Patent Application
20230073741
The invention relates to a novel composition comprising n-type organic semiconducting (OSC) polymers and p-type OSCs, to its use as organic semiconductors in, or for the preparation of, organic electronic (OE) devices, especially organic photovoltaic (OPV) devices, perovskite-based solar cell (PSC) devices, organic photo-detectors (OPD), organic field effect transistors (OFET) and organic light emitting diodes (OLED), and to OE, OPV, PSC, OPD, OFET and OLED devices comprising the compositions.
In recent years, there has been development of organic semiconducting (OSC) materials in order to produce more versatile, lower cost electronic devices. Such materials find application in a wide range of devices or apparatus, including organic field effect transistors (OFETs), organic light emitting diodes (OLEDs), organic photodetectors (OPDs), organic photovoltaic (OPV) cells, sensors, memory elements and logic circuits to name just a few. The organic semiconducting materials are typically present in the electronic device in the form of a thin layer, for example of between 50 and 300 nm thickness.
One particular area of importance is organic photovoltaics (OPV). Conjugated polymers have found use in OPVs as they allow devices to be manufactured by solution-processing techniques such as spin casting, dip coating or ink jet printing. Solution processing can be carried out cheaper and on a larger scale compared to the evaporative techniques used to make inorganic thin film devices. Currently, polymer based photovoltaic devices are achieving efficiencies above 10%.
Organic photodetectors (OPDs) are a further particular area of importance, for which conjugated light-absorbing polymers offer the hope of allowing efficient devices to be produced by solution-processing technologies, such as spin casting, dip coating or ink jet printing, to name a few only.
Another particular area of importance are OFETs. The performance of OFET devices is principally based upon the charge carrier mobility of the semiconducting material and the current on/off ratio, so the ideal semiconductor should have a low conductivity in the off state, combined with high charge carrier mobility (>1×10−3 cm2V−1s−1) . In addition, it is important that the semiconducting material is stable to oxidation i.e. it has a high ionisation potential, as oxidation leads to reduced device performance. Further requirements for the semiconducting material are good processibility, especially for large-scale production of thin layers and desired patterns, and high stability, film uniformity and integrity of the organic semiconductor layer.
The photosensitive layer in an OPV or OPD device is usually composed of at least two materials, a p-type semiconductor, which is typically a conjugated polymer, an oligomer or a defined molecular unit, and an n-type semiconductor, which is typically a fullerene or substituted fullerene, graphene, a metal oxide, or quantum dots.
However, the OSC materials disclosed in prior art for use in OE devices have several drawbacks. They are often difficult to synthesize or purify (fullerenes), and/or do not absorb light strongly in the near IR spectrum >700 nm. In addition, other OSC materials do not often form a favourable morphology and/or donor phase miscibility for use in organic photovoltaics or organic photodetectors.
Therefore there is still a need for OSC materials for use in OE devices like OPVs, PSCs, OPDs and OFETs, which have advantageous properties, in particular good processability, a high solubility in organic solvents, good structural organization and film-forming properties. In addition, the OSC materials should be easy to synthesize, especially by methods suitable for mass production. For use in OPV cells, the OSC materials should especially have a low bandgap, which enables improved light harvesting by the photoactive layer and can lead to higher cell efficiencies, high stability and long lifetime. For use in OFETs the OSC materials should especially have high charge-carrier mobility, high on/off ratio in transistor devices, high oxidative stability and long lifetime.
In particular there is a need for n-type OSC polymers. These can be used for example in all-polymer photodiodes or solar cells, where they enable better control of the morphology thus leading to higher power conversion efficiency (PCE) and better thermal stability of the device. However, despite the recent progress of organic photovoltaics there is still a lack of n-type polymers showing satisfactory performance, like for example sufficiently high PCE in OPV devices and sufficiently high external quantum efficiency (EQE) in OPD devices.
It was an aim of the present invention to provide new OSC polymers, especially n-type polymers, which can overcome the drawbacks of the OSCs from prior art, and which provide one or more of the above-mentioned advantageous properties, especially easy synthesis by methods suitable for mass production, good processibility, high stability, long lifetime in OE devices, good solubility in organic solvents, high charge carrier mobility, and a low bandgap. Another aim of the invention was to extend the pool of OSC polymer materials and n-type polymers available to the expert. Other aims of the present invention are immediately evident to the expert from the following detailed description.
The inventors of the present invention have found that these aims can be achieved by providing semiconducting materials as described hereinafter. These materials are based on polymers comprising one or more polycyclic units of formula I as shown below and where the polymer shows n-type behaviour.
In prior art there is a report [J. Mater. Chem. A, 2016, 4, 5810] of the use of an indacenodithiophene-naphthalene diimide copolymer P(IDT-NDI) as shown below as an acceptor in an OPV cell. However, compositions as disclosed and claimed hereinafter have not been reported in prior art.
The invention relates to a composition comprising a p-type organic semiconductor and an n-type organic semiconductor, wherein the n-type organic semiconductor is a conjugated polymer (hereinafter also being shortly referred to as “n-type polymer”) comprising one or more repeating units of formula I
and optionally comprising one or more divalent repeating units Ar6,
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
and the pair of R1 and R2, together with the C, Si or Ge atom to which they are attached, may also form a spiro group with 5 to 20 ring atoms which is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
wherein the conjugated polymer comprises at least one unit of formula I having electron acceptor properties and/or at least one unit Ar6 having electron acceptor properties, and wherein the conjugated polymer does not contain a naphthalene-1,4,5,8-tetracarboxy diimide moiety or a perylene-3,4,9,10-tetracarboxy diimide moiety.
The invention further relates to novel conjugated polymers comprising a unit of formula I and at least one unit Ar6 and being as defined above and below.
The invention further relates to a semiconducting material, formulation, polymer blend, device or component of a device comprising a composition according to the present invention, and preferably further comprising one or more compounds having electron donor or electron acceptor properties.
The invention further relates to a composition according to the present invention further comprising one or more additional compounds selected from compounds having one or more of semiconducting, charge transport, hole or electron transport, hole or electron blocking, electrically conducting, photoconducting or light emitting properties.
The invention further relates to a composition according to the present invention further comprising a second n-type semiconductor, which is preferably a fullerene or fullerene derivative, a non-fullerene acceptor small molecule, or an n-type conjugated polymer.
The invention further relates to a formulation comprising a composition according to the present invention, and further comprising one or more solvents, preferably selected from organic solvents.
The invention further relates to an organic semiconducting formulation according to the present invention further comprising one or more organic binders or precursors thereof, preferably having a permittivity ε at 1,000 Hz and 20° C. of 3.3 or less, and optionally one or more solvents preferably selected from organic solvents.
The invention further relates to an optical, electronic, optoelectronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which is prepared using a formulation according to the present invention.
The invention further relates to the use of a composition according to the present invention as semiconducting, charge transport, electrically conducting, photoconducting or light emitting material, or in an optical, electronic, optoelectronic, electroluminescent or photoluminescent device, or in a component of such a device or in an assembly comprising such a device or component.
The invention further relates to a semiconducting, charge transport, electrically conducting, photoconducting or light emitting material comprising a composition according to the present invention.
The invention further relates to an optical, electronic, optoelectronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a composition according to the present invention, or comprises a semiconducting, charge transport, electrically conducting, photoconducting or light emitting material according to the present invention.
The optical, electronic, optoelectronic, electroluminescent and photoluminescent deviced include, without limitation, organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, dye-sensitized solar cells (DSSC), perovskite-based solar cells (PSC), laser diodes, Schottky diodes, photoconductors and photodetectors.
Preferred devices are OFETs, OTFTs, OPVs, PSCs, OPDs and OLEDs, in particular OTFTs, PSCs, OPDs and bulk heterojunction (BHJ) OPVs or inverted BHJ OPVs.
The component of the above devices includes, without limitation, charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.
The assembly comprising such a device or component includes, without limitation, integrated circuits (IC), radio frequency identification (RFID) tags or security markings or security devices containg them, flat panel displays or backlights thereof, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips.
In addition, the compositions and formulations of the present invention can be used as electrode materials in batteries and in components or devices for detecting and discriminating DNA sequences.
The invention further relates to a bulk heterojunction which comprises, or is being formed from, a composition according to the present invention.
The invention further relates to a bulk heterojunction (BHJ) OPV or OPD device or inverted BHJ OPV or OPD device, comprising such a bulk heterojunction.
As used herein “naphthalene-1,4,5,8-tetracarboxy diimide” means the following moiety
and “perylene-3,4,9,10-tetracarboxy diimide” means the following moiety
wherein R denotes any substituent and the benzene rings may be further substituted.
As used herein, the terms “indaceno-type group” and “indaceno group” mean a group comprising two cyclopentadiene rings, or heterocyclic or vinylidene derivatives thereof, that are fused to a central aromatic or heteroaromatic aromatic ring Ar, and which can have cis- or trans-configuration, as exemplarily shown below
wherein U is e.g. C, Si or Ge and R is a carbyl or hydrocarbyl group.
In the units of formula I adjacent rings Ar1-5 are understood to be fused, i.e. having at least two atoms and one covalent bond in common. In the rings Ar1 and Ar2 of formula A1 and A2 the pi-electrons may also be delocalised into adjacent rings Ar3, Ar4 or Ar5, so that e.g. the following structure
may also include e.g. its mesomeric structure
As used herein, the terms “donor” or “donating” and “acceptor” or “accepting” will be understood to mean an electron donor or electron acceptor, respectively. “Electron donor” will be understood to mean a chemical entity that donates electrons to another compound or another group of atoms of a compound. “Electron acceptor” will be understood to mean a chemical entity that accepts electrons transferred to it from another compound or another group of atoms of a compound. See also International Union of Pure and Applied Chemistry, Compendium of Chemical Technology, Gold Book, Version 2.3.2, 19. August 2012, pages 477 and 480.
As used herein, the term “donor unit” will be understood to mean a unit, preferably a conjugated arylene or heteroarylene unit, which has an electron donating or electron pushing property towards a neighboured conjugated unit. The term “acceptor unit” will be understood to mean a unit, preferably a conjugated arylene or heteroarylene unit, which has an electron accepting or electron withdrawing property towards a neighboured conjugated unit. The term “spacer unit” will be understood to mean a unit which can be conjugated or non-conjugated and is located between a donor and an acceptor unit, and is preferably selected such that it does not have electron accepting property towards a neighboured donor unit.
As used herein, the term “spacer unit” will be understood to mean a unit, preferably a conjugated arylene or heteroarylene unit, which is located between two donor units, or between two acceptor units, or between an acceptor unit and a donor unit, such that said donor and acceptor units are not connected directly with each other.
As used herein, the term “n-type” or “n-type semiconductor” will be understood to mean an extrinsic semiconductor in which the conduction electron density is in excess of the mobile hole density, and the term “p-type” or “p-type semiconductor” will be understood to mean an extrinsic semiconductor in which mobile hole density is in excess of the conduction electron density (see also, J. Thewlis, Concise Dictionary of Physics, Pergamon Press, Oxford, 1973).
As used herein, the term “conjugated” will be understood to mean a compound (for example a polymer) that contains mainly C atoms with sp2-hybridization (or optionally also sp-hybridization), and wherein these C atoms may also be replaced by hetero atoms. In the simplest case this is for example a compound with alternating C—C single and double (or triple) bonds, but is also inclusive of compounds with aromatic units like for example 1,4-phenylene. The term “mainly” in this connection will be understood to mean that a compound with naturally (spontaneously) occurring defects, or with defects included by design, which may lead to interruption of the conjugation, is still regarded as a conjugated compound.
As used herein, the term “polymer” will be understood to mean a molecule of high relative molecular mass, the structure of which essentially comprises multiple repetitions of units derived, actually or conceptually, from molecules of low relative molecular mass (Pure Appl. Chem., 1996, 68, 2291). The term “oligomer” will be understood to mean a molecule of intermediate relative molecular mass, the structure of which essentially comprises a small plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass (Pure Appl. Chem., 1996, 68, 2291). In a preferred meaning as used herein present invention a polymer will be understood to mean a compound having >1, i.e. at least 2 repeat units, preferably ≥5, very preferably ≥10, repeat units, and an oligomer will be understood to mean a compound with >1 and <10, preferably <5, repeat units.
Further, as used herein, the term “polymer” will be understood to mean a molecule that encompasses a backbone (also referred to as “main chain”) of one or more distinct types of repeat units (the smallest constitutional unit of the molecule) and is inclusive of the commonly known terms “oligomer”, “copolymer”, “homopolymer”, “random polymer” and the like. Further, it will be understood that the term polymer is inclusive of, in addition to the polymer itself, residues from initiators, catalysts and other elements attendant to the synthesis of such a polymer, where such residues are understood as not being covalently incorporated thereto. Further, such residues and other elements, while normally removed during post polymerization purification processes, are typically mixed or co-mingled with the polymer such that they generally remain with the polymer when it is transferred between vessels or between solvents or dispersion media.
As used herein, in a formula showing a polymer or a repeat unit an asterisk (*) will be understood to mean a chemical linkage, usually a single bond, to an adjacent unit or to a terminal group in the polymer backbone. In a ring, like for example a benzene or thiophene ring, an asterisk (*) will be understood to mean a C atom that is fused to an adjacent ring.
As used herein, in a formula showing a ring, a polymer or a repeat unit a dashed line () will be understood to mean a single bond.
