbonyloxy groups can be achiral or chiral. For example, a particularly preferred chiral group is 2-butyl (=1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl , 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-propylpentyl, especially 2-methylbutyl, 2-methylbutoxy, 2-methyl Pentyloxy, 3-methyl-pentyloxy, 2-ethyl-hexyloxy, 2-butyloctyloxy, 2-hexyldecyloxy, 2-octyldodecyloxy, 1-methyl Hexyloxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methyl-pentyl, 4-methylhexyl, 2-hexyl, 2-octyl , 2-indenyl, 2-indenyl, 2-dodecyl, 6-methoxy-octyloxy, 6-methyloctyloxy, 6-methyloctyloxy, 5-methylheptyloxy -carbonyl, 2-methylbutanoxy, 3-methylpentyloxy, 4-methylhexyloxy, 2-chloro-propenyloxy, 2-chloro-3-methylbutanyl Oxyl, 2-chloro-4-methyl-pentanyl-oxy, 2-chloro-3-methylpentyloxy, 2-methyl-3-oxapentyl, 2-methyl-3 -oxa-hexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxy Propyl-2-oxyl, 2-fluorooctyloxy Base, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy. Excellently 2-ethylhexyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1 -Trifluoro-2-hexyl, 1,1,1-trifluoro-2-octyl and 1,1,1-trifluoro-2-octyloxy.

Preferred achiral branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), tert-butyl, isopropoxy, 2 -Methyl-propoxy and 3-methylbutoxy.

In a preferred embodiment, the alkyl groups are each independently selected from the group consisting of 1 to 30 C atoms, a secondary or tertiary alkyl group or an alkoxy group, wherein one or more H atoms are optionally subjected to F. Displacement; or an aryl, aryloxy, heteroaryl or heteroaryloxy group optionally alkylated or alkoxylated and having 4 to 30 ring atoms. An excellent group of this type is selected from the group consisting of the following formula Wherein "ALK" means having 1 to 20 C atoms, preferably 1 to 12 C atoms, and in the case of a tertiary group, preferably 1 to 9 C atoms are optionally fluorinated. A linear alkyl or alkoxy group, and the dashed line indicates the linkage to the ring to which the groups are attached. Particularly preferred among these groups are the groups in which all of the ALK subgroups are the same.

As used herein, "halogen" or "hal" includes F, Cl, Br or I, preferably F, Cl or Br.

As used herein, -CO-, -C(=O)-, and -C(O)- are understood to mean carbonyl, that is, having a structure. The group.

As used herein, C=CR ¹ R ^{2 is} understood to mean a subunit, ie having a structure The group.

In the above and below, Y ¹ and Y ² are each independently H, F, Cl or CN.

In this context, R ⁰ and R ⁰⁰ are each independently H or an optionally substituted carbyl or hydrocarbyl group having 1 to 40 C atoms, and preferably represents H or an alkyl group having 1 to 12 C atoms.

Detailed description

The fullerene of formula F demonstrates the following improved properties compared to the previously disclosed fullerene derivatives and mixtures for OPV and OPD applications:

i) a substituent R ¹ which comprises an extended alkyl chain having 7 or more C atoms and, if present, a substituent L which may have any number of solubilizing groups capable of passing fullerene 2+2 The dimerization of the Diels Alder dimerization /oligomerization reaction allows the bulk heterojunction to have greater light stability, such as Adv. Energy Mater. 2014, 4 , 1300693 and ACS Nano 2014, 8 (2) , as described in 1297-1308.

Ii) Substituent R ¹ and, if present, the substituent L is capable of imparting greater stability to the luminescence of the bulk heterojunction via the modulation of fullerene crystallization and/or phase separation kinetics, thus stabilizing at BHJ The initial equilibrium thermodynamics.

Iii) the substituent R ¹ and, if present, the substituent L is capable of imparting greater thermal stability to the block heterostructure by means of fullerene crystallization and/or phase separation kinetics, thus stabilizing in BHJ Initial equilibrium thermodynamics.

iv) the position of the fullerene Ar and R ¹ is electron-accepting and / or electron donor unit to reduce the energy band gap of fullerenes and thus reduces the potential of improving the light absorption.

v) additional electron energy (HOMO / LUMO level) of the spinner can be carefully selected positions by Ar and R ¹ is electron-accepting and / or electron supply means to increase the open circuit potential (V _oc) and reached.

Vi) additional fine tuning of the electron energy (HOMO/LUMO level) can be achieved by carefully selecting the electron accepting and/or electron supply units at positions Ar and R ¹ to reduce the fullerene and p-type materials during electron transfer Caused by energy loss between (for example, polymers, oligomers or defined molecular units).

Vii) Substituent R ¹ and, if present, Substituent L, the fullerene has a higher solubility in the halogen-free solvent due to the increased number of solubilizing groups.

Viii) Substituent R ¹ and, if present, substituent L increases solubility and mutual compatibility (miscibility) of fullerenes with the polymer, minimizing thermal and photoinduced phase separation resulting in operational stability of the device Improvement.

The fullerene C _n in formula F and its subformula can be composed of any number n of carbon atoms. Preferably, in the compound of the formula F and its subformula, the number n of carbon atoms constituting the fullerene C _n is 60, 70, 76, 78, 82, 84, 90, 94 or 96, very preferably 60 or 70.

The mixture according to the invention may also comprise two or more compounds of the formula F, differing in the number of carbon atoms which form the fullerene.

The mixtures according to the invention may also comprise two or more compounds of the formula F, which differ in the structure of the substituents R ¹ and/or the number of carbon atoms.

Mixtures according to the invention may also comprise two or more compounds of formula F, differing in their substituent Ar structure.

Therefore, in another preferred embodiment of the present invention, the fullerene mixture comprises C60 fullerene and higher fullerene, preferably selected from C70, C76, C78, C82, C84, C90, C94 or C96, and very preferably C70, wherein optionally C60 fullerene and higher fullerenes differ in at least one of: - the structure of the substituents R ¹ and / or the number of carbon atoms, - The Ar structure of the substituent.

In another preferred embodiment of the present invention, the fullerene mixture comprises two or more fullerenes, preferably selected from C70, C76, C78, C82, C84, C90, C94 or C96, and very preferably C60 or C70, wherein the two or more fullerenes differ in at least one of: - the structure of the substituents R ¹ and/or the number of carbon atoms, - the structure of the substituents Ar.

The fullerene C _n in the formula F and its subformula is preferably selected from the group consisting of carbon-based fullerenes, inlaid fullerenes or mixtures thereof, and is preferably selected from carbon-based fullerenes.

Suitable and preferred carbon-based fullerenes include, but are not limited to, (C _60-Ih )[5,6]fullerene, (C _70-D5h )[5,6]fullerene, (C _{76-D2 *} ) [5,6] fullerenes, (C _84-D2* ) [5,6] fullerenes, (C _84-D2d ) [5,6] fullerenes or the aforementioned carbon-based fullerenes a mixture of two or more.

The embedded fullerene is preferably a metal fullerene. Suitable and preferred metal fullerenes include, but are not limited to, La@C ₆₀ , La@C ₈₂ , Y@C ₈₂ , Sc ₃ N@C ₈₀ , Y ₃ N@C ₈₀ , Sc ₃ C ₂ @C ₈₀ Or a mixture of two or more of the foregoing metal fullerenes.

In the compound of formula F, the adduct -C(Ar)(R ¹ )- is preferably appended to the fullerene C _n by a [6,6]-bond and/or a [5,6]-bond. Preferably, in the compound of formula F, the adduct -C(Ar)(R ¹ )- is attached to the fullerene C _n by a [6,6]-bond to form a [6,6]-aryl group. - A bridge fullerene.

If C _n is a less symmetric fullerene, such as C70, the compound of formula F may also comprise a mixture of regioisomers, wherein the adduct -C(Ar)(R ¹ )- is attached Different linkages to fullerenes are disclosed, for example, in C. Thilgen and F. Diederich, Top. Curr. Chem. 1999, 199 , 135-171.

