[go: up one dir, main page]

WO2024115329A1 - Composés utiles dans la préparation d'un dispositif photosensible - Google Patents

Composés utiles dans la préparation d'un dispositif photosensible Download PDF

Info

Publication number
WO2024115329A1
WO2024115329A1 PCT/EP2023/083051 EP2023083051W WO2024115329A1 WO 2024115329 A1 WO2024115329 A1 WO 2024115329A1 EP 2023083051 W EP2023083051 W EP 2023083051W WO 2024115329 A1 WO2024115329 A1 WO 2024115329A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
electron
occurrence
compound according
substituent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2023/083051
Other languages
English (en)
Inventor
Michal MACIEJCZYK
Florence BOURCET
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cambridge Display Technology Ltd
Sumitomo Chemical Co Ltd
Original Assignee
Cambridge Display Technology Ltd
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cambridge Display Technology Ltd, Sumitomo Chemical Co Ltd filed Critical Cambridge Display Technology Ltd
Publication of WO2024115329A1 publication Critical patent/WO2024115329A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/611—Charge transfer complexes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • Embodiments of the present disclosure relate to electron-accepting compounds and more specifically compounds suitable for use as an electron-accepting material in a photoresponsive device.
  • An organic photodetector may contain a photoactive layer of a blend of an electron-donating material and an electron- accepting material between an anode and a cathode.
  • Known electronaccepting materials include fullerenes and non-fullerene acceptors (NFAs).
  • WO 2015/044377A1 describes A-D-A compounds with a completely annelated midblock D and to the use thereof in optoelectronic components.
  • WO 2019/185578A1 describes organic semiconducting compounds.
  • CN 110028488A describes an A-D-A type organic photovoltaic small molecule receptor.
  • CN111978335B describes a photovoltaic material.
  • a 2 is a monovalent electron-accepting group; D is an electron-donating group; B 1 in each occurrence is independently a bridging group; n is at least 1; m is 0 or at least 1; p is 0 or 1; q is 0 or 1;
  • the present disclosure provides a composition comprising an electron-donating material and an electron-accepting material wherein the electron accepting material is a compound as described herein.
  • the present disclosure provides an organic electronic device comprising an active layer comprising a compound or composition as described herein.
  • the organic electronic device is an organic photoresponsive device comprising a photoactive layer disposed between an anode and a cathode and wherein the photoactive layer comprises a compound as described herein.
  • the photoactive layer is a bulk heterojunction layer comprising a composition as described herein.
  • the photoactive layer comprises two or more sub-layers including an electron-accepting sublayer comprising or consisting of a compound as described herein and an electron-donating sublayer comprising or consisting of an electron-donating material.
  • the organic photoresponsive device is an organic photodetector.
  • the present disclosure provides a photosensor comprising a light source and an organic photodetector as described herein wherein the organic photodetector is configured to detect light emitted from the light source.
  • the light source emits light having a peak wavelength of greater than 900 nm.
  • the present disclosure provides a formulation comprising a compound or composition as described herein dissolved or dispersed in one or more solvents.
  • the present disclosure provides a method of forming an organic electronic device as described herein wherein formation of the active layer comprises deposition of a formulation as described herein onto a surface and evaporation of the one or more solvents.
  • Figure 1 illustrates an organic photoresponsive device according to some embodiments.
  • Figure 2 is the absorption spectra of a compound according to an embodiment of the disclosure and a comparative compound.
  • Figure 3 shows the EQE of a device comprising a compound according to an embodiment of the disclosure and a device comprising a comparative compound.
  • Figure 4 shows the current density of a device comprising a compound according to an embodiment of the disclosure.
  • Figure 5 shows the EQE of devices comprising a compound according to an embodiment of the disclosure.
  • Figure 6 shows the current density of devices comprising a compound according to an embodiment of the disclosure.
  • references to a layer “over” another layer when used in this application means that the layers may be in direct contact or one or more intervening layers may be present. References to a layer “on” another layer when used in this application means that the layers are in direct contact. References to a specific atom include any isotope of that atom unless specifically stated otherwise.
  • Each of the electron-accepting groups A 1 and A 2 has a lowest unoccupied molecular orbital (LUMO) level that is deeper (i.e., further from vacuum) than the LUMO of any of the electrondonating groups D, preferably at least 1 eV deeper.
  • the LUMO levels of electron- accepting groups and electron-donating groups may be as determined by modelling the LUMO level of these groups, in which each bond to adjacent group is replaced with a bond to a hydrogen atom. Modelling may be performed using Gaussian09 software available from Gaussian using Gaussian09 with B3LYP (functional) and LACVP* (Basis set).
  • a 2 is a monovalent electron-accepting group
  • D is an electron-donating group
  • B 1 in each occurrence is independently a bridging group
  • n is at least 1
  • m is 0 or at least 1
  • p is 0 or 1
  • q is 0 or 1
  • a 1 is a group represented by formula (II)
  • R 4 in each occurrence is H or an electron withdrawing group, with the proviso that at least one R 4 is CN.