As used herein, the terms “repeat unit”, “repeating unit” and “monomeric unit” are used interchangeably and will be understood to mean the constitutional repeating unit (CRU), which is the smallest constitutional unit the repetition of which constitutes a regular macromolecule, a regular oligomer molecule, a regular block or a regular chain (Pure Appl. Chem., 1996, 68, 2291). As further used herein, the term “unit” will be understood to mean a structural unit which can be a repeating unit on its own, or can together with other units form a constitutional repeating unit.
As used herein, a “terminal group” will be understood to mean a group that terminates a polymer backbone. The expression “in terminal position in the backbone” will be understood to mean a divalent unit or repeat unit that is linked at one side to such a terminal group and at the other side to another repeat unit. Such terminal groups include endcap groups, or reactive groups that are attached to a monomer forming the polymer backbone which did not participate in the polymerization reaction, like for example a group having the meaning of RE1 or RE2 as defined below.
As used herein, the term “endcap group” will be understood to mean a group that is attached to, or replacing, a terminal group of the polymer backbone. The endcap group can be introduced into the polymer by an endcapping process. Endcapping can be carried out for example by reacting the terminal groups of the polymer backbone with a monofunctional compound (“endcapper”) like for example an alkyl- or arylhalide, an alkyl- or arylstannane or an alkyl- or arylboronate. The endcapper can be added for example after the polymerization reaction.
Alternatively the endcapper can be added in situ to the reaction mixture before or during the polymerization reaction. In situ addition of an endcapper can also be used to terminate the polymerization reaction and thus control the molecular weight of the forming polymer. Typical endcap groups are for example H, phenyl and lower alkyl.
As used herein, the term “small molecule” will be understood to mean a monomeric compound which typically does not contain a reactive group by which it can be reacted to form a polymer, and which is designated to be used in monomeric form. In contrast thereto, the term “monomer” unless stated otherwise will be understood to mean a monomeric compound that carries one or more reactive functional groups by which it can be reacted to form a polymer.
As used herein, the term “leaving group” will be understood to mean an atom or group (which may be charged or uncharged) that becomes detached from an atom in what is considered to be the residual or main part of the molecule taking part in a specified reaction (see also Pure Appl. Chem., 1994, 66, 1134).
As used herein, unless stated otherwise the molecular weight is given as the number average molecular weight Mn or weight average molecular weight Mw, which is determined by gel permeation chromatography (GPC) against polystyrene standards in eluent solvents such as tetrahydrofuran, trichloromethane (TCM, chloroform), chlorobenzene or 1,2,4-trichloro-benzene. Unless stated otherwise, chlorobenzene is used as solvent. The degree of polymerization, also referred to as total number of repeat units, n, will be understood to mean the number average degree of polymerization given as n=Mn/MU, wherein Mn is the number average molecular weight and MU is the molecular weight of the single repeat unit, see J. M. G. Cowie, Polymers: Chemistry & Physics of Modern Materials, Blackie, Glasgow, 1991.
As used herein, the term “carbyl group” will be understood to mean any monovalent or multivalent organic moiety which comprises at least one carbon atom either without any non-carbon atoms (like for example —C≡C—), or optionally combined with at least one non-carbon atom such as B, N, O, S, P, Si, Se, As, Te or Ge (for example carbonyl etc.).
As used herein, the term “hydrocarbyl group” will be understood to mean a carbyl group that does additionally contain one or more H atoms and optionally contains one or more hetero atoms like for example B, N, O, S, P, Si, Se, As, Te or Ge.
As used herein, the term “hetero atom” will be understood to mean an atom in an organic compound that is not a H- or C-atom, and preferably will be understood to mean B, N, O, S, P, Si, Se, Sn, As, Te or Ge.
A carbyl or hydrocarbyl group comprising a chain of 3 or more C atoms may be straight-chain, branched and/or cyclic, and may include spiro-connected and/or fused rings.
Preferred carbyl and hydrocarbyl groups include alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has up to 40, preferably up to 25, very preferably up to 18 C atoms, furthermore optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 C atoms, furthermore alkylaryloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy, each of which is optionally substituted and has 1 to 40, preferably 6 to 40 C atoms, wherein each of these groups optionally contains one or more hetero atoms, preferably selected from B, N, O, S, P, Si, Se, As, Te and Ge.
Further preferred carbyl and hydrocarbyl group include for example: a C1-C40 alkyl group, a C1-C40 fluoroalkyl group, a C1-C40 alkoxy or oxaalkyl group, a C2-C40 alkenyl group, a C2-C40 alkynyl group, a C3-C40 allyl group, a C4-C40 alkyldienyl group, a C4-C40 polyenyl group, a C2-C40 ketone group, a C2-C40 ester group, a C6-C18 aryl group, a C6-C40 alkylaryl group, a C6-C40 arylalkyl group, a C4-C40 cycloalkyl group, a C4-C40 cycloalkenyl group, and the like. Preferred among the foregoing groups are a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 allyl group, a C4-C20 alkyldienyl group, a C2-C20 ketone group, a C2-C20 ester group, a C6-C12 aryl group, and a C4-C20 polyenyl group, respectively.
Also included are combinations of groups having carbon atoms and groups having hetero atoms, like e.g. an alkynyl group, preferably ethynyl, that is substituted with a silyl group, preferably a trialkylsilyl group.
The carbyl or hydrocarbyl group may be an acyclic group or a cyclic group. Where the carbyl or hydrocarbyl group is an acyclic group, it may be straight-chain or branched. Where the carbyl or hydrocarbyl group is a cyclic group, it may be a non-aromatic carbocyclic or heterocyclic group, or an aryl or heteroaryl group.
A non-aromatic carbocyclic group as referred to above and below is saturated or unsaturated and preferably has 4 to 30 ring C atoms. A non-aromatic heterocyclic group as referred to above and below preferably has 4 to 30 ring C atoms, wherein one or more of the C ring atoms are each optionally replaced by a hetero atom, preferably selected from N, O, P, S, Si and Se, or by a —S(O)— or —S(O)2— group. The non-aromatic carbo- and heterocyclic groups are mono- or polycyclic, may also contain fused rings, preferably contain 1, 2, 3 or 4 fused or unfused rings, and are optionally substituted with one or more groups L.
L is selected from F, Cl, —CN, —NO2, —NC, —NCO, —NCS, —OCN, —SCN, —R0, —OR0, —SR0, —C(═O)X0, —C(═O)R0, —C(═O)—OR0, —O—C(═O)—R0, —NH2, —NHR0, —NR0R00, —C(═O)NHR0, —C(═O)NR0R00, —SO3R0, —SO2R0, —OH, —CF3, —SF5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30, preferably 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, wherein X0 is halogen, preferably F or Cl, and R0, R00 each independently denote H or straight-chain or branched alkyl with 1 to 20, preferably 1 to 12 C atoms that is optionally fluorinated.
Preferably L is selected from F, —CN, R0, —OR0, —SR0, —C(═O)—R0, —C(═O)—OR0, —O—C(═O)—R0, —O—C(═O)—OR0, —C(═O)—NHR0 and —C(═O)—NR0R00 .
Further preferably L is selected from F or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl, fluoroalkoxy, alkylcarbonyl, alkoxycarbonyl, with 1 to 16 C atoms, or alkenyl or alkynyl with 2 to 16 C atoms.
Preferred non-aromatic carbocyclic or heterocyclic groups are tetrahydrofuran, indane, pyran, pyrrolidine, piperidine, cyclopentane, cyclohexane, cycloheptane, cyclopentanone, cyclohexanone, dihydro-furan-2-one, tetrahydro-pyran-2-one and oxepan-2-one.
An aryl group as referred to above and below preferably has 4 to 30, very preferably 5 to 20, ring C atoms, is mono- or polycyclic and may also contain fused rings, preferably contains 1, 2, 3 or 4 fused or unfused rings, and is optionally substituted with one or more groups L as defined above.
A heteroaryl group as referred to above and below preferably has 4 to 30, very preferably 5 to 20, ring C atoms, wherein one or more of the ring C atoms are replaced by a hetero atom, preferably selected from N, O, S, Si and Se, is mono- or polycyclic and may also contain fused rings, preferably contains 1, 2, 3 or 4 fused or unfused rings, and is optionally substituted with one or more groups L as defined above.
An arylalkyl or heteroarylalkyl group as referred to above and below preferably denotes —(CH2)a-aryl or —(CH2)a-heteroaryl, wherein a is an integer from 1 to 6, preferably 1, and “aryl” and “heteroaryl” have the meanings given above and below. A preferred arylalkyl group is benzyl which is optionally substituted by L.
As used herein, “arylene” will be understood to mean a divalent aryl group, and “heteroarylene” will be understood to mean a divalent heteroaryl group, including all preferred meanings of aryl and heteroaryl as given above and below.
Preferred aryl and heteroaryl groups are phenyl in which, in addition, one or more CH groups may each be replaced by N, naphthalene, thiophene, selenophene, thienothiophene, dithienothiophene, fluorene and oxazole, all of which can be unsubstituted, mono- or polysubstituted with L as defined above. Very preferred aryl and heteroaryl groups are selected from phenyl, pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably 2-selenophene, 2,5-dithiophene-2′,5′-diyl, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, furo[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, indole, isoindole, benzo[b]furan, benzo[b]thiophene, benzo[1,2-b,4,5-b′]dithiophene, benzo[2,1-b;3,4-b′]dithiophene, quinole, 2-methylquinole, isoquinole, quinoxaline, quinazoline, benzotriazole, benzimidazole, benzothiazole, benzisothiazole, benzisoxazole, benzoxadiazole, benzoxazole, benzothiadiazole, 4H-cyclopenta[2,1-b,3,4-b′]dithiophene, 7H-3,4-dithia-7-sila-cyclopenta[a]pentalene, all of which can be unsubstituted, mono- or polysubstituted with L as defined above. Further examples of aryl and heteroaryl groups are those selected from the groups shown hereinafter.
An alkyl group or an alkoxy group, i.e., where the terminal CH2 group is replaced by —O—, can be straight-chain or branched. Particularly preferred straight-chains have 2, 3, 4, 5, 6, 7, 8, 12 or 16 carbon atoms and accordingly denote preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl or hexadecyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, dodecoxy or hexadecoxy, furthermore methyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, tridecoxy or tetradecoxy, for example.
An alkenyl group, i.e., wherein one or more CH2 groups are each replaced by —CH═CH— can be straight-chain or branched. It is preferably straight-chain, has 2 to 10 C atoms and accordingly is preferably vinyl, prop-1-, or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.
Especially preferred alkenyl groups are C2-C7-1E-alkenyl, C4-C7-3E-alkenyl, C5-C7-4-alkenyl, C6-C7-5-alkenyl and C7-6-alkenyl, in particular C2-C7-1E-alkenyl, C4-C7-3E-alkenyl and C5-C7-4-alkenyl. Examples for 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 and the like. Groups having up to 5 C atoms are generally preferred.
An oxaalkyl group, i.e., where one CH2 group is replaced by —O—, can be straight-chain. Particularly preferred straight-chains are 2-oxapropyl (=methoxymethyl), 2-(=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-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or 9-oxadecyl, for example.
In an alkyl group wherein one CH2 group is replaced by —O— and one CH2 group is replaced by —C(O)—, these radicals are preferably neighboured. Accordingly, these radicals together form a carbonyloxy group —C(O)—O— or an oxycarbonyl group —O—C(O)—. Preferably this group is straight-chain and has 2 to 6 C atoms. It is accordingly preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl or 4-(methoxycarbonyl)-butyl.
An alkyl group wherein two or more CH2 groups are replaced by —O— and/or —C(O)O— can be straight-chain or branched. It is preferably straight-chain and has 3 to 12 C atoms. Accordingly, 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-nonyl, 10,10-bis-carboxy-decyl, 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 or 5,5-bis-(ethoxycarbonyl)-hexyl.
A thioalkyl group, i.e., where one CH2 group is replaced by —S—, is preferably straight-chain thiomethyl (—SCH3), 1-thioethyl (—SCH2CH3), 1-thiopropyl (═—SCH2CH2CH3), 1-(thiobutyl), 1-(thiopentyl), 1-(thiohexyl), 1-(thioheptyl), 1-(thiooctyl), 1-(thiononyl), 1-(thiodecyl), 1-(thioundecyl) or 1-(thiododecyl), wherein preferably the CH2 group adjacent to the sp2 hybridized vinyl carbon atom is replaced.
A fluoroalkyl group can be perfluoroalkyl CiF2i+1, wherein i is an integer from 1 to 15, in particular CF3, C2F5, C3F7, C4F9, C5F11, C6F13, C7F15 or C8F17, very preferably C6F13, or partially fluorinated alkyl, preferably with 1 to 15 C atoms, in particular 1,1-difluoroalkyl, all of the aforementioned being straight-chain or branched.
Preferably “fluoroalkyl” means a partially fluorinated (i.e. not perfluorinated) alkyl group.
Alkyl, alkoxy, alkenyl, oxaalkyl, thioalkyl, carbonyl and carbonyloxy groups can be achiral or chiral groups. Particularly preferred chiral groups are 2-butyl (=1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 3,7-dimethyloctyl, 3,7,11-trimethyldodecyl, 2-propylpentyl, in particular 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methyl-pentoxy, 2-ethyl-hexoxy, 2-butyloctoxyo, 2-hexyldecoxy, 2-octyldodecoxy, 3,7-dimethyloctoxy, 3,7,11-trimethyldodecoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methyl-pentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methoxy-octoxy, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxy-carbonyl, 2-methylbutyryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy, 2-chloro-propionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methyl-valeryl-oxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxa-hexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl and 2-fluoromethyloctyloxy for example. Very preferred are 2-methylbutyl, 2-ethylhexyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 3,7-dimethyloctyl, 3,7,11-trimethyldodecyl, 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 substituents on an aryl or heteroaryl ring are independently of each other selected from primary, secondary or tertiary alkyl, alkoxy, oxaalkyl, thioalkyl, alkylcarbonyl or alkoxycarbonyl with 1 to 30 C atoms, wherein one or more H atoms are each optionally replaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated, alkoxylated, alkylthiolated or esterified and has 4 to 30, preferably 5 to 20, ring atoms. Further preferred substituents are selected from the group consisting of the following formulae
wherein RSub1-3 each denote L as defined above and below and where at least, preferably all, of RSub1-3 is alkyl, alkoxy, oxaalkyl, thioalkyl, alkyl-carbonyl or alkoxycarbonyl with up to 24 C atoms, preferably up to 20 C atoms, that is optionally fluorinated, and wherein the dashed line denotes the link to the ring to which these groups are attached. Very preferred among these substituents are those wherein all RSub1-3 subgroups are identical.