Compounds of formula F can also be subjected to fullerene 2+2 Diels Alder II as described in Adv. Energy Mater. 2014, 4 , 1300693 and ACS Nano 2014, 8(2) , 1297-1308. Polymerization / oligomerization reaction.

In the compound of the formula F and its subformula, o preferably represents 1, 2, 3 or 4, very good for 1 or 2. In another preferred embodiment, o is a non-integer of >1, such as 1.5.

In the compound of the formula F and its subformula, R ¹ preferably denotes an alkyl group having 7 to 20, preferably 7 to 15, a C atom, wherein one or more CH ₂ groups may be via -O- , -C(O)-, -C(O)-O- or -OC(O)-substitution, and wherein one or more H atoms are optionally replaced by F.

Very preferably R ¹ is selected from the following formula:

Wherein each group independently has the following meaning a, b0 or an integer from 1 to 15, and a+b 5, c, d, e 0 or an integer from 1 to 15, and c + d + e 4, f is an integer from 6 to 15, g 0 or an integer from 1 to 15, R ¹¹ has a linear or branched alkyl group of 5 to 15 C atoms, wherein one or more H atoms are optionally subjected to F Replacement, or, if g 5, R ¹¹ may also represent H, F, CN or an alkyl group having 1 to 4 C atoms, wherein one or more H atoms are optionally substituted by F.

Substituents of the formulae R1, R2, R3 and R4 are preferred, wherein a is 3 or greater. Further preferred are substituents of the formulae R1, R2, R3 and R4, wherein b is 5 or more.

Substituents of formula R5 and R6 are preferred, wherein d is 3 or greater. Further preferred are substituents of the formulae R5 and R6 wherein e is 5 or more.

Substituents of the formulae R10 and R11 are preferred, wherein g is 3 or greater.

In the compounds of formula F and its subformulae, Ar is preferably selected from the group consisting of formulas C1 and C2, optionally substituted with one or more groups L as defined above.

Very preferably Ar represents a benzene optionally substituted with one or more groups L as defined above.

In addition to the adduct -C(Ar)(R ¹ )- in formula F, the fullerene C _n may have any number (m) of a second adduct different from -C(Ar)(R ¹ )- Ad. The second adduct Ad can be any possible adduct or combination of adducts having any connectivity to fullerenes.

The adduct Ad is preferably attached to the fullerene C _n by a [6,6]-bond and/or a [5,6]-bond, preferably at least one [6,6]-bond.

In the compound of the formula F and its subformula, the number m of the second adducts Ad attached to the fullerene C _n is 0, An integer of 1, or a non-integer of >0 such as 0.5 or 1.5, and preferably 0, 1 or 2.

In a preferred embodiment, the number m of second adducts Ad added to the fullerene C _n is zero.

In another preferred embodiment, the number m of second adducts Ad appended to the fullerene C _n is > 0, preferably 1 or 2.

The second adduct Ad of Formula I and its subformula is preferably selected from the following formula

Wherein R ^S1 , R ^S2 , R ^S3 , R ^S4 and R ^S5 independently of each other represent H, halogen or CN, or have one of the meanings of R ¹ or L as given by the context, and Ar ^S1 and Ar ^S2 are independent of each other Is an aromatic or heteroaromatic group having 4 to 30 ring C atoms, which is mono- or polycyclic, optionally containing a fused ring, and optionally via one or more groups as defined above and below. L is substituted.

Preferably, Ar ^S1 and Ar ^S2 are selected from the following formula It is optionally substituted with a group R ¹¹ or L as defined above and below.

In the compound of the formula F and the sub-formulas, all adduct ^{-C (Ar) (R 1)} - or in any combination and Ad connected to each other in the final product during the synthesis, facilitate the preferred properties of the final product.

Further preferred compounds of formula F and its subformulae are selected from the following preferred embodiments, including any combination thereof:

- m is 0,

- o is 1 or 2,

- m is 0 and o is 1 or 2,

- n is 60 or 70,

- n is 60,

- Ar represents benzene or thiophene, very preferably benzene, which is optionally One or more groups L are substituted.

- R ¹ is selected from the group consisting of the formulae R1 to R11, very preferably selected from the formula R1 or R10.

Examples of compounds of the preferred formula F are listed below:

Among them, fullerenes are C60.

Further preferred compounds are the compounds of formula F1 to F6 above, wherein the fullerenes are C70 rather than C60.

The compound of the formula F is easy to synthesize, in particular by a method suitable for mass production, and exhibits advantageous properties such as good structural organization and film-forming properties, good electronic properties (especially high carrier mobility), Good processability (especially high solubility in organic solvents), and high gloss and thermal stability.

Compounds of formula F can be synthesized according to or analogous to methods known to those skilled in the art and described in the literature. For example, the synthetic routes of various fullerenes of formula I have been previously outlined in the literature: J. Mater. Chem., 1997, 7(7), 1097-1109; Chem. Soc. Rev., 1999, 28, 263-277; Chem. Rev. 2013, 113, 5262-5321; J. Am. Chem. Soc. 2011, 133, 2402-2405; and Chem. Rev., 2006, 106(12), 5049-5135.

As used in the mixture of the invention (hereinafter also referred to simply as "polymer"), the conjugated polymer comprises one or more units of formula 1 and one or more units of formula 2

Each of the groups is as defined above.

Preferably, the polymer comprises, in addition to the units of the formulae 1 and 2, one or more spacer units selected from the group consisting of the following formulas Sp

Wherein R ¹¹ and R ¹² are as defined in formula 1.

Preferably, the spacer unit is selected from the group consisting of the formulas Sp1, Sp4 and Sp6, wherein preferably one of R ¹¹ and R ¹² is H, or both R ¹¹ and R ¹² are H.

Preferably, the polymer comprises one or more units of the formula 1a and one or more units of the formula 2a, very preferably composed of it, -(D-Sp)-1a

-(A-Sp)- 2a where D represents a unit of formula 1, A represents a unit of formula 2, and Sp represents The unit selected from the group consisting of Sp1 to Sp16 is very preferably selected from the group consisting of Sp1 and Sp6.

Preferred polymers consist of one or more units of formula 1, one or more units of formula 2, and optionally one or more spacer units selected from the group consisting of Sp1 to Sp16.

Very preferred is a polymer of formula P-[(D-Sp) _x -(A-Sp) _y ] _n - P wherein A, D and Sp are as defined in formulas 1a and 2a, and x represents a unit (D-Sp) The molar fraction, y represents the molar fraction of the unit (A-Sp), x and y are each independently > 0 and < 1, and x + y = 1, and n is an integer > 1 .

The polymer of the preferred formula P is selected from the following subtypes

Wherein R ^11-16 , x, y and n are as defined in formulas 1, 2 and P.

Preferably, R ¹¹ and R ¹² in Sp1 to Sp16, P1 and P2 are H.

Preferably, R ¹³ and R ¹⁴ in Formula 1, P1 and P2 are different from H.

Preferably, R ¹⁵ and R ¹⁶ in Formula 1, P1 and P2 are H.

Preferably, R ¹⁷ and R ¹⁸ in Formulas 2, P1 and P2 are different from H.

Preferably, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ in the formulas 1, 2, Sp1-Sp16, P1 and P2, when different from H, are selected From the following groups: - a group consisting of randomly fluorinated linear or branched alkyl groups having 1 to 30 (preferably 1 to 20) C atoms, - a group consisting of the following a linear or branched alkyl, alkoxy or sulfanylalkyl having 1 to 30 (preferably 1 to 20) C atoms, and having 2 to 30 (preferably 2 to 20) a linear or branched alkylcarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyl group of a C carbon atom, each of which is unsubstituted or substituted by one or more F atoms.

It is very preferred that R ¹³ and R ¹⁴ in the formulae 1, P1 and P2 represent -CO-OR ^x , and R ^x is a linearly or branched alkyl group having 1 to 20 C atoms which is arbitrarily fluorinated.

Very good as Formula 2, P1 and P2 of R ¹⁷ and R ¹⁸ represents R ^x or -OR ^x, and R ^x is optionally fluorinated straight-chain having 1 to 20 C atoms or a branched alkyl group.