As used herein, if an aryl(oxy) or heteroaryl(oxy) group is “alkylated or alkoxylated”, this means that it is substituted with one or more alkyl or alkoxy groups having from 1 to 24 C-atoms and being straight-chain or branched and wherein one or more H atoms are each optionally substituted by an F atom.
Above and below, Y1 and Y2 are independently of each other H, F, Cl or CN.
As used herein, —CO—, —C(═O)— and —C(O)— will be understood to mean a carbonyl group, i.e. a group having the structure
As used herein, C═CR1R2 will be understood to mean a group having the structure
As used herein, “halogen” includes F, Cl, Br or I, preferably F, Cl or Br. A halogen atom that represents a substituent on a ring or chain is preferably F or Cl, very preferably F. A halogen atom that represents a reactive group in a monomer or an intermediate is preferably Br or I.
Above and below, the term “mirror image” means a moiety that can be obtained from another moiety by flipping it vertically or horizontally across an external symmetry plane or a symmetry plane extending through the moiety. For example the moiety
also includes the mirror images
The n-type polymers used in a composition according to the present invention are easy to synthesize and exhibit advantageous properties. They show good processibility for the device manufacture process, high solubility in organic solvents, and are especially suitable for large scale production using solution processing methods.
The synthesis of the repeating units of formula I and polymers comprising them can be achieved based on methods that are known to the skilled person and described in the literature, as will be further illustrated herein.
Preferred groups Ar1 and Ar2 in formula I are on each occurrence identically or differently selected from the following formulae and their mirror images
Especially preferred groups Ar1 and Ar2 are selected from formulae A1a and A2a.
A first preferred embodiment of the present invention relates to units of formula I wherein k=0.
Preferred units of formula I according to this first preferred embodiment are selected from the following subformula
wherein U1 Ar4 and Ar5, independently of each other and on each occurrence identically or differently, have the meanings given in formula I or one of the preferred meanings given above and below.
Preferred units of formula I1 are those wherein U1 denotes CR1R2.
In the units of formula I where k>1 the groups Ar1 and Ar2 can be selected such that the resulting indaceno-type groups have trans- or cis-configuration.
A second preferred embodiment of the present invention relates to units of formula I wherein k>0, preferably 1, 2 or 3, and the indaceno-type groups have an all-trans-configuration, i.e. one of the two groups Ar1 and Ar2 that are fused to the same group Ar3 is of formula A1 and the other is of formula A2, as exemplarily illustrated below.
Preferred units of formula I according to this second preferred embodiment are selected from the following subformulae
wherein U1, U2, Ar3, Ar4 and Ar5, independently of each other and on each occurrence identically or differently, have the meanings given in formula I or one of the preferred meanings given above and below.
Preferred units of formula 12-14 are those wherein all of the groups U1 and U2 denote CR1R2.
A third preferred embodiment of the present invention relates to units of formula I wherein k>0, preferably 1, 2 or 3, and at least one, preferably all, indaceno-type groups have cis-configuration, i.e. the groups Ar1 and Ar2 that are fused to the same group Ar3 are both of formula A1 or both of formula A2, as exemplarily illustrated below.
This third preferred embodiment includes units of formula I having an “all-cis” configuration as exemplarily shown in formula I5 and I6 below, and units of formula I including both trans-configuration and cis-configuration, as exemplarily shown in formula I7 below.
Preferred units of formula I according to this third preferred embodiment are selected from the following subformulae
wherein U1, U2, Ar3, Ar4 and Ar5, independently of each other and on each occurrence identically or differently, have the meanings given in formula I or one of the preferred meanings given above and below.
Preferred units of formula 15-17 are those wherein all groups U1 and U2 denote CR1R2.
Especially preferred are units of formula I1, I2, I3 and I4, very preferred those of formula I1 and I2.
Preferred groups Ar3 in formula I, I2-I7 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
Preferred groups Ar3 are selected from formulae A3b, A3d, A3e and A3t, very preferably from formulae A3b and A3d.
Further preferred groups Ara are selected from formula A3d wherein R5 and R6 denote F.
Further preferred groups Ar3 are selected from formulae A3e and A3f wherein R5 and R6 are different from H.
Preferred groups Ar4 in formula I, I1-I7 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
wherein W1, W2, W3 and R5-8 have the meanings given above, V1 denotes CR5 or N, and R9 has one of the meanings given for R5.
Preferred groups Ar4 are selected from formulae A4a, A4b, A4c, A4d, A4f, A4g, A4h, A4i, A4k, A4l, A4m, A4n, A4o, A4p, A4q, A4u and A4v, very preferably from formula A4a, A4b, A4c, A4d, A4l, A4m, A4n, A4o, A4p, A4q, A4u and A4v.
Further preferred groups Ar4 are selected from formulae A4r and A4s wherein R5 and R6 are different from H.
Preferred groups Ar5 in formula I, I1-I7 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
wherein W1, W2, W3, V1 and R5-9 have the meanings given above,
Preferred groups Ar5 are selected from formulae A5a, A5b, A5c, A5d, A5f, A5g, A5h, A5i, A5k, A5l, A5m, A5n, A5o, A5p, A5q, A5u and A5v, very preferably from formula A5a, A5b, A5c, A5d, A5l, A5m, A5n, A5o, A5p, A5q, A5u and A5v.
Further preferred groups Ar5 are selected from formulae A5r and A5s wherein R5 and R6 are different from H.
Very preferred groups Ara in formula I and I2-I7 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
wherein R5-8 have the meanings given above and below.
Very preferred groups Ar3 are selected from formulae A3b1, A3d1, A3e1 and A3t1, very preferably from formulae A3b1 and A3d1.
Further preferred groups Ar3 are selected from formula A3d1 wherein R5 and R6 denote F.
Further preferred groups Ar3 are selected from formulae A3e1 and A3f1 wherein R5 and R6 are different from H.
Very preferred groups Ar4 in formula I and I1-I7 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
wherein R5-9 have the meanings given above and below.
Very preferred groups Ar4 are selected from formulae A4a1, A4b1, A4c1, A4d1, A4f1, A4g1, A4h1, A4i1, A4k1, A4l1, A4m1, A4n1, A4o1, A4p1, A4q1, A4u and A4v1, very preferably from formula A4a1, A4b1, A4c1, A4d1, A4l1, A4m1, A4n1, A4o1, A4p1, A4q1, A4u1 and A4v1.
Further preferred groups Ar4 are selected from formula A4r1 and A4s1 wherein R5 and R6 are different from H.
Very preferred groups Ar5 in formula I and I1-I7 and their subformulae are on each occurrence identically or differently selected from the following formulae and their mirror images
wherein R5-9 have the meanings given above and below.
Very preferred groups Ar5 are selected from formulae A5a1, A5b1, A5c1, A5d1, A5f1, A5g1, A5h1, A5i1, A5k1, A5l1, A5m1, A5n1, A5o1, A5p1, A5q1, A5u and A5v1, very preferably from formula A5a1, A5b1, A5c1, A5d1, A5l1, A5m1, A5n1, A5o1, A5p1, A5q1, A5u1 and A5v1.
Further preferred groups Ar5 are selected from formula A5r1 and A5s1 wherein R5 and R6 are different from H.
Preferred units of formula I and I1-I7 are selected from the the group consisting of the following subformulae
wherein R1, R2, R5 and R6 have the meanings given above and below, R3 and R4 have one of the meanings given for R1 and R2 above and below, and the benzene and thiophene rings are optionally substituted in free positions by one or more groups R5.
Very preferred are the units of subformulae I1-3, I1-4, I2-1, I2-2 and I2-22.
In a preferred embodiment of the present invention, in the repeating units of formula I, I1-I7 and I1-1 to I5-I3 R1-4, when being different from H, are selected from F, Cl, CN, or from straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each of which has 1 to 20 C atoms and is unsubstituted or substituted by one or more F atoms, most preferably from F, Cl or formulae SUB1-SUB6 above.
In another preferred embodiment of the present invention, in the repeating units of formula I, I1-I7 and I1-1 to I5-I3 R1-4, when being different from H, are selected from mono- or polycyclic aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula 1 and has 5 to 20 ring atoms, and wherein two or more rings may be fused to each other or connected with each other by a covalent bond, very preferably phenyl that is optionally substituted, preferably in 4-position, 2,4-positions, 2,4,6-positions or 3,5-positions, or thiophene that is optionally substituted, preferably in 5-position, 4,5-positions or 3,5-positions, with alkyl, alkoxy or thioalkyl having 1 to 16 C atoms, most preferably from formulae SUB7-SUB18 above.
In another preferred embodiment of the present invention, in the repeating units of formula I, I1-I7 and I1-1 to I5-I3 R5-9 are H.
In another preferred embodiment of the present invention, in the repeating units of formula I, I1-I7 and I1-1 to I5-I3 at least one of R5-9 is different from H.
In a preferred embodiment of the present invention, in the repeating units of formula I, I1-I7 and I1-1 to I5-I3 R5-9, when being different from H, are each independently selected from F, Cl, CN, or from straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each of which has 1 to 20 C atoms and is unsubstituted or substituted by one or more F atoms, most preferably from F, Cl or formulae SUB1-SUB6 above.
In another preferred embodiment of the present invention, in the repeating units of formula I, I1-I7 and I1-1 to I5-I3 R5-9, when being different from H, are each independently selected are selected from mono- or polycyclic aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula I and has 5 to 20 ring atoms, and wherein two or more rings may be fused to each other or connected with each other by a covalent bond, very preferably phenyl that is optionally substituted, preferably in 4-position, 2,4-positions, 2,4,6-positions or 3,5-positions, or thiophene that is optionally substituted, preferably in 5-position, 4,5-positions or 3,5-positions, with alkyl, alkoxy or thioalkyl having 1 to 16 C atoms, more preferably from formulae SUB7-SUB18 above, most preferably from formulae SUB14-SUB18 above.
Preferred aryl and heteroaryl groups R1-9, when being different from H, are each independently selected from the following formulae
wherein R21-27, independently of each other, and on each occurrence identically or differently, denote H, F, Cl, CN, or straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CH2 groups are each optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —CF2—, —CR0═CR00 —, —CY1═CY2— or —in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are each optionally replaced by F, Cl, Br, I or CN, and in which one or more CH2 or CH3 groups are each optionally replaced by a cationic or anionic group.
Very preferred aryl and heteroaryl groups R1-9, when being different from H, are each independently selected from formulae S1, S4, S5, S7 and S10.
Most preferred aryl and heteroaryl groups R1-9 are each independently selected from formulae SUB7-SUB16 as defined above.
In another preferred embodiment one or more of R1-9 denote a straight-chain, branched or cyclic alkyl group with 1 to 50, preferably 2 to 50, very preferably 2 to 30, more preferably 2 to 24, most preferably 2 to 16 C atoms, in which one or more CH2 or CH3 groups are replaced by a cationic or anionic group.
The cationic group is preferably selected from the group consisting of phosphonium, sulfonium, ammonium, uronium, thiouronium, guanidinium or heterocyclic cations such as imidazolium, pyridinium, pyrrolidinium, triazolium, morpholinium or piperidinium cation.
Preferred cationic groups are selected from the group consisting of tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, N,N-dialkylpyrrolidinium, 1,3-dialkylimidazolium, wherein “alkyl” preferably denotes a straight-chain or branched alkyl group with 1 to 12 C atoms and very preferably is selected from formulae SUB1-6 .
Further preferred cationic groups are selected from the group consisting of the following formulae
wherein R1′, R2′, R3′ and R4′ denote, independently of each other, H, a straight-chain or branched alkyl group with 1 to 12 C atoms or non-aromatic carbo- or heterocyclic group or an aryl or heteroaryl group, each of the aforementioned groups having 3 to 20, preferably 5 to 15, ring atoms, being mono- or polycyclic, and optionally being substituted by one or more identical or different substituents L as defined above, or denote a link to the respective group R1-9.
In the above cationic groups of the above-mentioned formulae any one of the groups R1′, R2′, R3′ and R4′ (if they replace a CH3 group) can denote a link to the respective group R1-10, or two neighbored groups R1′, R2′, R3′ or R4′ (if they replace a CH2 group) can denote a link to the respective group R1.
The anionic group is preferably selected from the group consisting of borate, imide, phosphate, sulfonate, sulfate, succinate, naphthenate or carboxylate, very preferably from phosphate, sulfonate or carboxylate.
Further preferred repeating units of formula I, I1-I7 and I1-1 to I5-I3 are selected from the following preferred embodiments or any combination thereof:
Preferably the n-type polymer comprises one or more repeating units of formula I, I1-I7 or I1-1 to I5-I3 and one or more units Ar6.
In a preferred embodiment the n-type polymer comprises one or more units Ar6, which preferably have electron donor properties, and are selected from the group consisting of the formulae D1-D151 and their mirror images
wherein R11, R12, R13, R14, R15, R16, R17 and R18 independently of each other have one of the meanings of R1 as given in formula I or one of its preferred meanings as given above and below.
Preferred units are selected from formulae D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D37, D44, D55, D84, D87, D88, D89, D93, D94, D106, D111, D139, D140, D141, D146 or D150 wherein preferably at least one of R11-18 is different from H.
In another preferred embodiment the n-type polymer comprises one or more units Ar6, which preferably have electron acceptor properties, and are selected from the group consisting of the formulae A1-A101 and their mirror images
wherein R11, R12, R13, R14, R15 and R16 independently of each other have one of the meanings of R1 as given in formula I or one of its preferred meanings as given above and below, and preferably at least one of the substituents R11-18 is different from H.
Preferred units are selected from formulae A1, A36, A37, A38, A39, A40, A48, A74, A75, A76, A77, A79, A88, A89, A90, A91 and A101, very preferably from the formulae A36, A39, A48, A74, A88 and A101, wherein preferably at least one of R11-14 is different from H, and preferably at least one of R11-18 is different from H.
In a further preferred embodiment, the n-type polymer comprises one or more units Ar6 which are selected from the group consisting of the formulae Sp1-Sp18 and their mirror images
wherein R11, R12, R13, R14 independently of each other have one of the meanings of R1 as given in formula I or one of its preferred meanings as given above and below,
In the formulae Sp1 to Sp17 preferably R11 and R12 are H or F. In formula Sp18 preferably R11-14 are H or F.
Very preferred are units selected from formulae Sp1, Sp2, Sp6, Sp10, Sp11, Sp12, Sp13 and Sp14, wherein preferably one of R11 and R12 is H or both R11 and R12 are H or F.
Further preferred are n-type polymers comprising, preferably consisting of, one or more, preferably two or more, units of formula I, I1-I7 or or I1-1 to I5-I3, and one or more units Ar6 selected from the following groups
Further preferred are n-type polymers comprising, preferably consisting of, one or more, preferably two or more, units of formula I, I1-I7 or or I1-1 to I5-I3, and one or more units Ar6 selected from groups B2 and C2 as defined above.
In another preferred embodiment, the n-type polymer further comprises one or more units Ar6 selected from —CY1═CY2— and —C≡C—, wherein Y1 and Y2 are independently of each other H, F, Cl or CN.
In another preferred embodiment, the n-type polymer comprises, very preferably consists of, one or more units selected from the following groups
and wherein the n-type polymer contains at least one unit selected from groups 1A and 1D.
Preferred n-type polymers comprise one or more units of group 1D and one or more units of group 2A.
Further preferred n-type polymers comprise one or more units of group 1A and one or more units of group 2D.
Further preferred n-type polymers comprise one or more units of group 1D and one or more units of group 2D, and optionally one or more units selected from group 3.
Further preferred n-type polymers comprise one or more units of group 1A and one or more units of group 2A, and optionally one or more units selected from group 3.
Further preferably the n-type polymer comprises one or more units selected from groups 1D and 2D, one or more units selected from groups 1A and 2A, and one or more units selected from the group 3.
Further preferably the n-type polymer comprises, preferably consists of, one or more, preferably two or more, repeating units of formula II1 and/or II2, and optionally one or more repeating units of formula II3:
—(C1)a—U—(C2)b—(C3)c—(C4)d— II1
—(C1)a—(C2)b—U—(C3)c—(C4)d— II2
—(C1)a—(C2)b—(C3)c—(C4)d— II3
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
a, b, c, d 0 or 1, wherein in formula II3 a+b+c+d÷1
Preferably the n-type polymer comprises one or more repeating units of formula II1 or II2 wherein a+b+c+d≥1
Further preferably the n-type polymer comprises one or more repeating units of formula II1 wherein b=1 and a=c=d=0 and one or more repeating units of formula II3 wherein a=b=0 and c=d=1.
Further preferably the n-type polymer comprises two or more distinct repeating units of formula II1 wherein b=1 and a=c=d=0.
Further preferably C1, C2, C3 and C4 are selected from groups 2A, 2D and 3 as defined above and below.
Further preferably the n-type polymer is selected of formula III:
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
Further preferably the n-type polymer comprises, very preferably consists of, one or more units selected from the group consisting of the following formulae and their mirror images
—(U)— U1
—(U—Sp)— U2
—(Sp—U—Sp)— U3
-(D-Sp)— U4
-(A-Sp)— U5
—(Sp-A-Sp)— U7
-(A-D)- U8
-(D)- U9
—(Sp-D-Sp-D)- U10
-(A)- U11
—(Sp-A-Sp-A)— U12
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
and wherein the n-type polymer comprises at least one unit selected from formulae U1, U2 and U3.
Preferred n-type polymers are selected from formulae Pi-Pix
—[(U—Sp]n— Pi
—[(U—Sp)x—(Ar6—Sp)y]n— Pii
—[(U—Sp)x-(A—Sp)y]n— Piii
—[(U—Sp)x-(D-Sp)y]n— Piv
—[(U-D)x-(U-Sp)y]n— Pv
—[(U-A)x-(U-Sp)y]n— Pvi
—[(D)x-(Sp—U—Sp)y]n— Pvii
-[(A)x-(Sp—U—Sp)y]n— Pviii
—[Sp—U1—Sp—U2]n— Pix
wherein A, D and Sp are as defined in formulae U2-U12, A, D and Sp can each, in case of multiple occurrence, also have different meanings, U1 and U2 have one of the meanings given for U and are different from each other, x and y denote the molar fractions of the corresponding units, x and y are each, independently of one another, a non-integer >0 and <1, with x+y=1, and n is an integer >1.
Further preferred are n-type polymers, repeating units of formula U2-U12 contained therein and polymers of formulae Pi-Pix wherein
Very preferred n-type polymers are selected from the following subformulae
wherein x, y and n have the meanings given above and below. Especially preferred are formulae N7 to N50, very preferred formulae N9 and N10.
The composition according to the present invention further comprises one or more p-type organic semiconductors.
In a preferred embodiment of the present invention the p-type organic semiconductor is a conjugated polymer.
A preferred p-type semiconductor is poly-3-alkylthiophene wherein “alkyl” denotes C1-12 alkyl, very preferably poly-3-hexylthiophene (P3HT).
Another preferred p-type semiconductor is a conjugated polymer (hereinafter shortly referred to as “p-type polymer”) comprising at least one donor unit and at least one acceptor unit, and optionally at least one spacer unit separating a donor unit from an acceptor unit, wherein each donor and acceptor units is directly connected to another donor or acceptor unit or to a spacer unit, and wherein all of the donor, acceptor and spacer units are each independently selected from arylene or heteroarylene that has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, are is unsubstituted or substituted by one or more identical or different groups L as defined above.
A preferred p-type polymer comprises one or more units selected from formulae U4-U12 as defined above.
Another preferred p-type polymer is selected from the following formulae
-[D-A]n- Px
-[(D-Sp)x-(A-Sp)y]n— Pxi
-[A-D-A]n— Pxii
wherein A, D, Sp, x, y and n are as defined above.
In another preferred embodiment, the p-type polymer further comprises one or more units selected from —CY1═CY2— and —C≡C—, wherein Y1 and Y2 are independently of each other H, F, Cl or CN.
Further preferred are p-type polymers, repeating units of formula U4-U12 contained therein and polymers of formulae Px-Pxii wherein
Very preferred p-type polymers are selected from the following subformulae
wherein x, y and n have the meanings given above and below.
Further preferably the n-type and p-type polymers are selected of formula IV
RR1-chain-RE2 IV
wherein “chain” denotes a polymer chain selected from formulae III, Pi to Pxii, N1 to N50 or P1 to P47, and RE1 and RE2 have independently of each other one of the meanings of L as defined above, or denote, independently of each other, H, F, Br, Cl, I, —CH2Cl, —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—SO2—R′, —C≡CH, —≡C—SiR′3, —ZnX′ or an endcap group, X′ and X″ denote halogen, R′, R″ and R′″ have independently of each other one of the meanings of R0 given in formula I, and preferably denote alkyl with 1 to 12 C atoms, and two of R′, R″ and R′″ may also form a cyclosilyl, cyclostannyl, cycloborane or cycloboronate group with 2 to 20 C atoms together with the respective hetero atom to which they are attached.
Preferred endcap groups RE1 and RE2 are H, C1-20 alkyl, or optionally substituted C6-12 aryl or C2-10 heteroaryl, very preferably H or phenyl.
Above and below the n-type polymer and p-type polymer are also shortly referred to as “polymers according to the present invention”.
In the polymers according to the present invention the indices v, w, x, y and z denote the mole fraction of the corresponding repeating units, such as units A-E in formula III, and n denotes the degree of polymerisation or total number of repeating units. These formulae include block copolymers, random or statistical copolymers and alternating copolymers, as well as homopolymers for the case when x>0 and v=w=y=z=0.
In the polymers according to the present invention wherein one of v, w, y and z is not 0 and the others of v, w, y and z are 0, x and the one of v, w, y and z which is not 0 are each preferably from 0.1 to 0.9, very preferably from 0.3 to 0.7.
In the polymers according to the present invention wherein two of v, w, y and z are not 0 and the others of v, w, y and z are 0, x and those of v, w, y and z which are not 0 are each preferably from 0.1 to 0.8, very preferably from 0.2 to 0.6.
In the polymers according to the present invention wherein three of v, w, y and z are not 0 and the others of v, w, y and z are 0, x and those of v, w, y and z which are not 0 are each preferably from 0.1 to 0.7, very preferably from 0.2 to 0.5.
In the polymers according to the present invention wherein all of v, w, y and z are not 0, x, v, w, y and z are each preferably from 0.1 to 0.6, very preferably from 0.2 to 0.4.
In the polymers according to the present invention, the total number of repeating units n is preferably from 2 to 10,000, very preferably from 5 to 10,000. The total number of repeating units n is preferably ≥5, very preferably ≥10, most preferably ≥50, and preferably ≤500, very preferably ≤1,000, most preferably ≤2,000, including any combination of the aforementioned lower and upper limits of n.
The polymers of the present invention include homopolymers and copolymers, like statistical or random copolymers, alternating copolymers and block copolymers, as well as combinations thereof.
Further preferred units and polymers of formulae I, I1-I7, I1-1 to I5-I3, II1, II2, II3, III, Pi-Pxii, N1 to N50, P1 to P47, IV, V1-V3, V1a-d and I1-1 to I5-I3 are selected from the following embodiments, including any combination thereof:
The polymers according to the present invention can be synthesized according to or in analogy to methods that are known to the skilled person and are described in the literature. Other methods of preparation can be taken from the examples.
The polymers of the present invention can be prepared from the corresponding monomers, for example by polymerising or co-polymerising one or more of such monomers in an aryl-aryl coupling reaction
Preferred aryl-aryl coupling methods used in the synthesis methods as described above and below are Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling, C—H activation coupling, Ullmann coupling or Buchwald coupling. Especially 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 in 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 and C—H activation is described for example in M. Leclerc et al, Angew. Chem. Int. Ed., 2012, 51, 2068-2071.For example, when using Yamamoto coupling, educts having two reactive halide groups are preferably used. When using Suzuki coupling, educts having two reactive boronic acid or boronic acid ester groups or two reactive halide groups are preferably used. When using Stille coupling, educts having two reactive stannane groups or two reactive halide groups are preferably used. When using Negishi coupling, educts having two reactive organozinc groups or two reactive halide groups are preferably used.
Preferred catalysts, especially for Suzuki, Negishi or Stille coupling, are selected from Pd(0) complexes or Pd(II) salts. Preferred Pd(0) complexes are those bearing at least one phosphine ligand such as Pd(Ph3P)4. Another preferred phosphine ligand is tris(ortho-tolyl)phosphine, i.e. Pd(o-Tol3P)4. Preferred Pd(II) salts include palladium acetate, i.e. Pd(OAc)2. Alternatively the Pd(0) complex can be prepared by mixing a Pd(0) dibenzylideneacetone complex, for example tris(dibenzylideneacetone)dipalladium(0), bis(dibenzylideneacetone)palladium(0), or Pd(II) salts e.g. palladium acetate, with a phosphine ligand, for example triphenylphosphine, tris(ortho-tolyl)phosphine or tri(tert-butyl)phosphine. Suzuki coupling is performed in the presence of a base, for example sodium carbonate, potassium carbonate, cesium carbonate, lithium hydroxide, potassium phosphate or an organic base such as tetraethylammonium carbonate or tetraethylammonium hydroxide. Yamamoto coupling employs a Ni(0) complex, for example bis(1,5-cyclooctadienyl) nickel(0).
As alternatives to halogens as described above, leaving groups of formula —O—SO2Z0 can be used wherein Z0 is an alkyl or aryl group, preferably C1-10 alkyl or C6-12 aryl. Particular examples of such leaving groups are tosylate, mesylate and triflate.
The polymer according to the present invention can also be used in compositions, for example together with monomeric or polymeric compounds having charge-transport, semiconducting, electrically conducting, photoconducting and/or light emitting semiconducting properties, or for example with compounds having hole blocking or electron blocking properties for use as interlayers or charge blocking layers in PSCs or OLEDs.
Thus, another aspect of the invention relates to a composition comprising one or more polymers according to the present invention and one or more small molecule compounds and/or polymers having one or more of a charge-transport, semiconducting, electrically conducting, photoconducting, hole blocking and electron blocking property.