In the polymers of the formulae P, P1 and P2, x and y are preferably from 0.1 to 0.9, very preferably from 0.3 to 0.7, most preferably from 0.4 to 0.6.

In the polymer according to the invention, the total number n of repeating units is preferably from 2 to 10,000. The total number n of repeating units is preferably 5, very good for 10, the best is 50, and preferably 500, very good for 1,000, the best is 2,000, including any combination of the above lower and upper limits of n.

The polymers of the invention are preferably statistical or random copolymers.

Further preferred is a conjugated polymer R ³¹ -chain-R ³² PT according to the invention selected from the formula PT

Wherein "chain" means a selected polymer chain of formula P, P1 or P2, and R ³¹ and R ³² independently of one another have one of the meanings of R ¹¹ as defined above, or independently of each other, H, F, Br, Cl, I, -CH ₂ Cl, -CHO, -CR'=CR" ₂ , -SiR'R"R"', -SiR'X'X", -SiR'R"X', -SnR'R"R"',-BR'R",-B(OR')(OR"), -B(OH) ₂ , -O-SO ₂ -R', -C≡CH, -C≡C-SiR ' ₃ , -ZnX' or a capping group, X' and X" represent a halogen, and R', R" and R'" independently of each other have one of the meanings of R ⁰ given in Formula 1, and Preferably, it represents an alkyl group having 1 to 12 C atoms, and both of R', R" and R'" may form a cyclic fluorenyl group having 2 to 20 C atoms together with each of the hetero atoms to which they are attached. a cyclostannyl, cycloborane or cyclic boronate group.

Preferred capping groups R ³¹ and R ³² are H, C _1-20 alkyl, or optionally substituted C _6-12 aryl or C _2-10 heteroaryl, very preferably H or phenyl.

The conjugated polymer can be prepared, for example, by copolymerizing one or more monomers selected from the group consisting of the following formulas in an aryl-aryl coupling reaction to prepare R ³³ -DR ³⁴ MI

R ³³ -AR ³⁴ MII

R ³³ -Sp-R ³⁴ MIII

Wherein at least one single system is selected from the group consisting of the formula MI and at least one single system is selected from the group consisting of the formula MII, D is a unit of the formula 1, A is a unit of the formula 2, and Sp is a spacer unit selected from the group consisting of the formulae Sp1 to Sp16, R ³³ and R ³⁴ is independently selected from the group consisting of H (preferably activated CH bond), Cl, Br, I, O-toluenesulfonate, O-trifluoromethanesulfonate, O-A Sulfonic acid, O-perfluorobutanesulfonate, -SiMe ₂ F, -SiMeF ₂ , -O-SO ₂ Z ¹ , -B(OZ ² ) ₂ , -CZ ³ =C(Z ³ ) ₂ , -C≡ CH, -C≡CSi(Z ¹ ) ₃ , -ZnX ⁰⁰ and -Sn(Z ⁴ ) ₃ , wherein X ⁰⁰ halogen, preferably Cl, Br or I, Z ^1-4 is selected from the group consisting of Group: alkyl (preferably C _1-10 alkyl) and aryl (preferably C _6-12 aryl), each optionally substituted, and two groups Z ² may also be associated with B- and O- The atom forms a cyclic boronate group having 2 to 20 C atoms.

The monomers of formula MI-MIII can be copolymerized with one another and/or with other suitable co-monomers.

The polymers according to the present invention can be synthesized according to or in a manner similar to that known to those skilled in the art and described in the literature. Other preparation methods are available from The examples were obtained.

For example, the polymer can be suitably prepared by an aryl-aryl coupling reaction such as Yamamoto coupling, C-H activation coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling. Suzuki coupling, Stille coupling and Yamamoto coupling are preferred. Monomers which are polymerized to form repeating units of the polymer can be prepared according to methods known to those skilled in the art.

Preferably, the polymer is prepared from a monomer selected from the group consisting of MI-MVI as described above.

Another aspect of the present invention is a process for preparing a polymer by coupling one or more selected from the group consisting of the formula MI-MIII in a polymerization reaction (preferably in an aryl-aryl coupling reaction) or Different monomers are mutually and/or with one or more comonomers.

Preferred aryl-aryl coupling and polymerization methods for use in the methods described above are Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling, CH activation coupling, Ullmann coupling or Buchwald coupling. Particularly preferred are Suzuki coupling, Negishi coupling, Stille coupling and Yamamoto coupling. Suzuki coupling is described, for example, in WO 00/53656 A1. Negishi coupling is described, for example, in J. Chem. Soc., Chem. Commun., 1977, 683-684. Yamamoto coupling is described, for example, in T. Yamamoto et al, Prog. Polym. Sci., 1993, 17, 1153-1205 or WO 2004/022626 A1. Stille coupling is described, for example, in Z. Bao et al, J. Am. Chem. Soc., 1995, 117, 12426-12435. The CH activation system is described, for example, in M. Leclerc et al, Angew. Chem. Int. Ed. 2012, 51, 2068-2071. For example, when Yamamoto coupling is used, it is preferred to use a monomer having two reactive halide groups. When Suzuki coupling is used, it is preferred to use a monomer having two reactive boric acid or borate groups or two reactive halide groups. When Stille coupling is used, it is preferred to use a monomer having two reactive tin alkyl groups or two reactive halide groups. When a Negishi coupling is used, it is preferred to use a monomer having two reactive organozinc groups or two reactive halide groups. When a linear polymer is synthesized by CH activating polymerization, it is preferred to use a monomer as described above, wherein at least one of the reactive groups is an activated hydrogen bond.

Preferred catalysts (especially for Suzuki, Negishi or Stille coupling) are selected from the group consisting of Pd(0) complexes or Pd(II) salts. Preferably, the Pd(0) complex is one having at least one phosphine ligand such as Pd(Ph ₃ P) ₄ . Another preferred phosphine ligand is cis (o-tolyl)phosphine, i.e., Pd(o-Tol ₃ P) ₄ . Preferably, the Pd(II) salt comprises palladium acetate, i.e., Pd(OAc) ₂ , or trans-di(μ-acetate)-bis[o-(di-o-tolylphosphino)benzyl]dipalladium ( II). Alternatively, the Pd(0) complex can be obtained by making Pd(0) dibenzylideneacetone complex (for example, bis(dibenzylideneacetone) dipalladium (0), bis(dibenzylideneacetone) palladium. (0)) or a Pd(II) salt (such as palladium acetate) with a phosphine ligand (such as triphenylphosphine, cis (o-tolyl) phosphine, cis (o-methoxyphenyl) phosphine or tri (third Butyl) phosphine) is prepared by mixing. The Suzuki polymerization is carried out in the presence of a base such as sodium carbonate, potassium carbonate, cesium carbonate, lithium hydroxide, potassium phosphate or an organic base such as tetraethylammonium carbonate or tetraethylammonium hydroxide. Yamamoto polymerization employs a Ni(0) complex such as bis(1,5-cyclooctadienyl)nickel (0).

Suzuki, Stille or C-H activated coupling polymerization can be used to prepare homopolymers as well as statistical, alternating and block random copolymers. The statistical, block random copolymer or block copolymer can be prepared, for example, from the above monomers, wherein one reactive group is a halogen and the other reactive group is a CH activating bond, a boronic acid, a boronic acid derivative group or an alkyl group. Stanane. The synthesis of the statistical, alternating and block copolymers is described in detail in, for example, WO 03/048225 A2 or WO 2005/014688 A2.

As an alternative to the halogen described above, a leaving group of the formula -O-SO ₂ Z ¹ wherein Z ¹ is as defined above can be used. Specific examples of such cleavage groups are tosylate, mesylate and triflate.

A general preparation method of the BTZ-F ₂ monomer of the formula A has been described, for example, in WO 2011/060526 A1.

The synthesis of thiophene monomers of formula D has been described, for example , in Macromolecules, 2007, 40 (26), Organometallics 2011, 30 , 3233-3236, Macromolecules, 2007, 40 (6) and J. Am. Chem. Soc. 130 , 13167-13176.

In the mixture according to the invention (i.e. without solvent), the concentration of the compound of formula F is preferably from 40 to 90% by weight, very preferably from 50 to 70% by weight.

In the mixture according to the invention (i.e., excluding the solvent), the concentration of the conjugated polymer is preferably from 10 to 60% by weight, very preferably from 30 to 50% by weight.

In the mixture according to the invention, the ratio of polymer:fullerene is preferably from 5:1 to 1:5, more preferably from 1:1 to 1:3, most preferably 1:1. To 1:2, all of the above are by weight.

In another preferred embodiment of the invention, the mixture additionally comprises one or more binders to adjust the rheological properties, as described, for example, in WO 2005/055248 A1. Suitable and preferred adhesives are polymeric binders such as polystyrene (PS), polypropylene (PP) and polymethyl methacrylate (PMMA). The binder can be added to the mixture at a concentration of from 5 to 95% by weight of the total solids (i.e., no solvent).

The mixture according to the present invention can be used with other monomeric compounds or polymers having one or more of semiconductor, charge transport, hole transport, electron transport, hole blocking, electron blocking, conducting, photoconductive, and luminescent properties.

Accordingly, another aspect of the invention pertains to a mixture comprising a conjugated polymer and fullerene as defined above, and additionally comprising one or more additional compounds, preferably having a semiconductor, charge transport, electricity One or more of hole transport, electron transport, hole blocking, electron blocking, electrical conduction, light guiding, and luminescent properties.

Another aspect of the invention pertains to a blend comprising a mixture of a conjugated polymer as described above and a fullerene compound of formula F, and additionally comprising one or more solvents, preferably selected from the group consisting of organic solvents.

The blend is preferably used as a support for the preparation of a semiconductor layer of an OE device such as an OPV or OPD device, wherein the fullerene derivative or fullerene composition is used, for example, in a photoactive layer.

In the blend according to the invention (i.e. comprising a solvent), the concentration of the mixture according to the invention is preferably from 0.1 to 10% by weight, more preferably from 0.5 to 5 weight. the amount%.

The blend according to the invention preferably forms a solution.

The invention further provides an OE device comprising a mixture according to the invention, and an OE device comprising a semiconductor or photoactive layer (hereinafter also referred to as "activation layer") comprising, according to the invention, as described above and below mixture.

Preferred OE devices are OFET, TFT, IC, logic circuit, capacitor, RFID tag, OLED, OLET, OPED, OPV, OPD, organic solar cell, DSSC, perovskite-based solar cell, laser diode, photoconductor , photodetector, electrophotographic device, electrophotographic recording device, organic memory device, sensor device, charge injection layer, Schottky diode, planarization layer, antistatic film, conductive substrate and conductive pattern .

The Yujia electronic devices are OFET, OLED, OPV and OPD devices, especially block heterojunction (BHJ) OPV devices and OPD devices. In OPV or OPD, for example, the photoactive layer may comprise a mixture according to the invention. In an OFET, for example, an active semiconductor channel between a drain and a source can comprise a semiconductor layer comprising a mixture according to the invention. As another example, in an OLED device, a charge (hole or electron) injection or transport layer can comprise a mixture according to the invention.

The mixtures according to the invention are particularly suitable as photoactive materials for use in photoactive layers of OPV, BHJ OPV or OPD devices. A conjugated polymer comprising units of the formulae 1 and 2 serving as an electron donor or a P-type semiconductor component, and a fullerene of the formula F serving as an electron acceptor or an n-type semiconductor component are contained therein. Preferably, the fullerene and the conjugated polymer are selected to form a mixture into a block Material heterojunction.

The OPV or OPD device preferably further comprises a first transparent or translucent electrode on the transparent or translucent substrate on one side of the active layer, and a second metal or translucent electrode on the other side of the active layer.

In another preferred embodiment, the photoactive layer comprises a mixture according to the invention additionally comprising one or more organic and inorganic compounds or materials to enhance device properties. Suitable and preferred examples of such additional compounds or materials are selected from metal particles, such as Au or Ag nanoparticles or Au or Ag nanopyrene, which enhance light due to near field effects (i.e., plasmonic effect) Harvesting, for example, as described in Adv. Mater. 2013, 25(17), 2385-2396 and Adv. Ener . Mater. 10.1002/aenm. 201400206, molecular dopants for improving photoconductivity, such as 2, 3, 5 , 6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, as described in Adv. Mater. 2013, 25 (48), 7038-7044, or by UV absorbers and/or Stabilizers composed of anti-free radical agents and/or antioxidants, such as 2-hydroxybenzophenone, 2-hydroxyphenylbenzotriazole, oxalyl benzene, hydroxyphenyl three Anthocyanins, hindered phenols, N-aryl-thiomorpholine, N-aryl-thiomorpholine-1-oxide, N-aryl-thiomorpholine-1,1-dioxide , N-aryl-thiazolidine, N-aryl-thiazolidine-1-oxide, N-aryl-thiazolidine-1,1-dioxide and 1,4-diazabicyclo[2.2. 2] Octane, as described in WO2012095796 A1 and WO2013021971 A1.

The OPV or OPD device preferably additionally comprises a UV to visible light conversion layer such as described, for example, in J. Mater. Chem. 2011, 21 , 12331, or a NIR to visible or IR to NIR light conversion layer, such as, for example, J. Appl .Phys. 2013, 113 , 124509.

The OPV or OPD device may additionally comprise an additional interfacial layer interposed between the active layer and the electrode to serve as a hole blocking layer, a hole transport layer, an electron blocking layer and/or an electron transport layer, typically comprising a metal oxide (eg ZnO _{x , TiO x, ZTO, MoO x} , NiO x), salts (e.g.: LiF, NaF), conjugated polymer electrolyte (e.g.: PEDOT: PSS or PFN), a conjugated polymer (for example: PTAA) or organic compound ( For example: NPB, Alq ₃ , TPD).

Preferably the OPV or OPD device comprises one or more additional buffer layers interposed between the active layer and the first or second electrode, which when used as a hole transport layer and/or an electron blocking layer, comprise the following materials Such as: metal oxides (such as ZTO, MoO _x , NiO _x ), doped conjugated polymers (such as PEDOT: PSS and polypyrrole-polystyrene sulfonate (PPy: PSS)), conjugated polymers (such as Polytriarylamine (PTAA), organic compound (eg substituted triarylamine derivatives such as N,N'-diphenyl-N,N'-bis(1-naphthyl)(1,1'-biphenyl) -4,4'diamine (NPB), N,N'-diphenyl-N,N'-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD)), a graphene-based material such as graphene oxide, reduced graphene oxide, graphene, graphene nanobelts, and graphene quantum dots; or when the additional buffer layer acts as a hole barrier and/or Or an electron transport layer, which comprises the following materials such as: metal oxides (for example, ZnO _x , TiO _x , AZO (aluminum-doped zinc oxide)), salts (for example, LiF, NaF, CsF), conjugated polymer electrolytes ( For example, poly[3-(6-trimethylammonium hexyl)thiophene], poly(9,9-bis(2-ethylhexyl) )-茀]-b-poly[3-(6-trimethylammonium hexyl)thiophene], or poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-) 2,7-茀)-alt-2,7-(9,9-dioctylfluorene)]); a polymer such as poly(ethyleneimine) or a crosslinked N-containing compound derivative or an organic compound (for example) reference (8-quinolinolato) - aluminum (III) (Alq _3), a phenanthroline derivative, or C ₇₀ to C ₆₀ or fullerene based of, for example, in Adv.Energy Mater.2012,2,82-86 Said.

To make a thin layer in an OE device, such as a BHJ OPV device, the mixture or blend according to the present invention can be deposited by any suitable method. Liquid coating of the device is more desirable than vacuum deposition techniques. A solution deposition method is particularly preferred. The compositions of the present invention are capable of using a number of liquid coating techniques. Preferred deposition techniques include, but are not limited to, dip coating, spin coating, ink jet printing, nozzle printing, letterpress printing, screen printing, gravure printing, knife coating, roll printing, reverse roll printing, lithography, dry lithography. , flexographic, web printing, spray coating, curtain coating, brush coating, slot dye coating or pad printing. For the manufacture of OPV devices and modules, regional printing methods compatible with flexible substrates are preferred, such as slot dye coating, spray coating, and the like.