Another preferred embodiment of the present invention relates to a composition comprising a p-type semiconductor, which is preferably a conjugated polymer as described above and below, a first n-type semiconductor which is a polymer comprising a unit of formula I as described above and below, and a second n-type semiconductor, which is preferably a small molecule, very preferably a fullerene or fullerene derivative or a non-fullerene acceptor (NFA) small molecule.
In a preferred embodiment the second n-type semiconductor is a non-fullerene acceptor (NFA) small molecule having an A-D-A structure as described above with an electron donating polycyclic core and two terminal electron withdrawing groups attached thereto.
Suitable and preferred NFA small molecules for use as second n-type OSC in this preferred embodiment are for example those disclosed in Y. Lin et al., Adv. Mater., 2015, 27, 1170; H. Lin et al., Adv. Mater., 2015, 27, 7299; N. Qiu et al., Adv. Mater., 2017, 29, 1604964; CN104557968 A and CN105315298 A, furthermore those disclosed in WO 2018/007479 A1.
In another preferred embodiment the second n-type semiconductor is a fullerene or substituted fullerene.
The fullerene is for example an indene-C60-fullerene bisadduct like ICBA, or a (6,6)-phenyl-butyric acid methyl ester derivatized methano C60 fullerene, also known as “PCBM-C60” or “C60PCBM”, as disclosed for example in G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A.J. Heeger, Science 1995, Vol. 270, p. 1789 ff and having the structure shown below, or structural analogous compounds with e.g. a C61 fullerene group, a C70 fullerene group, or a C71 fullerene group, or an organic polymer (see for example Coakley, K. M. and McGehee, M. D. Chem. Mater. 2004, 16, 4533).
Preferably the polymer according to the present invention is blended with an n-type semiconductor such as a fullerene or substituted fullerene of formula Full-I to form the active layer in an OPV or OPD device,
wherein
In the formula Full-I and its subformulae, k preferably denotes 1, 2, 3 or, 4, very preferably 1 or 2.
The fullerene Cn in formula Full-I and its subformulae may be composed of any number n of carbon atoms Preferably, in the compounds of formula XII and its subformulae the number of carbon atoms n of which the fullerene Cn is composed is 60, 70, 76, 78, 82, 84, 90, 94 or 96, very preferably 60 or 70.
The fullerene Cn in formula Full-I and its subformulae is preferably selected from carbon based fullerenes, endohedral fullerenes, or mixtures thereof, very preferably from carbon based fullerenes.
Suitable and preferred carbon based fullerenes include, without limitation, (C60-Ih)[5,6]fullerene, (C70-D5h)[5,6]fullerene, (C76-D2*)[5,6]fullerene, (C084-D2*) [5,6]fullerene, (C84-D2d)[5,6]fullerene, or a mixture of two or more of the aforementioned carbon based fullerenes.
The endohedral fullerenes are preferably metallofullerenes. Suitable and preferred metallofullerenes include, without limitation, La@C60, La@C82, Y@C82, Sc3N@C80, Y3N@C80, Sc3C2@C80 or a mixture of two or more of the aforementioned metallofullerenes.
Preferably the fullerene Cn is substituted at a [6,6] and/or [5,6] bond, preferably substituted on at least one [6,6] bond.
Primary and secondary adducts, named “Adduct1” and “Adduct 2” in formula Full-I and its subformulae, are each preferably selected from the following formulae
wherein
RS1, RS2, RS3, RS4 and RS5 independently of each other denote H, CN or have one of the meanings of L as defined above and below,
and i is an integer from 1 to 20, preferably from 1 to 12.
Preferred compounds of formula Full-I are selected from the following subformulae:
wherein
RS1, RS2, RS3, RS4, RS5 and RS6 independently of each other denote H or have one of the meanings of RS as defined above and below.
Most preferably the fullerene is PCBM-C60, PCBM-C70, bis-PCBM-C60, bis-PCBM-C70, ICMA-c60 (1′,4′-dihydro-naphtho[2′,3′:1,2][5,6]fullerene-C60), ICBA, oQDM-C60 (1′,4′-dihydro-naphtho[2′,3′:1,9][5,6]fullerene-C60-Ih), or bis-oQDM-C60.
In another preferred embodiment the second n-type semiconductor is a small molecule which does not contain a fullerene moiety, and which is selected from naphthalene or perylene carboximide derivatives.
Preferred naphthalene or perylene carboximide derivatives for use as n-type OSC compounds are described for example in Adv. Sci. 2016, 3, 1600117, Adv. Mater. 2016, 28, 8546-8551, J. Am. Chem. Soc., 2016, 138, 7248-7251 and J. Mater. Chem. A, 2016, 4, 17604.
Preferred n-type semiconductor of this preferred embodiment are selected from the following formulae
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
The composition according to the present invention can be prepared by conventional methods that are described in prior art and known to the skilled person. Typically the compounds and/or polymers are mixed with each other or dissolved in suitable solvents and the solutions combined.
Another aspect of the invention relates to a formulation comprising one or more polymers according to the present invention or compositions as described above and below and one or more organic solvents.
Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and mixtures thereof. Further suitable and preferred solvents used include 1,2,4-trimethylbenzene, 1,2,3,4-tetra-methyl benzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, indane, 1,5-dimethyltetraline, decalin, 1-methylnaphthalene, 2,6-lutidine, 2-chlorobenzotrifluoride, N,N-dimethylformamide, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3-dimethylpyrazine, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoro-methylanisole, 2-methylanisole, phenetol, 4-methylanisole, 3-methylanisole, 4-fluoro-3-methylanisole, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, 3-fluorobenzo-nitrile, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethyl-anisole, N,N-dimethylaniline, ethyl benzoate, 1-fluoro-3,5-dimethoxy-benzene, N-methylpyrrolidinone, 3-fluorobenzo-trifluoride, benzotrifluoride, dioxane, trifluoromethoxy-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, chloro-benzene, o-dichlorobenzene, 2-chlorofluorobenzene, p-xylene, m-xylene, o-xylene, a mixture of o-, m-, and p-xylene, 2-fluoro-m-xylene, 3-fluoro-o-xylene, tetrahydrofuran, morpholine, 1,4-dioxane, 2-methylthiophene, 3-methylthiophene, chloroform, 1,2-dichloroethane, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, acetone, methylethylketone, propiophenone, acetophenone, cyclohexanone, ethyl acetate, n-butyl acetate, ethyl benzoate, ethyl benzoate, dimethylacetamide, dimethylsulfoxide, or mixtures of the aforementioned. Solvents with relatively low polarity are generally preferred.
Examples of especially preferred solvents include, without limitation, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methylethylketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1,5-dimethyltetraline, propiophenone, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decaline, indane, methyl benzoate, ethyl benzoate, mesitylene, or mixtures thereof.
The concentration of the compounds or polymers in the solution is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. Optionally, the solution also comprises one or more binders to adjust the rheological properties, as described for example in WO 2005/055248 A1.
After the appropriate mixing and ageing, solutions are evaluated as one of the following categories: complete solution, borderline solution or insoluble. The contour line is drawn to outline the solubility parameter-hydrogen bonding limits dividing solubility and insolubility. ‘Complete’ solvents falling within the solubility area can be chosen from literature values such as published in “Crowley, J. D., Teague, G. S. Jr and Lowe, J. W. Jr., Journal of Paint Technology, 1966, 38 (496), 296”. Solvent blends may also be used and can be identified as described in “Solvents, W. H. Ellis, Federation of Societies for Coatings Technology, p9-10, 1986”. Such a procedure may lead to a blend of ‘non’ solvents that will dissolve both the polymers of the present invention, although it is desirable to have at least one true solvent in a blend.
The compositions and formulations according to the present invention can additionally comprise one or more further components or additives selected for example from surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents which may be reactive or non-reactive, auxiliaries, colourants, dyes or pigments, sensitizers, stabilizers, nanoparticles or inhibitors.
In a composition according to the present invention comprising a first polymer, which is polymer according to the present invention, and a second conjugated polymer, the ratio 1st polymer: 2nd polymer is preferably from 5:1 to 1:5 by weight, more preferably from 3:1 to 1:3 by weight, most preferably 2:1 to 1:2 by weight.
The composition according to the present invention may also comprise a polymeric binder, preferably from 0.001 to 95% by weight. Examples of binder include polystyrene (PS), polydimethylsilane (PDMS), polypropylene (PP) and polymethylmethacrylate (PMMA).
A binder to be used in the formulation as described before, which is preferably a polymer, may comprise either an insulating binder or a semiconducting binder, or mixtures thereof, may be referred to herein as the organic binder, the polymeric binder or simply the binder.
Preferably, the polymeric binder comprises a weight average molecular weight in the range of 1,000 to 5,000,000 g/mol, especially 1,500 to 1,000,000 g/mol and more preferable 2,000 to 500,000 g/mol. Surprising effects can be achieved with polymers having a weight average molecular weight of at least 10,000 g/mol, more preferably at least 100,000 g/mol.
In particular, the polymer can have a polydispersity index Mw/Mn in the range of 1.0 to 10.0, more preferably in the range of 1.1 to 5.0 and most preferably in the range of 1.2 to 3.
Preferably, the inert binder is a polymer having a glass transition temperature in the range of −70 to 160° C., preferably 0 to 150° C., more preferably 50 to 140° C. and most preferably 70 to 130° C. The glass transition temperature can be determined by measuring the DSC of the polymer (DIN EN ISO 11357, heating rate 10° C. per minute).
The weight ratio of the polymeric binder to the OSC polymer according to the present invention is preferably in the range of 30:1 to 1:30, particularly in the range of 5:1 to 1:20 and more preferably in the range of 1:2 to 1:10.
According to a preferred embodiment the binder preferably comprises repeating units derived from styrene monomers and/or olefin monomers.
Preferred polymeric binders can comprise at least 80%, preferably 90% and more preferably 99% by weight of repeating units derived from styrene monomers and/or olefins.
Styrene monomers are well known in the art. These monomers include styrene, substituted styrenes with an alkyl substituent in the side chain, such as α-methylstyrene and α-ethylstyrene, substituted styrenes with an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
Olefin monomers consist of hydrogen and carbon atoms. These monomers include ethylene, propylene, butylenes, isoprene and 1,3-butadiene.
According to a preferred embodiment of the present invention, the polymeric binder is polystyrene having a weight average molecular weight in the range of 50,000 to 2,000,000 g/mol, preferably 100,000 to 750,000 g/mol, more preferably in the range of 150,000 to 600,000 g/mol and most preferably in the range of 200,000 to 500,000 g/mol.
Further examples of suitable binders are disclosed for example in US 2007/0102696 A1. Especially suitable and preferred binders are described in the following.
The binder should preferably be capable of forming a film, more preferably a flexible film.