When preparing a suitable solution or blend containing a mixture of fullerene (as n-component) and polymer (as p-component) according to the present invention, a suitable solvent should be selected to ensure p-type and n-type groups. The parts are completely dissolved and the boundary conditions (e.g., rheological properties) introduced by the selected printing method are considered.

Organic solvents are usually used for this purpose. Typical solvents can be aromatic solvents, halogenated solvents or chlorine containing solvents, including chlorine containing aromatic solvents. Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers, and mixtures thereof. Examples include, but are not limited to, dichloromethane, chloroform, tetrachloromethane, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2-dichloroethane, 1,1,1 -trichloroethane, 1,1,2,2-tetrachloroethane, 1,8-diiodooctane, 1-chloronaphthalene, 1,8-octane-dithiol, anisole, 2- Methylanisole, phenylethyl ether, 4-methylanisole, 3-methylanisole, 2,6-dimethylanisole, 2,5-dimethylanisole, 2,4 - dimethylanisole, 3,5-dimethyl-anisole, 4-fluoroanisole, 3-fluoro-anisole, 3-trifluoro-methylanisole, 4-fluoro- a mixture of 3-methylanisole, 2-fluoroanisole, toluene, o-xylene, m-xylene, p-xylene, xylene o-, m- and p-isomer, 1, 2,4-trimethylbenzene, 1,2,3,4-tetramethylbenzene, pentylbenzene, mesitylene, cumene, isopropyl toluene, cyclohexylbenzene, diethylbenzene, cyclohexyl Alkane, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, tetrahydronaphthalene, decahydronaphthalene, indoline, 1-methyl-4-(1-methylvinyl) -cyclohexene (d-limonene), 6,6-dimethyl-2-methylenebicyclo[3.1.1]heptane (β-pinene), 2,6-dimethylpyridine, 2-fluoro- Between-two Phenyl, 3-fluoro - o - xylene, 2-chloro - trifluoromethylphenyl, 2-chloro-6-fluoro-toluene, 2,3-dimethylpyrazole , 2-fluorobenzonitrile, 4-fluororisin, 3-fluorobenzonitrile, 1-fluoro-3,5-dimethoxy-benzene, 3-fluorobenzotrifluoride, trifluorotoluene, trifluoro Methoxy-benzene, 4-fluorobenzotrifluoride, 3-fluoropyridine, toluene, 2-fluoro-toluene, 2-fluorobenzotrifluoride, 3-fluorotoluene, 4-isopropylbiphenyl, phenyl ether, Pyridine, 4-fluorotoluene, 2,5-difluorotoluene, 1-chloro-2,4-difluorobenzene, 2-fluoropyridine, 3-chlorofluoro-benzene, 1-chloro-2,5-difluorobenzene , 4-chlorofluorobenzene, 2-chlorofluorobenzene, methyl benzoate, ethyl benzoate, nitrobenzene, benzaldehyde, benzonitrile, tetrahydrofuran, 1,4-two Alkane, 1,3-two Alkane, morpholine, acetone, methyl ethyl ketone, ethyl acetate, n-butyl acetate, N,N-dimethylaniline, N,N-dimethylformamide, N-methylpyrrolidone , dimethyl acetamide, dimethyl hydrazine and/or mixtures thereof.

It is especially preferred to be a solvent selected from the group consisting of aliphatic or aromatic hydrocarbons free of chlorine or mixtures thereof.

Further preferred is an aliphatic or aromatic hydrocarbon selected from the group consisting of chlorine-free aliphatic or aromatic hydrocarbons or mixtures thereof containing less than 5% halogen-containing but chlorine-free (e.g., fluorine, bromine or iodine), such as , a solvent of 8-diiodooctane).

Preferred solvents of this type are selected from the group consisting of 1,2,4-trimethylbenzene, 1,2,3,4-tetramethylbenzene, pentylbenzene, mesitylene, cumene, isopropyltoluene, Cyclohexylbenzene, diethylbenzene, tetrahydronaphthalene, decahydronaphthalene, 2,6-dimethylpyridine, N,N-dimethylformamide, 2,3-dimethylpyrryl , 2-methylanisole, phenylethyl ether, 4-methyl-anisole, 3-methylanisole, 2,5-dimethyl-anisole, 2,4-dimethylbenzate Ether, 3,5-dimethyl-anisole, N,N-dimethylaniline, ethyl benzoate, 1-methylnaphthalene, 2-methylnaphthalene, N-methylpyrrolidone, two Alkane, 4-isopropylbiphenyl, phenyl ether, pyridine, 1,8-octane dithiol, nitrobenzene, 1-chloronaphthalene, p-xylene, m-xylene, o-xylene or a mixture of o-, m-, and p-isomers.

The OPV device can be of any type of OPV device known in the literature (see, for example, Waldauf et al, Appl. Phys. Lett. , 2006, 89 , 233517).

A first preferred OPV device in accordance with the present invention comprises the following layers (in order from bottom to top):

- Randomly substrate,

a high work function electrode acting as an anode or a conductive gate, preferably comprising a metal oxide (eg ITO),

- a random conductive polymer layer or hole transport layer, preferably comprising Polymer or polymer blend, for example: PEDOT: PSS (poly(3,4-ethylenedioxythiophene): poly(styrene-sulfonate), substituted triarylamine derivative, such as TBD (N,N'-diphenyl-N-N'-bis(3-methylphenyl)-1,1'biphenyl-4,4'-diamine) or NBD (N,N'-diphenyl) --N-N'-bis(1-naphthylphenyl)-1,1'biphenyl-4,4'-diamine),

Forming a layer of BHJ (also referred to as a "photoactivated layer") comprising p-type and n-type organic semiconductors, which may, for example, be in the form of p-type/n-type bilayers or in different p-types and n-types Layer, or in the form of a blend or p-type and n-type semiconductor,

a layer optionally having electron transport properties, for example, containing LiF, TiO _x , ZnO _x , PFN, poly(ethyleneimine) or a crosslinked nitrogen-containing compound derivative or a phenanthroline derivative

a low work function electrode serving as a cathode, preferably comprising a metal (e.g., aluminum), wherein at least one of the electrodes, preferably an anode, is at least partially transparent to visible light, and wherein the photoactive layer contains A mixture of the invention.

A second preferred OPV device in accordance with the present invention is an inverted OPV device and includes the following layers (in order from bottom to top): - a random substrate, - a high work function metal or metal oxide that acts as a cathode or a conductive gate An electrode comprising, for example, ITO, a layer having hole blocking properties, preferably comprising a metal oxide (such as TiO _x or ZnO _x ), or comprising an organic compound (such as a polymer such as poly(ethyleneimine)) or a crosslinked nitrogen-containing compound derivative or a phenanthroline derivative, forming a photoactive layer comprising a p-type and an n-type organic semiconductor between the electrodes of BHJ, which may be, for example, a p-type/n-type double layer, or Different p-type layers and n-type layers, or in the form of blends or p-type and n-type semiconductors, - a random conductive polymer layer or a hole transport layer, preferably comprising an organic polymer or polymer blend , for example PEDOT:PSS or a substituted triarylamine derivative (such as TBD or NBD), acting as an electrode of the anode, comprising a high work function metal, such as silver, wherein at least one electrode, preferably a cathode, is at least partially visible Transparent, and its intermediate light-activated layer contains The mixture invention.

In the OPV device of the present invention, the p-type and n-type semiconductor materials are preferably selected from materials as described above, such as a polymer/fullerene system.

When the photoactive layer is deposited on the substrate, it forms a phase-separated BHJ to the nanometer level. For a discussion of nanophase phase separation, see Dennler et al, Proceedings of the IEEE , 2005, 93(8) , 1429 or Hoppe et al, Adv . Func . Mater , 2004, 14(10) , 1005. A random annealing step is then required to optimize the blend morphology and thus optimize the effectiveness of the OPV device.