Suitable polymers as binders include poly(1,3-butadiene), polyphenylene, polystyrene, poly(α-methylstyrene), poly(α-vinylnaphtalene), poly(vinyltoluene), polyethylene, cis-polybutadiene, polypropylene, polyisoprene, poly(4-methyl-1-pentene), poly (4-methylstyrene), poly(chorotrifluoroethylene), poly(2-methyl-1,3-butadiene), poly(p-xylylene), poly(α-α-α′-α′ tetrafluoro-p-xylylene), poly[1,1-(2-methyl propane)bis(4-phenyl)carbonate], poly(cyclohexyl methacrylate), poly(chlorostyrene), poly(2,6-dimethyl-1,4-phenylene ether), polyisobutylene, poly(vinyl cyclohexane), poly(vinylcinnamate), poly(4-vinylbiphenyl), 1,4-polyisoprene, polynorbornene, poly(styrene-block-butadiene); 31% wt styrene, poly(styrene-block-butadiene-block-styrene); 30% wt styrene, poly(styrene-co-maleic anhydride) (and ethylene/butylene) 1-1.7% maleic anhydride, poly(styrene-block-ethylene/butylene-block-styrene) triblock polymer 13% styrene, poly(styrene-block-ethylene-propylene -block-styrene) triblock polymer 37% wt styrene, poly(styrene-block-ethylene/butylene-block-styrene) triblock polymer 29% wt styrene, poly(1-vinylnaphthalene), poly(1-vinylpyrrolidone-co-styrene) 64% styrene, poly(1-vinylpyrrolidone-co-vinyl acetate) 1.3:1, poly(2-chlorostyrene), poly(2-vinylnaphthalene), poly(2-vinylpyridine-co-styrene) 1:1, poly(4,5-Difluoro-2,2-bis(CF3)-1,3-dioxole-co-tetrafluoroethylene) Teflon, poly(4-chlorostyrene), poly(4-methyl-1-pentene), poly(4-methylstyrene), poly(4-vinylpyridine-co-styrene) 1:1, poly(alpha-methylstyrene), poly(butadiene-graft-poly(methyl acrylate-co-acrylonitrile)) 1:1:1, poly(butyl methacrylate-co-isobutyl methacrylate) 1:1, poly(butyl methacrylate-co-methyl methacrylate) 1:1, poly(cyclohexylmethacrylate), poly(ethylene-co-1-butene-co-1-hexene) 1:1:1, poly(ethylene-co-ethylacrylate-co-maleic anhydride); 2% anhydride, 32% ethyl acrylate, poly(ethylene-co-glycidyl methacrylate) 8% glycidyl methacrylate, poly(ethylene-co-methyl acrylate-co-glycidyl meth-acrylate) 8% glycidyl metha-crylate 25% methyl acrylate, poly(ethylene-co-octene) 1:1, poly(ethylene-co-propylene-co-5-methylene-2-norbornene) 50% ethylene, poly(ethylene-co-tetrafluoroethylene) 1:1, poly(isobutyl methacrylate), poly(isobutylene), poly(methyl methacrylate)-co-(fluorescein O-methacrylate) 80% methyl methacrylate, poly(methyl methacrylate-co-butyl methacrylate) 85% methyl methacrylate, poly(methyl methacrylate-co-ethyl acrylate) 5% ethyl acrylate, poly(propylene-co-butene) 12% 1-butene, poly(styrene-co-allyl alcohol) 40% allyl alcohol, poly(styrene-co-maleic anhydride) 7% maleic anhydride, poly(styrene-co-maleic anhydride) cumene terminated (1.3:1), poly(styrene-co-methyl methacrylate) 40% styrene, poly(vinyltoluene-co-alpha-methylstyrene) 1:1, poly-2-vinylpyridine, poly-4-vinylpyridine, poly-alpha-pinene, polymethylmethacrylate, polybenzylmethacrylate, polyethylmethacrylate, polyethylene, polyethylene terephthalate, polyethylene-co-ethylacrylate 18% ethyl acrylate, polyethylene-co-vinylacetate 12% vinyl acetate, polyethylene-graft-maleic anhydride 0.5% maleic anhydride, polypropylene, polypropylene-graft-maleic anhydride 8-10% maleic anhydride, polystyrene poly(styrene-block-ethylene/butylene-block-styrene) graft maleic anhydride 2% maleic anhydride 1:1:1 others, poly(styrene-block-butadiene) branched 1:1, poly(styrene-block-butadiene-block-styrene), 30% styrene, poly(styrene-block-isoprene) 10% wt styrene, poly(styrene-block-isoprene-block-styrene) 17% wt styrene, poly(styrene-co-4-chloromethylstyrene-co-4-methoxymethylstyrene 2:1:1, polystyrene-co-acrylonitrile 25% acrylonitrile, polystyrene-co-alpha-methylstyrene 1:1, polystyrene-co-butadiene 4% butadiene, polystyrene-co-butadiene 45% styrene, polystyrene-co-chloromethylstyrene 1:1, polyvinylchloride, polyvinylcinnamate, polyvinylcyclohexane, polyvinylidenefluoride, polyvinylidenefluoride-co-hexafluoropropylene assume 1:1, poly(styrene-block-ethylene/propylene-block-styrene) 30% styrene, poly(styrene-block-ethylene/propylene-block-styrene) 18% styrene, poly(styrene-block-ethylene/propylene-block-styrene) 13% styrene, poly(styrene-block ethylene block-ethylene/propylene-block styrene) 32% styrene, poly(styrene-block ethylene block-ethylene/propylene-block styrene) 30% styrene, poly(styrene-block-ethylene/butylene-block-styrene) 31% styrene, poly(styrene-block-ethylene/butylene-block-styrene) 34% styrene, poly(styrene-block-ethylene/butylene-block-styrene) 30% styrene, poly(styrene-block-ethylene/butylene-block-styrene) 60%, styrene, branched or non-branched polystyrene-block-polybutadiene, polystyrene-block(polyethylene-ran-butylene)-block-polystyrene, polystyrene-block-polybutadiene-block-polystyrene, polystyrene-(ethylene-propylene)-diblock-copolymers (e.g. KRATON®-G1701E, Shell), poly(propylene-co-ethylene) and poly(styrene-co-methylmethacrylate).
Preferred insulating binders to be used in the formulations as described before are polystyrene, poly(α-methylstyrene), polyvinylcinnamate, poly(4-vinylbiphenyl), poly(4-methylstyrene), and polymethyl methacrylate. Most preferred insulating binders are polystyrene and polymethyl methacrylate.
The binder can also be selected from crosslinkable binders, like e.g. acrylates, epoxies, vinylethers, thiolenes etc. The binder can also be mesogenic or liquid crystalline.
The organic binder may itself be a semiconductor, in which case it will be referred to herein as a semiconducting binder. The semiconducting binder is still preferably a binder of low permittivity as herein defined. Semiconducting binders for use in the present invention preferably have a number average molecular weight (Mn) of at least 1500-2000, more preferably at least 3000, even more preferably at least 4000 and most preferably at least 5000. The semiconducting binder preferably has a charge carrier mobility of at least 10−5 cm2V−1s−1 more preferably at least 10−4 cm2V−1s−1.
A preferred semiconducting binder comprises a homo-polymer or copolymer (including block-copolymer) containing arylamine (preferably triarylamine).
The polymers and compositions according to the present invention are useful as charge transport, semiconducting, electrically conducting, photoconducting or light emitting materials in optical, electronic, optoelectronic, electroluminescent or photoluminescent components or devices. In these devices, the polymers and compositions of the present invention are typically applied as thin layers or films.
Thus, the present invention also provides the use of the polymer or composition or layer in an electronic device. The polymer or composition may be used as a high mobility semiconducting material in various devices and apparatus. The polymer or composition may be used, for example, in the form of a semiconducting layer or film. Accordingly, in another aspect, the present invention provides a semiconducting layer for use in an electronic device, the layer comprising a polymer or composition according to the invention. The layer or film may be less than about 30 microns. For various electronic device applications, the thickness may be less than about 1 micron thick. The layer may be deposited, for example on a part of an electronic device, by any of the aforementioned solution coating or printing techniques.
The polymers according to the present invention can also be used in patterned OSC layers in the devices as described above and below. For applications in modern microelectronics it is generally desirable to generate small structures or patterns to reduce cost (more devices/unit area), and power consumption. Patterning of thin layers comprising a compound according to the present invention can be carried out for example by photolithography, electron beam lithography or laser patterning.
For use as thin layers in electronic or optoelectronic devices the compounds, compositions or formulations of the present invention may be deposited by any suitable method. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred. The formulations of the present invention enable the use of a number of liquid coating techniques. Preferred deposition techniques include, without limitation, dip coating, spin coating, ink jet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, flexographic printing, web printing, spray coating, curtain coating, brush coating, slot dye coating or pad printing.
For the fabrication of OPV devices and modules area printing method compatible with flexible substrates are preferred, for example slot dye coating, spray coating and the like.
Ink jet printing is particularly preferred when high resolution layers and devices needs to be prepared. Selected formulations of the present invention may be applied to prefabricated device substrates by ink jet printing or microdispensing. Preferably industrial piezoelectric print heads such as but not limited to those supplied by Aprion, Hitachi-Koki, InkJet Technology, On Target Technology, Picojet, Spectra, Trident, Xaar may be used to apply the organic semiconductor layer to a substrate. Additionally semi-industrial heads such as those manufactured by Brother, Epson, Konica, Seiko Instruments Toshiba TEC or single nozzle microdispensers such as those produced by Microdrop and Microfab may be used.
In order to be applied by ink jet printing or microdispensing, the compounds or polymers should be first dissolved in a suitable solvent.
Suitable solvents should be selected to ensure full dissolution of all components, like p-type and n-type OSCs, and take into account the boundary conditions (for example rheological properties) introduced by the chosen printing method. For inkjet printing solvents and solvent mixtures with high boiling temperatures are preferred. For spin coating alkylated benzenes like xylene and toluene are preferred.
Apart from the requirements stated above the solvents should not have any detrimental effect on the chosen print head. Additionally, the solvents should preferably have boiling points >100° C., preferably >140° C. and more preferably >150° C. in order to prevent operability problems caused by the solution drying out inside the print head.
Apart from the solvents mentioned above, suitable solvents include substituted and non-substituted xylene derivatives, di-C1-2-alkyl formamide, substituted and non-substituted anisoles and other phenol-ether derivatives, substituted heterocycles such as substituted pyridines, pyrazines, pyrimidines, pyrrolidinones, substituted and non-substituted N,N-di-C1-2-alkylanilines and other fluorinated or chlorinated aromatics.
A preferred solvent for depositing a polymer by ink jet printing comprises a benzene derivative which has a benzene ring substituted by one or more substituents wherein the total number of carbon atoms among the one or more substituents is at least three. For example, the benzene derivative may be substituted with a propyl group or three methyl groups, in either case there being at least three carbon atoms in total. Such a solvent enables an ink jet fluid to be formed comprising the solvent with the polymer, which reduces or prevents clogging of the jets and separation of the components during spraying. The solvent(s) may include those selected from the following list of examples: dodecylbenzene, 1-methyl-4-tert-butylbenzene, terpineol, limonene, isodurene, terpinolene, cymene, and diethylbenzene. The solvent may be a solvent mixture, that is a combination of two or more solvents, each solvent preferably having a boiling point >100° C., more preferably >140° C. Such solvent(s) also enhance film formation in the layer deposited and reduce defects in the layer.
The ink jet fluid (that is mixture of solvent, binder and semiconducting compound) preferably has a viscosity at 20° C. of 1-100 mPa·s, more preferably 1-50 mPa·s and most preferably 1-30 mPa·s.
The invention additionally provides an OE device comprising a polymer or composition or organic semiconducting layer according to the present invention.
Preferred OE devices are OFETs, TFTs, ICs, logic circuits, capacitors, RFID tags, OLEDs, OLETs, OPEDs, OPVs, PSCs, OPDs, solar cells, laser diodes, photoconductors, photodetectors, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, charge injection layers, Schottky diodes, planarizing layers, antistatic films, conducting substrates and conducting patterns, .
Very preferred OE devices are OPV, PSC and OPD devices, OFETs, and OLEDs, in particular OPD, PSC and bulk heterojunction (BHJ) OPV devices. In an OFET, for example, the active semiconductor channel between the drain and source may comprise the polymer or composition of the invention. As another example, in an OLED device, the charge (hole or electron) injection or transport layer may comprise the polymer or composition of the invention.
An OPV or OPD device according to the present invention preferably further comprises a first transparent or semi-transparent electrode on a transparent or semi-transparent substrate on one side of the photoactive layer, and a second metallic or semi-transparent electrode on the other side of the photoactive layer.
Further preferably the OPV or OPD device comprises, between the photoactive layer and the first or second electrode, one or more additional buffer layers acting as hole transporting layer and/or electron blocking layer, which comprise a material such as metal oxide, like for example, ZTO, MoOx, NiOx, a conjugated polymer electrolyte, like for example PEDOT:PSS, a conjugated polymer, like for example polytriarylamine (PTAA), an insulating polymer, like for example nafion, polyethyleneimine or polystyrenesulphonate, an organic compound, like for example 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), or alternatively as hole blocking layer and/or electron transporting layer, which comprise a material such as metal oxide, like for example, ZnOx, TiOx, a salt, like for example LiF, NaF, CsF, a conjugated polymer electrolyte, like for example poly[3-(6-trimethylammoniumhexyl)thiophene], poly(9,9-bis(2-ethylhexyl)-fluorene]-b-poly[3-(6-trimethylammoniumhexyl)thiophene], or poly [(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] or an organic compound, like for example tris(8-quinolinolato)-aluminum(III) (Alq3), 4,7-diphenyl-1,10-phenanthroline.
The OPV device can for example be of any type known from the literature (see e.g. Waldauf et al., Appl. Phys. Lett., 2006, 89, 233517).
A first preferred OPV device according to the invention comprises the following layers (in the sequence from bottom to top):
A second preferred OPV device according to the invention is an inverted OPV device and comprises the following layers (in the sequence from bottom to top):
In the OPV devices of the present invention the p-type and n-type semiconductor materials are preferably selected from the materials, like the polymer/polymer/fullerene systems, as described above.
When the photoactive layer is deposited on the substrate, it forms a BHJ that phase separates at nanoscale level. For discussion on nanoscale 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. An optional annealing step may be then necessary to optimize blend morpohology and consequently OPV device performance.
Another method to optimize device performance is to prepare formulations for the fabrication of OPV(BHJ) devices that may include high boiling point additives to promote phase separation in the right way. 1,8-Octanedithiol, 1,8-diiodooctane, nitrobenzene, chloronaphthalene, and other additives have been used 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.
Another preferred embodiment of the present invention relates to the use of a polymer or composition according to the present invention as dye, hole transport layer, hole blocking layer, electron transport layer and/or electron blocking layer in a DSSC or a perovskite-based solar cell (PSC), and to a DSSC or PSC comprising a polymer or composition according to the present invention.
DSSCs and PSCs can be manufactured as described in the literature, for example in Chem. Rev. 2010, 110, 6595-6663, Angew. Chem. Int. Ed.
2014, 53, 2-15 or in W02013171520A1
A preferred OE device according to the invention is a solar cell, preferably a PSC, comprising a light absorber which is at least in part inorganic as described below.
In a solar cell comprising the light absorber according to the invention there are no restrictions per se with respect to the choice of the light absorber material which is at least in part inorganic.
The term “at least in part inorganic” means that the light absorber material may be selected from metalorganic complexes or materials which are substantially inorganic and possess preferably a crystalline structure where single positions in the crystalline structure may be allocated by organic ions.
Preferably, the light absorber comprised in the solar cell according to the invention has an optical band-gap ≤2.8 eV and ≥0.8 eV.
Very preferably, the light absorber in the solar cell according to the invention has an optical band-gap ≤2.2 eV and ≥1.0 eV.
The light absorber used in the solar cell according to the invention does preferably not contain a fullerene. The chemistry of fullerenes belongs to the field of organic chemistry. Therefore fullerenes do not fulfil the definition of being “at least in part inorganic” according to the invention.
Preferably, the light absorber which is at least in part inorganic is a material having perovskite structure or a material having 2D crystalline perovskite structure.
The term “perovskite” as used above and below denotes generally a material having a perovskite crystalline structure or a 2D crystalline perovskite structure.
The term perovskite solar cell (PSC) means a solar cell comprising a light absorber which is a material having perovskite structure or a material having 2D crystalline perovskite structure.
The light absorber which is at least in part inorganic is without limitation composed of a material having perovskite crystalline structure, a material having 2D crystalline perovskite structure (e.g. CrystEngComm, 2010,12, 2646-2662), Sb2S3 (stibnite), Sb2(SxSe(x-1))3, PbSxSe(x-1), CdSxSe(x-1), ZnTe, CdTe, ZnSxSe(x-1), InP, FeS, FeS2, Fe2S3, Fe2SiS4, Fe2GeS4, Cu2S, CuInGa, CuIn(SexS(1-x))2, Cu3SbxBi(x-1), (SySe(y-1))3, Cu2SnS3, SnSxSe(x-1), Ag2S, AgBiS2, BiSI, BiSeI, Bi2(SxSe(x-1))3, BiS(1-x)SexI, WSe2, AlSb, metal halides (e.g. BiI3, Cs2SnI6), chalcopyrite (e.g. CuInxGa(1-x)(SySe(1-y))2), kesterite (e.g. Cu2ZnSnS4, Cu2ZnSn(SexS(1-x))4, Cu2Zn(Sn1-xGex)S4) and metal oxide (e.g. CuO, Cu2O) or a mixture thereof.
Preferably, the light absorber which is at least in part inorganic is a perovskite.
In the above definition for light absorber, x and y are each independently defined as follows: (0≤x≤1) and (0≤y≤1).
Very preferably, the light absorber is a special perovskite namely a metal halide perovskite as described in detail above and below. Most preferably, the light absorber is an organic-inorganic hybrid metal halide perovskite contained in the perovskite solar cell (PSC).
In one particularly preferred embodiment of the invention, the perovskite denotes a metal halide perovskite with the formula ABX3, where
Preferably, the monovalent organic cation of the perovskite is selected from alkylammonium, wherein the alkyl group is straight chain or branched having 1 to 6 C atoms, formamidinium or guanidinium or wherein the metal cation is selected from K+, Cs+ or Rb+.
Suitable and preferred divalent cations B are Ge2+, Sn2+ or Pb2+.
Suitable and preferred perovskite materials are CsSnI3, CH3NH3Pb(I1-xClx)3, CH3NH3PbI3, CH3NH3Pb(I1-xBrx)3, CH3NH3Pb(I1-x(BF4)x)3, CH3NH3Sn(I1-xClx)3, CH3NH3SnI3 or CH3NH3Sn(I1-xBrx)3 wherein x is each independently defined as follows: (0<x≤1).
Further suitable and preferred perovskites may comprise two halides corresponding to formula Xa(3-x)Xb(x), wherein Xa and Xb are each independently selected from Cl, Br, or I, and x is greater than 0 and less than 3.
Suitable and preferred perovskites are also disclosed in WO 2013/171517, claims 52 to 71 and claims 72 to 79, which is entirely incorporated herein by reference. The materials are defined as mixed-anion perovskites comprising two or more different anions selected from halide anions and chalcogenide anions. Preferred perovskites are disclosed on page 18, lines 5 to 17. As described, the perovskite is usually selected from CH3NH3PbBrI2, CH3NH3PbBrCl2, CH3NH3PbIBr2, CH3NH3PbICl2, CH3NH3SnF2Br, CH3NH3SnF2I and (H2N═CH—NH2)PbI3zBr3(1-z), wherein z is greater than 0 and less than 1.
The invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the polymer according to the present invention is employed as a layer between one electrode and the light absorber layer.
The invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the polymer according to the present invention is comprised in an electron-selective layer.
The electron selective layer is defined as a layer providing a high electron conductivity and a low hole conductivity favoring electron-charge transport.
The invention further relates to a solar cell comprising the light absorber, preferably a PSC, as described above and below, wherein the polymer according to the present invention is employed as electron transport material (ETM) or as hole blocking material as part of the electron selective layer.
Preferably, the polymer according to the present invention is employed as electron transport material (ETM).
In an alternative preferred embodiment, the polymer according to the present invention is employed as hole blocking material.
The device architecture of a PSC device according to the invention can be of any type known from the literature.
A first preferred device architecture of a PSC device according to the invention comprises the following layers (in the sequence from bottom to top):
and a back electrode which can be metallic, for example made of Au, Ag, Al, Cu, Ca, Ni or combinations thereof, or non-metallic and transparent, semi-transparent or non-transparent.
A second preferred device architecture of a PSC device according to the invention comprises the following layers (in the sequence from bottom to top):
and a back electrode which can be metallic, for example made of Au, Ag, Al, Cu, Ca, Ni or combinations thereof, or non-metallic and transparent, semi-transparent or non-transparent.
To produce electron selective layers in PSC devices according to the invention, the polymers according to the present invention, optionally together with other compounds or additives in the form of blends or mixtures, may be deposited by any suitable method. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred. Formulations comprising the polymers according to the present invention enable the use of a number of liquid coating techniques. Preferred deposition techniques include, without limitation, dip coating, spin coating, ink jet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, flexographic printing, web printing, spray coating, curtain coating, brush coating, slot die coating or pad printing. For the fabrication of PSC devices and modules, deposition techniques for large area coating are preferred, for example slot die coating or spray coating.
Formulations that can be used to produce electron selective layers in optoelectronic devices according to the invention, preferably in PSC devices comprise one or more polymers according to the present invention or preferred embodiments as described above in the form of blends or mixtures optionally together with one or more further electron transport materials and/or hole blocking materials and/or binders and/or other additives as described above and below, and one or more solvents.
The formulation may include or comprise, essentially consist of or consist of the said necessary or optional constituents as described above or below. All compounds or components which can be used in the formulations are either known or commercially available, or can be synthesized by known processes.
The formulation as described before may be prepared by a process which comprises:
In step (i) the solvent may be a single solvent for the polymer according to the present invention and the organic binder and/or further electron transport material may each be dissolved in a separate solvent followed by mixing the resultant solutions to mix the compounds.
Alternatively, the binder may be formed in situ by mixing or dissolving a polymer according to the present invention in a precursor of a binder, for example a liquid monomer, oligomer or crosslinkable polymer, optionally in the presence of a solvent, and depositing the mixture or solution, for example by dipping, spraying, painting or printing it, on a substrate to form a liquid layer and then curing the liquid monomer, oligomer or crosslinkable polymer, for example by exposure to radiation, heat or electron beams, to produce a solid layer. If a preformed binder is used it may be dissolved together with the polymer in a suitable solvent as described before, and the solution deposited for example by dipping, spraying, painting or printing it on a substrate to form a liquid layer and then removing the solvent to leave a solid layer. It will be appreciated that solvents are chosen which are able to dissolve all ingredients of the formulation, and which upon evaporation from the solution blend give a coherent defect free layer.
Besides the said components, the formulation as described before may comprise further additives and processing assistants. These include, inter alia, surface-active substances (surfactants), lubricants and greases, additives which modify the viscosity, additives which increase the conductivity, dispersants, hydrophobicizing agents, adhesion promoters, flow improvers, antifoams, deaerating agents, diluents, which may be reactive or unreactive, fillers, assistants, processing assistants, dyes, pigments, stabilizers, sensitizers, nanoparticles and inhibitors.
Additives can be used to enhance the properties of the electron selective layer and/or the properties of any of the neighbouring layers and/or the performance of the optoelectronic device according to the invention. Additives can also be used to facilitate the deposition, the processing or the formation of the electron selective layer and/or the deposition, the processing or the formation of any of the neighbouring layers. Preferably, one or more additives are used which enhance the electrical conductivity of the electron selective layer and/or passivate the surface of any of the neighbouring layers.
Suitable methods to incorporate one or more additives include, for example exposure to a vapor of the additive at atmospheric pressure or at reduced pressure, mixing a solution or solid containing one or more additives and a material or a formulation as described or preferably described before, bringing one or more additives into contact with a material or a formulation as described before, by thermal diffusion of one or more additives into a material or a formulation as described before, or by ion-implantation of one or more additives into a material or a formulation as described before.
Additives used for this purpose can be organic, inorganic, metallic or hybrid materials. Additives can be molecular compounds, for example organic molecules, salts, ionic liquids, coordination complexes or organometallic compounds, polymers or mixtures thereof. Additives can also be particles, for example hybrid or inorganic particles, preferably nanoparticles, or carbon based materials such as fullerenes, carbon nanotubes or graphene flakes.
Examples for additives that can enhance the electrical conductivity are for example halogens (e.g. I2, Cl2, Br2, ICl, ICl3, IBr and IF), Lewis acids (e.g. PF5, AsF5, SbF5, BF3, BCl3, SbCl5, BBr3 and SO3), protonic acids, organic acids, or amino acids (e.g. HF, HCl, HNO3, H2SO4, HClO4, FSO3H and ClSO3H), transition metal compounds (e.g. FeCl3, FeOCl, Fe(ClO4)3, Fe(4-CH3C6H4SO3)3, TiCl4, ZrCl4, HfCl4, NbF5, NbCl5, TaCl5, MoF5, MoCl5, WF5, WCl6, UF6 and LnCl3 (wherein Ln is a lanthanoid)), anions (e.g. Cl−, Br−, I−, I3−, HSO4−, SO42−, NO3−, ClO4−, BF4−, PF6−, Fe(CN)63−, and anions of various sulfonic acids, such as aryl-SO3−), cations (e.g. H+, Li+, Na+, K+, Rb+, Cs+, Co3+ and Fe3+), O2, redox active salts (e.g. XeOF4, (NO2+) (SbF6−), (NO2+) (SbCl6−), (NO2+) (BF4−), NOBF4, NOPF6, AgClO4, H2IrCl6 and La(NO3)3.6H2O), strongly electron-accepting organic molecules (e.g. 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ)), transition metal oxides (e.g. WO3, Re2O7 and MoO3), metal-organic complexes of cobalt, iron, bismuth and molybdenum, (p-BrC6H4)3NSbCl6, bismuth(III) tris(trifluoroacetate), FS2OOSO2F, acetylcholine, R4N+, (R is an alkyl group), R4P+ (R is a straight-chain or branched alkyl group 1 to 20), R6As+ (R is an alkyl group), R3S+ (R is an alkyl group) and ionic liquids (e.g. 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide). Suitable cobalt complexes beside of tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)-cobalt(III) tris(bis(trifluoromethylsulfonyl)imide)) are cobalt complex salts as described in WO 2012/114315, WO 2012/114316, WO 2014/082706, WO 2014/082704, EP 2883881 or JP 2013-131477.
Suitable lithium salts are beside of lithium bis(trifluoromethylsulfonyl)imide, lithium tris(pentafluoroethyl)trifluorophosphate, lithium dicyanamide, lithium methylsulfate, lithium trifluormethanesulfonate, lithium tetracyanoborate, lithium dicyanamide, lithium tricyanomethide, lithium thiocyanate, lithium chloride, lithium bromide, lithium iodide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroantimonate, lithium hexafluoroarsenate or a combination of two or more. A preferred lithium salt is lithium bis(trifluoromethylsulfonyl)imide.
Preferably, the formulation comprises from 0.1 mM to 50 mM, preferably from 5 to 20 mM of the lithium salt.
Suitable device structures for PSCs comprising a polymer according to the present invention and a mixed halide perovskite are described in WO 2013/171517, claims 52 to 71 and claims 72 to 79, which is entirely incorporated herein by reference.
Suitable device structures for PSCs comprising a polymer according to the present invention and a dielectric scaffold together with a perovskite are described in WO 2013/171518, claims 1 to 90 or WO 2013/171520, claims 1 to 94 which are entirely incorporated herein by reference.
Suitable device structures for PSCs comprising a polymer according to the present invention, a semiconductor and a perovskite are described in WO 2014/020499, claims 1 and 3 to 14, which is entirely incorporated herein by reference The surface-increasing scaffold structure described therein comprises nanoparticles which are applied and/or fixed on a support layer, e.g. porous TiO2.
Suitable device structures for PSCs comprising a polymer according to the present invention and comprising a planar heterojunction are described in WO 2014/045021, claims 1 to 39, which is entirely incorporated herein by reference. Such a device is characterized in having a thin film of a light-absorbing or light-emitting perovskite disposed between n-type (electron conducting) and p-type (hole-conducting) layers. Preferably, the thin film is a compact thin film.
The invention further relates to a method of preparing a PSC as described above or below, the method comprising the steps of:
The invention relates furthermore to a tandem device comprising at least one device according to the invention as described above and below. Preferably, the tandem device is a tandem solar cell.
The tandem device or tandem solar cell according to the invention may have two semi-cells wherein one of the semi cells comprises the compounds, oligomers or polymers in the active layer as described or preferably described above. There exists no restriction for the choice of the other type of semi cell which may be any other type of device or solar cell known in the art.
There are two different types of tandem solar cells known in the art. The so called 2-terminal or monolithic tandem solar cells have only two connections. The two subcells (or synonymously semi cells) are connected in series. Therefore, the current generated in both subcells is identical (current matching). The gain in power conversion efficiency is due to an increase in voltage as the voltages of the two subcells add up.
The other type of tandem solar cells is the so called 4-terminal or stacked tandem solar cell. In this case, both subcells are operated independently. Therefore, both subcells can be operated at different voltages and can also generate different currents. The power conversion efficiency of the tandem solar cell is the sum of the power conversion efficiencies of the two subcells.
The invention furthermore relates to a module comprising a device according to the invention as described before or preferably described before.
The polymers and compositions according to the present invention can also be used as dye or pigment in other applications, for example as an ink dye, laser dye, fluorescent marker, solvent dye, food dye, contrast dye or pigment in coloring paints, inks, plastics, fabrics, cosmetics, food and other materials.