Another method of optimizing device performance is to prepare a blend for the manufacture of OPV (BHJ) devices, which may include additives having different boiling points to promote phase separation in an appropriate manner. 1,8-octanedithiol, 1,8-diiodooctane, nitrobenzene, 1-chloronaphthalene, N,N-dimethylformamide, dimethylacetamide, dimethyl Aachen and other additives to obtain high efficiency solar cells. Examples are disclosed in J. Peet et al, Nat. Mater. , 2007, 6 , 497, or Fréchet et al . J. Am. Chem. Soc. , 2010, 132 , 7595-7597.

As further exemplified in the non-limiting examples, photovoltaic devices having a power conversion efficiency (PCE) of, for example, at least 2.5%, or at least 3.0%, or at least 4.0%, or at least 5.0% can be prepared. Although there is no specific upper limit for PCE, the PCE can be, for example, less than 20%, or less than 15%, or less than 10%.

A further preferred embodiment of the invention relates to the use of a mixture according to the invention as a dye, a hole transport layer, a hole barrier layer, an electron transport layer and/or an electron blocking layer in a DSSC or perovskite based solar cell And a DSSC or perovskite based solar cell comprising a mixture according to the invention.

DSSC and perovskite-based solar cells can be fabricated as described in the literature, for example, in Rev. 2010, 110, 6595-6663, Angew. Chem. Int. Ed. 2014, 53, 2-15 or in WO 2013171520 A1. .

The mixture of the invention can also be used as a dye or pigment in other applications, for example as ink dyes, laser dyes, fluorescent labels, solvent dyes, foods in pigmented paints, inks, plastics, fabrics, cosmetics, foods and other materials. Dyes, contrast dyes or pigments.

The mixtures and semiconductor layers of the present invention are also suitable for use in other OE devices or device components, such as in semiconductor channels of OFET devices or in An n-type semiconductor in a buffer layer, an electron transport layer (ETL) or a hole blocking layer (HBL) of an OLED or OPV device.

Therefore, the present invention also provides an OFET including a gate electrode, an insulating (or gate insulating) layer, a source electrode, a drain electrode, and an organic semiconductor channel connecting the source electrode and the drain electrode, wherein the organic The semiconductor channel comprises a mixture according to the invention as a semiconductor. Other features of OFET are well known to those skilled in the art.

An OFET in which the OSC material is disposed in a thin film between a gate dielectric and a drain electrode and a source electrode is generally known, and is described in, for example, US 5,892,244, US 5,998,804, US 6,723,394, and references cited in the background section. in. Preferred applications of such FETs are, for example, integrated circuits, TFT displays, and security applications due to, for example, the advantages of using the solubility properties of the compounds according to the invention and thus the low surface manufacturing processability.

The gate, source and drain electrodes and the insulating and semiconductor layers in the OFET device may be arranged in any order, provided that the source electrode and the drain electrode are separated from the gate electrode by an insulating layer, and both the gate electrode and the semiconductor layer Both are in contact with the insulating layer, and both the source electrode and the drain electrode are in contact with the semiconductor layer.

The OFET device according to the invention preferably comprises: - a source electrode, a - a drain electrode, - a gate electrode, - a semiconductor layer, - one or more gate insulator layers, - Randomly substrate.

Wherein the semiconductor layer comprises a mixture according to the invention.

The OFET device can be a top gate device or a bottom gate device. Suitable structures and methods of manufacture of OFET devices are known to those skilled in the art and are described in the literature, for example in US 2007/0102696 A1.

The gate insulator layer preferably comprises a fluoropolymer such as the commercially available Cytop 809M® or Cytop 107M® (from Asahi Glass). Preferably, the insulator material and one or more solvents (fluorosolves) having one or more fluorine atoms are contained, for example, by spin coating, knife coating, wire bar coating, spray coating or dip coating or other known methods ( A blend of a perfluoro-solvent is preferred to deposit a gate insulator layer. A suitable perfluorosolvent is, for example, FC75® (available from Acros, Cat. No. 12380). Other fluoropolymers and fluorosolvents are known in the prior art, such as perfluoropolymer Teflon AF® 1600 or 2400 (from DuPont) or Fluoropel® (from Cytonix) or perfluorosolvent FC 43 ® (Acros, number 12377) ). Particularly preferred are organic dielectric materials ("low-k materials") having a low permittivity (or dielectric constant) from 1.0 to 5.0, very preferably from 1.8 to 4.0, such as in US 2007/0102696 A1 or US 7,095,044. Revealed in.

In safety applications, OFETs and other devices (such as transistors or diodes) having semiconductor materials in accordance with the present invention can be used in RFID tags or security tags to identify and prevent counterfeit securities (such as banknotes, credit cards, or ID cards). , National ID documents, licenses or any products of monetary value (such as stamps, tickets, stocks, checks, etc.).

Alternatively, the mixture and the semiconductor layer according to the invention can be used for OLEDs Medium, for example, used in buffer layers, ETL or HBL of OLEDs. The OLED device can be used, for example, as an activated display layer in a flat panel display device, or as a backlight for a flat panel display such as a liquid crystal display. Common OLEDs are achieved using a multilayer structure. The luminescent layer is typically sandwiched between one or more electron transport layers and/or hole transport layers. By applying a voltage, electrons and holes as charge carriers move toward the light-emitting layer, which is equivalent to the recombination leading to excitation of the luminophore unit contained in the light-emitting layer and thus light emission.

The mixture or semiconducting layer according to the invention can be used in one or more of ETL, HBL or buffer layers, especially such water-soluble derivatives (for example with polar or ionic pendant groups) or ion doped forms. The treatment of layers comprising the semiconductor material of the invention in OLEDs is generally known to those skilled in the art, see, for example, Müller et al, Synth. Metals, 2000, 111-112, 31-34, Alcala, J. Appl. Phys., 2000, 88, 7124-7128; O'Malley et al., Adv. Energy Mater. 2012, 2, 82-86 and references cited therein.

According to another use, the mixtures according to the invention, especially those exhibiting photoluminescent properties, can be used as materials for, for example, light sources of display devices, such as EP 0 889 350 A1 or C. Weder et al., Science, 1998. , 279, 835-837.

Another aspect of the invention pertains to both oxidized and reduced forms of the mixture according to the invention. Loss or acquisition of electrons results in the formation of highly delocalized ion forms with high electrical conductivity. This can occur when exposed to common dopants. Suitable dopants and doping methods are known to those skilled in the art, for example from EP 0 528 662, US 5,198, 153 or WO 96/21659.

Doping methods generally mean the use of an oxidizing or reducing agent in the redox reaction to treat the semiconductor material to form a non-localized ion center in the material, corresponding to the counter ion derived from the applied dopant. Suitable doping methods include, for example, exposure to doping vapor at atmospheric or reduced pressure, electrochemical doping in a solution containing a dopant, contact of a dopant with a quasi-thermally diffused semiconductor material, and dopant passage. Ion implantation of semiconductor materials.

When electrons are used as carriers, suitable dopants are, for example, halogens (e.g., I ₂ , Cl ₂ , Br ₂ , ICl, ICl ₃ , IBr, and IF), Lewis acids (e.g., PF ₅ , AsF). ₅ , SbF ₅ , BF ₃ , BCl ₃ , SbCl ₅ , BBr ₃ and SO ₃ ), protic acid, organic acid or amino acid (eg HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H And ClSO ₃ H), transition metal compounds (such as FeCl ₃ , FeOCl, Fe(ClO ₄ ) ₃ , Fe(4-CH ₃ C ₆ H ₄ SO ₃ ) ₃ , TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , _{NbCl 5, TaCl 5, MoF 5} , MoCl 5, WF 5, WCl 6, UF 6 and LnCl ₃ (wherein Ln is a lanthanoid)), anions (e.g. ^{Cl -, Br -, I -} , I 3 -, HSO ₄ ^- , SO ₄ ^2- , NO ₃ ^- , ClO ₄ ^- , BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , FeCl ₄ ^- , Fe(CN) ₆ ^3- , and anions of various sulfonic acids For example, aryl-SO ₃ ^- ). When a hole is used as a carrier, examples of the dopant are cations (for example, H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ^{+ ,} and Cs ⁺ ), and alkali metals (for example, Li, Na, K, Rb, and Cs). ), alkaline earth metals (such as Ca, Sr and Ba), O ₂ , XeOF ₄ , (NO ₂ ⁺ ) (SbF ₆ ^- ), (NO ₂ ⁺ ) (SbCl ₆ ^- ), (NO ₂ ⁺ ) (BF ₄ ^- ), AgClO ₄ , H ₂ IrCl ₆ , La(NO ₃ ) ₃ . 6H ₂ O, FSO ₂ OOSO ₂ F, Eu, acetylcholine, R ₄ N ⁺ (R is an alkyl group), R ₄ P ⁺ (R is an alkyl group), R ₆ As ⁺ (R is an alkyl group), and R ₃ S ⁺ (R is an alkyl group).

The electrically conductive form of the mixture of the present invention can be used as an organic "metal" in applications including, but not limited to, charge injection layers and ITO planarization layers in OLED applications, films for flat panel displays and touch screens, antistatic films, such as Printed conductive substrates, patterns or traces in electronic applications of printed circuit boards and capacitors.

According to another use, the mixture according to the invention can be used alone or in combination with other materials in an LCD or OLED device or as an alignment layer therein, for example as described in US 2003/0021913. The use of a charge transporting compound according to the present invention increases the conductivity of the alignment layer. When used in an LCD, this increased conductivity can reduce unfavorable residual dc effects in the switchable LCD unit and suppress image sticking, or, for example, in ferroelectric LCDs, by switching the ferroelectric type The residual charge generated by the spontaneous polarization charge of LC. This increased conductivity increases the electroluminescence of the luminescent material when used in an OLED device comprising a luminescent material provided on an alignment layer. Mixtures according to the invention may also be used in or in combination with photoisomerizable compounds and/or chromophores as described in US 2003/0021913 A1.

According to another use, the mixtures according to the invention, in particular their water-soluble derivatives (for example having polar or ionic pendant groups) or ion doped forms, can be used as chemical sensors or as materials for the detection and identification of DNA sequences. Such uses are described, for example, in L. Chen, DW McBranch, H. Wang, R. Helgeson, F. Wudl and DGWhitten, Proc. Natl. Acad. Sci. USA, 1999, 96 , 12287; D. Wang, X. Gong, PS Heeger, F. Rininsland, GC Bazan and AJ Heeger, Proc. Natl . Acad . Sci . USA, 2002, 99 , 49; N. DiCesare, MR Pinot, KSSchanze and JRLakowicz, Langmuir , 2002, 18 , 7785; DTMcQuade, AEPullen, TMSwager, Chem. Rev., 2000, 100 , 2537.

The plural forms of the terms herein are to be interpreted as including the singular, and vice versa, unless the context clearly indicates otherwise.

In the entire description and claims of the specification, the words "comprise" and "contain" and variations of the words (eg, "comprising and comprises") mean "including but not Limited to, and is not intended to (and does not exclude) other components.

It will be appreciated that modifications may be made to the foregoing embodiments of the invention, but are still within the scope of the invention. Each feature disclosed in this specification can be replaced by alternative features that are suitable for the same, equivalent or similar purpose, unless otherwise stated. Therefore, unless expressly stated otherwise, each feature disclosed is only one of the

All of the features disclosed in this specification can be combined in any combination, except at least some combinations of such features and/or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and can be used in any combination. Likewise, the features described in the non-essential combinations can be used separately (not in combination).

In this context, percentages are by weight and temperature is given in ° C unless otherwise stated. The value of the dielectric constant ε ("permittivity") refers to a value obtained at 20 ° C and 1,000 Hz.

The invention will now be described in more detail with reference to the following examples, which The invention is not intended to limit the scope of the invention.

Example 1

Bulk heterojunction organic photovoltaic device for fullerene mixture

An organic photovoltaic (OPV) device was fabricated on a pre-patterned ITO-glass substrate (13 Ω/sq.) commercially available from LUMTEC. The substrate was cleaned in an ultrasonic bath using a common solvent (acetone, isopropanol, deionized water). A layer of commercially available PV-E002 (Merck) was applied as a uniform coating by knife coating at 80 °C. The PV-E002 film was then annealed in air at 100 ° C for 10 minutes and then transferred to a nitrogen atmosphere. An active material solution (ie, polymer + fullerene) was prepared to completely dissolve the solute at 30 mg ^. Cm ^-3 solution concentration. The film was knife coated in a nitrogen atmosphere to achieve an active layer thickness between 50 nm and 800 nm, measured using a profilometer. A short drying period is then experienced to ensure removal of any residual solvent.

Typically, the drawdown film is dried on a hot plate between 70 ° C and 90 ° C for 2 minutes. Next, the device is transferred to an air atmosphere. 0.9 mL of poly(styrenesulfonic acid)-doped conductive polymer poly(ethylenedioxythiophene) [PEDOT:PSS Clevios HTL Solar SCA 246-12 (Heraeus)] was dispersed by spin coating at 1100 rpm and It was uniformly coated on the active layer for 130 seconds. The Ag (100 nm) cathode was then thermally evaporated via a shadow mask to define the cell. Regarding the final step in device fabrication, the devices were each encapsulated in a glass coverslip using UV-cured epoxy glue.

The current-voltage characteristics were measured using a Keithley 2400 SMU while the solar cells were illuminated with 100 mW.cm ^-2 white light by a Newport Solar Simulator. The solar simulator is equipped with an AM1.5G filter. The intensity of the illumination is calibrated using a Si photodiode. All device preparations and characterizations were carried out in a dry nitrogen atmosphere.

Calculate power conversion efficiency using the following formula The above apparatus was prepared using a blend containing a polymer 1 having the structure shown below and a blend of various prior art or fullerenes of the present invention. The characteristics of the blend are shown in Table 1 below. The total solid concentration in the organic solution was 3 wt%. Polymer 1 and its preparation are disclosed in WO 2011/131280.

Condenser C1 is a comparative example containing fullerene PCBM-C60 wherein the ester substituent is methyl butyrate and is not encompassed by Formula F.

Blends 1 and 2 represent an embodiment according to the present invention comprising fullerene PCBC ₆ -C60 wherein the ester substituent is hexyl butyrate and is not encompassed by Formula F.

Initial device properties

The BHJ OPV device was prepared from these blends and the OPV device characteristics were measured as described above.

Table 2 shows the device characteristics of each OPV device comprising a photoactive layer of BHJ formed from the active material (fullerene/polymer) solution of Table 1.

Thus, it can be seen that BHJ containing the fullerene of the present invention having an extended alkyl chain maintains increased device stability after 9 days of AM 1.5G 1 solar simulated solar irradiation (Tables 1 & 2).