The polymers and compositions of the present invention are also suitable for use in the semiconducting channel of an OFET. Accordingly, the invention also provides an OFET comprising a gate electrode, an insulating (or gate insulator) layer, a source electrode, a drain electrode and an organic semiconducting channel connecting the source and drain electrodes, wherein the organic semiconducting channel comprises a polymer or a composition according to the present invention. Other features of the OFET are well known to those skilled in the art.
OFETs where an OSC material is arranged as a thin film between a gate dielectric and a drain and a source electrode, are generally known, and are described for example in U.S. Pat. Nos. 5,892,244, 5,998,804, 6,723,394 and in the references cited in the background section. Due to the advantages, like low cost production using the solubility properties of the polymers according to the invention and thus the processibility of large surfaces, preferred applications of these OFETs are such as integrated circuitry, TFT displays and security applications.
The gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.
An OFET device according to the present invention preferably comprises:
wherein the semiconductor layer comprises a polymer or composition according to the present invention.
The OFET device can be a top gate device or a bottom gate device. Suitable structures and manufacturing methods of an OFET device are known to the 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, like e.g. the commercially available Cytop 809M® or Cytop 107M® (from Asahi Glass). Preferably the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a perfluorosolvent. A suitable perfluorosolvent is e.g. FC75® (available from Acros, catalogue number 12380). Other suitable fluoropolymers and fluorosolvents are known in prior art, like for example the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont) or Fluoropel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No. 12377). Especially preferred are organic dielectric materials having a low permittivity (or dielectric constant) from 1.0 to 5.0, very preferably from 1.8 to 4.0 (“low k materials”), as disclosed for example in US 2007/0102696 A1 or U.S. Pat. No. 7,095,044.
In security applications, OFETs and other devices with semiconducting materials according to the present invention, like transistors or diodes, can be used for RFID tags or security markings to authenticate and prevent counterfeiting of documents of value like banknotes, credit cards or ID cards, national ID documents, licenses or any product with monetary value, like stamps, tickets, shares, cheques etc.
Alternatively, the polymers and compositions (hereinafter referred to as “materials”) according to the present invention can be used in OLEDs, e.g. as the active display material in a flat panel display applications, or as backlight of a flat panel display like e.g. a liquid crystal display. Common OLEDs are realized using multilayer structures. An emission layer is generally sandwiched between one or more electron-transport and/or hole-transport layers. By applying an electric voltage electrons and holes as charge carriers move towards the emission layer where their recombination leads to the excitation and hence luminescence of the lumophor units contained in the emission layer. The materials according to the present invention may be employed in one or more of the charge transport layers and/or in the emission layer, corresponding to their electrical and/or optical properties. Furthermore their use within the emission layer is especially advantageous, if the materials according to the present invention show electroluminescent properties themselves or comprise electroluminescent groups or compounds. The selection, characterization as well as the processing of suitable monomeric, oligomeric and polymeric compounds or materials for the use in OLEDs is generally known by a person skilled in the art, see, e.g., Müller et al, Synth. Metals, 2000, 111-112, 31-34, Alcala, J. Appl. Phys., 2000, 88, 7124-7128 and the literature cited therein.
According to another use, the materials according to the present invention, especially those showing photoluminescent properties, may be employed as materials of light sources, e.g. in display devices, as described in EP 0 889 350 A1 or by C. Weder et al., Science, 1998, 279, 835-837.
A further aspect of the invention relates to both the oxidized and reduced form of the materials according to the present invention. Either loss or gain of electrons results in formation of a highly delocalized ionic form, which is of high conductivity. This can occur on exposure to common dopants. Suitable dopants and methods of doping are known to those skilled in the art, e.g. from EP 0 528 662, U.S. Pat. No. 5,198,153 or WO 96/21659.
The doping process typically implies treatment of the semiconductor material with an oxidating or reducing agent in a redox reaction to form delocalized ionic centers in the material, with the corresponding counterions derived from the applied dopants. Suitable doping methods comprise for example exposure to a doping vapor in the atmospheric pressure or at a reduced pressure, electrochemical doping in a solution containing a dopant, bringing a dopant into contact with the semiconductor material to be thermally diffused, and ion-implantation of the dopant into the semiconductor material.
When electrons are used as carriers, suitable dopants are for example halogens (e.g., I2, Cl2, Br2, ICl, ICl3, IBr and IF), Lewis acids (e.g., PF5, AsF5, SbF5, BF3, BCl3, SbCl5, BBr3 and SO3), protonic acids, organic acids, or amino acids (e.g., HF, HCl, HNO3, H2SO4, HClO4, FSO3H and ClSO3H), transition metal compounds (e.g., FeCl3, FeOCl, Fe(ClO4)3, Fe(4-CH3C6H4SO3)3, TiCl4, ZrCl4, HfCl4, NbF5, NbCl5, TaCl5, MoF5, MoCl5, WF5, WCl6, UF6 and LnCl3 (wherein Ln is a lanthanoid), anions (e.g., CI−, Br−, I−, I3−, HSO4−, SO42−, NO3, ClO4−, BF4−, PF6−, AsF6−, SbF6−, FeCl4−, Fe(CN)63−, and anions of various sulfonic acids, such as aryl-SO3−). When holes are used as carriers, examples of dopants are cations (e.g., H+, Li+, Na+, K+, Rb+ and Cs+), alkali metals (e.g., Li, Na, K, Rb, and Cs), alkaline-earth metals (e.g., Ca, Sr, and Ba), O2, XeOF4, (NO2+) (SbF6−), (NO2+) (SbCl6−), (NO2+) (BF4−), AgClO4, H2IrCl6, La(NO3)3.6H2O, FSO2OOSO2F, Eu, acetylcholine, R4N+, (R is an alkyl group), R4P+ (R is an alkyl group), R6As+ (R is an alkyl group), and R3S+ (R is an alkyl group).
The conducting form of the materials according to the present invention can be used as an organic “metal” in applications including, but not limited to, charge injection layers and ITO planarizing layers in OLED applications, films for flat panel displays and touch screens, antistatic films, printed conductive substrates, patterns or tracts in electronic applications such as printed circuit boards and condensers.
The materials according to the present invention may also be suitable for use in organic plasmon-emitting diodes (OPEDs), as described for example in Koller et al., Nat. Photonics, 2008, 2, 684.
According to another use, the materials according to the present invention can be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US 2003/0021913. The use of charge transport compounds according to the present invention can increase the electrical conductivity of the alignment layer. When used in an LCD, this increased electrical conductivity can reduce adverse residual dc effects in the switchable LCD cell and suppress image sticking or, for example in ferroelectric LCDs, reduce the residual charge produced by the switching of the spontaneous polarization charge of the ferroelectric LCs. When used in an OLED device comprising a light emitting material provided onto the alignment layer, this increased electrical conductivity can enhance the electroluminescence of the light emitting material.
The materials according to the present invention having mesogenic or liquid crystalline properties can form oriented anisotropic films as described above, which are especially useful as alignment layers to induce or enhance alignment in a liquid crystal medium provided onto said anisotropic film.
According to another use, the materials according to the present invention are suitable for use in liquid crystal (LC) windows, also known as smart windows.
The materials according to the present invention may also be combined with photoisomerizable compounds and/or chromophores for use in or as photoalignment layers, as described in US 2003/0021913 A1.
According to another use, the materials according to the present invention, especially their water-soluble derivatives (for example with polar or ionic side groups) or ionically doped forms, can be employed as chemical sensors or materials for detecting and discriminating DNA sequences. Such uses are described for example in L. Chen, D. W. McBranch, H. Wang, R. Helgeson, F. Wudl and D. G. Whitten, Proc. Natl. Acad. Sci. U.S.A., 1999, 96, 12287; D. Wang, X. Gong, P. S. Heeger, F. Rininsland, G. C. Bazan and A. J. Heeger, Proc. Natl. Acad. Sci. U.S.A., 2002, 99, 49; N. DiCesare, M. R. Pinot, K. S. Schanze and J. R. Lakowicz, Langmuir, 2002, 18, 7785; D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev., 2000, 100, 2537.
Unless the context clearly indicates otherwise, as used herein plural forms of the terms herein are to be construed as including the singular form and vice versa.
Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of the words, for example “comprising” and “comprises”, mean “including but not limited to”, and are not intended to (and do not) exclude other components.
It will be appreciated that variations to the foregoing embodiments of the invention can be made while still falling within the scope of the invention.
Each feature disclosed in this specification, unless stated otherwise, may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
All of the features disclosed in this specification may be combined in any combination, except combinations where at least some 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 may be used in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).
Above and below, unless stated otherwise percentages are percent by weight and temperatures are given in degrees Celsius.
The invention will now be described in more detail by reference to the following examples, which are illustrative only and do not limit the scope of the invention.
Polymer 1 was prepared as follows.
To a mixture of 2,8-dibromo-6,12-dihydro-6,6,12,12-tetrakis(4-hexadecylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′] dithiophene (7.50 g, 4.27 mmol) and anhydrous tetrahydrofuran (300 cm3) at −78° C. was added dropwise n-butyllithium (5.50 cm3, 13.8 mmol, 2.5 M in hexanes) over 10 minutes. The reaction mixture was stirred at −78° C. for 4 hours. Trimethyltin chloride (14.5 cm3, 14.5 mmol, 1 M in hexanes) was added in one portion and the mixture allowed to warm to 23° C. over 17 hours. The volatiles were removed in vacuo and the residue passed through a silica plug (80-100 petrol) followed by recrystallisation (80-100 petrol) to give 1,1′-[6,6,12,12-tetrakis(4-hexadecylphenyl)-6,12-dihydrodithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene-2,8-diyl]bis[1,1,1-trimethyl-stannane (7.52 g, 92%) as a bright yellow solid. 1H-NMR (400 MHz, CDCl3) 7.47 (2H, s), 7.30 (2H, s), 7.15-7.21 (8H, m), 7.04-7.10 (8H, m), 2.48-2.60 (8H, m), 1.51-1.65 (8H, m), 1.15-1.37 (104H, m), 0.82-0.93 (12H, m).
To a degassed mixture of 4,8-bis-(5-bromo-thiophen-2-yl)-6-octyl-[1,2,5]thiadiazolo[3,4-e]isoindole-5,7-dione (159.9 mg, 0.250 mmol), 1,1′-[6,6,12,12-tetrakis(4-hexadecylphenyl)-6,12-dihydrodithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene-2,8-diyl]bis[1,1,1-trimethyl-stannane (476.6 mg, 0.250 mmol), tri-o-tolylphosphine (6.1 mg, 0.020 mmol), anhydrous toluene (6.0 cm3) and anhydrous N,N-dimethylformamide (1.0 cm3) was added tris(dibenzylideneacetone)dipalladium(0) (3.5 mg, 0.005 mmol). The reaction mixture was then heated at 120° C. for 1 hour. Phenytributyltin (0.20 cm3) was added and the mixture heated at 120° C. for 30 minutes. Bromobenzene (0.20 cm3) was added and the mixture heated at 120° C. for 30 minutes. The mixture allowed to cool slightly and then precipitated into stirred acetone (150 cm3). The solid collected by filtration, washed with methanol (100 cm3) and acetone (100 cm3) and subjected to Soxhlet extraction: acetone, 40-60 petrol and chloroform. The chloroform extract was poured into stirred acetone (500 cm3) and the solid collected by filtration to give poly[2,8-{6,12-dihydro-6,6,12,12-tetrakis(4-hexadecylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene}-alt-{5,5-(4,8-bis(thiophen-2-yl)-6-octyl-[1,2,5]thiadiazolo[3,4-e]isoindole-5,7-dione)}] (500 mg, 97%) as a black solid. GPC (chlorobenzene, 50° C.) Mn=46,700 g/mol, Mw=132,000 g/mol.
Bulk Heterojunction Organic Photovoltaic Devices (OPVs)
Organic photovoltaic (OPV) devices are fabricated on pre-patterned ITO-glass substrates (130/sq.) purchased from LUMTEC Corporation. Substrates are cleaned using common solvents (acetone, iso-propanol, deionized-water) in an ultrasonic bath. A layer of commercially available N-21X (Nanograde) was applied as a uniform coating by doctor blade at 40° C. The N-21X Films are then annealed at 100° C. for 10 minutes in air. Active material solutions (i.e. n-type polymer+p-type polymer) are prepared to fully dissolve the solutes at a 25 mg·cm−3 solution concentration in o-dichlorobezene (oDCB). Thin films are blade-coated in air to achieve active layer thicknesses between 50 and 800 nm as measured using a profilometer. A short drying period follows to ensure removal of any residual solvent.
Typically, blade-coated films are dried at 70° C. for 2 minutes on a hotplate. Next the devices are transferred into an air atmosphere. On top of the active layer 0.14 mL of a conducting polymer poly(ethylene dioxythiophene) doped with poly(styrene sulfonic acid) [PEDOT:PSS Clevios HTL Solar 434-1 (Heraeus)] was uniformly coated by doctor blade. Afterwards Ag (100 nm) cathodes are thermally evaporated through a shadow mask to define the cells. Current-voltage characteristics are measured using a Keithley 2400 SMU while the solar cells are illuminated by a Newport Solar Simulator at 100 mW/cm2 white light. The solar simulator is equipped with AM1.5G filters. The illumination intensity is calibrated using a Si photodiode. All the device preparation and characterization is done in a dry-nitrogen atmosphere.
Power conversion efficiency is calculated using the following expression
where FF is defined as
| Number | Date | Country | Kind |
|---|---|---|---|
| 19161292.8 | Mar 2019 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/055596 | 3/4/2020 | WO |