Claims (26)

a mixture comprising a conjugated polymer comprising one or more units of formula 1 and one or more units of formula 2 And a substituted fullerene of formula F Wherein each group is independently or independently of each occurrence and has the following meaning R ^13-18 H, a straight or branched alkyl group having 1 to 30 C atoms, wherein one or more CH ₂ groups The group may be O-, -S-, -C(O)-, -C(S)-, -C(O)-O-, -OC(O) in such a manner that the O and/or S atoms are not directly connected to each other. )-, -NR ⁰ -, -SiR ⁰ R ⁰⁰ -, -CF ₂ -, -CHR ⁰ =CR ⁰⁰ -, -CY ¹ =CY ² - or -C≡C-, and one or more of them H The atomic system is optionally replaced by F, Cl, or CN, and C _n is a fullerene composed of n carbon atoms, and the inside thereof randomly captures one or more atoms, o An integer of 1 or a non-integer of >1, R ¹ has an alkyl group of 7 to 20 C atoms, which is straight or branched, and wherein one or more CH ₂ groups may be O and/or S atoms are not mutually The direct connection is optionally via -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, - NR ⁰ -, -C(=O)-NR ⁰ -, -NR ⁰ -C(=O)-, -SiR ⁰ R ⁰⁰ -, -CF ₂ -, -CR ⁰ =CR ⁰⁰ -, -CR ⁰ = N-, -N=N- or -C≡C-substitution, and/or wherein one or more of the H atoms are optionally substituted by F, Cl, or CN, and Ar is selected from the aryl or hetero-formula of formula C1 to C9 An aryl group optionally substituted by one or more identical or different groups L LF, Cl, -CN, or alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or alkoxycarbonyloxy, each having from 1 to 20 C Atom and optionally fluorinated, R ⁰ , R ⁰⁰ H or an alkyl group having 1 to 12 C atoms, Y ¹ , Y ² H, F, Cl or CN, Ad is attached to the fullerene by any connectivity An adduct of C _n , or a combination of adducts, m 0, An integer of 1, or a non-integer of >0. A mixture according to item 1 of the patent application, wherein n is 60 or 70. A mixture according to item 1 of the patent application, wherein m is 0, and o is 1 or 2. A mixture according to claim 1, wherein R ¹ in the formula F represents an alkyl group having 7 to 20 C atoms, wherein one or more CH ₂ groups are optionally subjected to -O-, -C(O) -, -C(O)-O- or -OC(O)-substitution, and one or more of the H atoms are optionally substituted by F. According to the mixture of claim 1 of the patent application, wherein R ^{1 in} formula F is selected from the following formula: Wherein each group independently has the following meaning a, b0 or an integer from 1 to 15, and a+b 5, c, d, e 0 or an integer from 1 to 15, and c + d + e 4, f is an integer from 6 to 15, g 0 or an integer from 1 to 15, R ¹¹ has a linear or branched alkyl group of 5 to 15 C atoms, wherein one or more H atoms are optionally subjected to F Replacement, or, if g 5, R ¹¹ may also represent H, F, CN or an alkyl group having 1 to 4 C atoms, wherein one or more H atoms are optionally substituted by F. A mixture according to claim 1, wherein Ar in the formula F is selected from the group consisting of the formulae C1 and C2, and optionally substituted with one or more groups L as defined in the first item of the patent application. According to the mixture of claim 1 of the patent application, wherein the compound of formula F is selected from the following formula The mixture according to claim 1, wherein the conjugated polymer, in addition to the units of the formulae 1 and 2, further comprises one or more units selected from the group consisting of the following formula: Wherein R ¹¹ and R ¹² are as defined in item 1 of the scope of the patent application. The mixture according to claim 1, wherein the conjugated polymer comprises one or more units of the formula 1a and one or more units of the formula 2a-(D-Sp)-1a-(A-Sp)-2a wherein D Representing a unit of formula 1 as defined in claim 1 of the patent application, A represents a unit of formula 2 as defined in claim 1 of the scope of the patent application, and Sp represents a selected from the group defined in item 8 of the scope of the patent application. formula The unit of Sp1 to Sp16. The mixture according to claim 1, wherein the conjugated polymer has the formula P-[(D-Sp) _x -(A-Sp) _y ] _n - P wherein A, D and Sp are as claimed in the patent scope As defined in 9 items, x represents the molar fraction of the unit (D-Sp), y represents the molar fraction of the unit (A-Sp), and x and y are each independently > 0 and < 1, and x +y=1, and n is an integer >1. The mixture according to claim 1, wherein the conjugated polymer is selected from the following subtypes Wherein R ^11-16 , x, y and n are as defined in items 1 and 10 of the patent application. According to the mixture of claim 11, wherein R ¹¹ and R ¹² in the formulas Sp1 to Sp16, P1 and P2 are H, and R ¹³ and R ¹⁴ in the formulas 1, P1 and P2 are different from H, and R ¹⁵ and R ¹⁶ in P1 and P2 are H, and R ¹⁷ and R ¹⁸ in the formulas 2, P1 and P2 are different from H. The mixture according to any one of claims 1 to 12, wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R in the formula 1, 2, Sp1-Sp16, P1 and P2 ¹⁷ and R ¹⁸ , when different from H, are selected from the group consisting of a group consisting of a linear or branched alkyl group having 1 to 30, preferably 1 to 20, C atoms, optionally The fluorination is carried out by a linear or branched alkyl group having 1 to 30, preferably 1 to 20 C atoms, an alkoxy group or a sulfanylalkyl group, and having 2 to 30, preferably A group consisting of a linear or branched alkylcarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyl group of 2 to 20 C carbon atoms, each of which is unsubstituted or substituted with one or more F atoms. The mixture according to claim 1, wherein the conjugated polymer is selected from the group consisting of the formula PT R ³¹ -chain-R ³² PT wherein "chain" means a formula P as defined in claim 10 or 11 a polymer chain of P1 or P2, and R ³¹ and R ³² independently of one another have one of the meanings of R ¹¹ as defined in claim 1 of the patent application, or independently of each other, H, F, Br, Cl , I, -CH ₂ Cl, -CHO, -CR'=CR" ₂ , -SiR'R"R"', -SiR'X'X", -SiR'R"X', -SnR'R"R "', -BR'R", -B(OR')(OR"), -B(OH) ₂ , -O-SO ₂ -R', -C≡CH, -C≡C-SiR' ₃ , -ZnX' or a capping group, X' and X" represent a halogen, and R', R" and R'" independently of one another have one of the meanings of R ⁰ given in the first item of the patent application, and Two of R', R" and R'" may also form, together with the individual heteroatoms to which they are attached, a cyclodecyl, cyclostannyl, cycloborane or cyclic boronate having from 2 to 20 C atoms. Group. The mixture according to claim 1 of the patent application, which additionally comprises one or more selected from the group consisting of semiconductor, charge transport, hole transport, electron transport, hole blocking, electron blocking, conducting, light guiding, photoactive and luminescent properties. Or a compound of a compound. A semiconductor, charge transport, conductive, photoconductive, photoactivated, thermoelectric or luminescent material comprising or consisting of a mixture according to any one of claims 1 to 14. Use of a mixture according to any one of claims 1 to 15 for an organic electronic (OE) device, or a component in the OE device, or a combination comprising the OE device or the component Used as a semiconductor, charge transport, conductive, light guide, photoactivated, thermoelectric or luminescent material. A blend comprising the mixture according to any one of claims 1 to 15 and additionally comprising one or more solvents selected from the group consisting of organic solvents. An OE device, or a component thereof, or a device or component thereof The combination is prepared using a blend according to claim 18 of the patent application. An OE device, or a component thereof, or a combination comprising the same, comprising a mixture according to any one of claims 1 to 15 or a semiconducting, charge transfer according to item 16 of the patent application. , conductive, light-guided, photoactivated or luminescent materials. An OE device according to claim 20, which is an optical, photoelectric, electronic, photoactivated, electroluminescent or photoluminescent device. According to the OE device of claim 21, it is an airport effect transistor (OFET), an organic thin film transistor (OTFT), an organic light emitting diode (OLED), an organic light emitting transistor (OLET), an organic photovoltaic device. Device (OPV), Organic Photodetector (OPD), Organic Solar Cell, Dye Sensitized Solar Cell (DSSC), Perovskite Based Solar Cell, Laser Diode, Schottky Diode, Light Conductor, photodetector or thermoelectric device. The OE device according to claim 20, wherein the component is a charge injection layer, a charge transport layer, an intermediate layer, a planarization layer, an antistatic film, a polymer electrolyte film (PEM), a conductive substrate, or a conductive pattern. An OE device according to claim 20, wherein the assembly is an integrated circuit (IC), a radio frequency identification (RFID) tag, a security mark or a security device, a flat panel display, a backlight, an electrophotographic device, an electrophotographic recording Device, organic memory device, sensor device, biosensor or biochip. According to the OE device of claim 22, which is a block Material heterojunction (BHJ) OPV device, or inverted BHJ OPV device. A BHJ comprising or formed from a mixture according to any one of claims 1 to 15.