  • R 4 in each occurrence is an electron withdrawing group selected from the group consisting of Ci-12 esters (such as C1-6 esters), Ci-12 ketones (such as C1-6 ketones), CF3, halogen, NO2, and CN, with the proviso that at least one R 4 is CN.
  • Ci-12 esters such as C1-6 esters
  • Ci-12 ketones such as C1-6 ketones
  • CF3, halogen, NO2, and CN with the proviso that at least one R 4 is CN.
  • two R 4 s are a substituent, optionally wherein the two R 4 s are CN.
  • each R 4 is an electron withdrawing group selected from the group consisting of Ci-12 esters (such as C1-6 esters), Ci-12 ketones (such as C1-6 ketones), CF3, halogen, NO2, and CN, with the proviso that at least one R 4 is CN.
  • each R 4 is a halogen or CN, with the proviso that at least one R 4 is CN. More preferably, when one or more R 4 is a substituent, each R 4 is CN.
  • n is 1, 2, 3, 4, or 5.
  • n is at least 1, 2, 3 or 4.
  • n is 1, 2, or 3.
  • n is 1 or 2.
  • n is independently 0, 1, 2, 3, 4, or 5.
  • m is at least 0, 1, 2, 3 or 4.
  • m is 1, 2, or 3.
  • m is 1 or 2.
  • n and m are the same. Alternatively, n and m are different. In some embodiments, p and q are the same. Alternatively, p and q are different.
  • the monovalent acceptor group A 2 may independently be selected from any such units known to the skilled person.
  • a 2 may be the same or different to A 1 , preferably the same.
  • Exemplary monovalent acceptor groups A 2 include, without limitation, groups of formulae (IXa)-(IXq) Rio , (IXq)
  • U is a 5- or 6-membered ring which is unsubstituted or substituted with one or more substituents and which may be fused to one or more further rings.
  • each R 6 of any NR 6 or PR 6 described anywhere herein is independently selected from H; Ci -20 alkyl wherein one or more non-adjacent C atoms other than the C atom bound to N or P may be replaced with O, S, NR 11 , COO or CO and one or more H atoms of the alkyl may be replaced with F; and phenyl which is unsubstituted or substituted with one or more substituents, optionally one or more Ci-12 alkyl groups wherein one or more non-adjacent C atoms of the alkyl may be replaced with O, S, NR 11 , COO or CO and one or more H atoms of the alkyl may be replaced with F wherein R 11 is H or a Ci-2ohydrocarbyl group.
  • Ci -20 hydrocarbyl group as described anywhere is preferably selected from Ci-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more Ci-12 alkyl groups
  • N atom of formula (IXe) may be unsubstituted or substituted.
  • R 10 is H or a substituent, preferably a substituent selected from the group consisting of Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; and an aromatic group, optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO.
  • R 10 is H.
  • R 13 in each occurrence is a substituent, optionally Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • R 15 in each occurrence is independently H; F; Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; aromatic group Ar 2 , optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO; or a group selected from:
  • R 16 is H or a substituent, preferably a substituent selected from:
  • Ar 3 in each occurrence is independently an unsubstituted or substituted aryl or heteroaryl group, preferably thiophene, and w is 1, 2 or 3;
  • C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • Ar 6 is a 5-membered heteroaromatic group, preferably thiophene or furan, which is unsubstituted or substituted with one or more substituents.
  • Substituents of Ar 3 and Ar 6 are optionally selected from Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • T 1 , T 2 and T 3 each independently represent an aryl or a heteroaryl ring, optionally benzene, which may be fused to one or more further rings.
  • Substituents of T 1 , T 2 and T 3 are optionally selected from non-H groups of R 25 .
  • T 3 is benzo thiadiazole .
  • z 1 is N or P.
  • Ar 8 is a fused heteroaromatic group which is unsubstituted or substituted with one or more substituents, optionally one or more non-H substituents R 10 , and which is bound to an aromatic C atom of B 1 and to a boron substituent of B 1 .
  • a 2 is a group of formula
  • R 10 is as described above;
  • Ar 9 is an unsubstituted or substituted monocyclic or fused aromatic or heteroaromatic group, preferably benzene or a monocyclic or bicyclic heteroaromatic group having C or N ring atoms only;
  • X 60 are each independently CN, CF3 or COOR 40 wherein R 40 in each occurrence is H or a substituent, preferably H or a Ci-2ohydrocarbyl group.
  • R 40 in each occurrence is H or a substituent, preferably H or a Ci-2ohydrocarbyl group.
  • each X 60 is CN.
  • Ar 9 may be unsubstituted or substituted with one or more substituents.
  • Substituents of Ar 9 are preferably selected from groups R 12 as described below.
  • the group of formula (IXa-1) has formula (IXa-2):
  • each X 7 -X 10 is independently CR 12 or N wherein R 12 in each occurrence is H or a substituent selected from Ci-20 hydrocarbyl and an electron withdrawing group.
  • the electron withdrawing group is F, Cl, Br or CN, more preferably F, Cl or CN; and for example F or CN.
  • the Ci -20 hydrocarbyl group R 12 may be selected from Ci-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more Ci-12 alkyl groups.
  • each of X 7 -X 10 is CR 12 and each R 12 is independently selected from H or an electron-withdrawing group, preferably H, F or CN.
  • R 12 of X 8 and X 9 is an electron-withdrawing group, preferably F or CN.
  • Exemplary groups of formula (IXd) include:
  • Exemplary groups of formula (IXe) include:
  • An exemplary group of formula (IXj) is: wherein Ak is a Ci-12 alkylene chain in which one or more C atoms may be replaced with O, S, NR 6 , CO or COO; An is an anion, optionally -SO3’; and each benzene ring is independently unsubstituted or substituted with one or more substituents selected from substituents described with reference to R 10 .
  • Exemplary groups of formula (IXm) are:
  • Groups of formula (IXo) are bound directly to a bridging group B 1 substituted with a group of formula -B(R 14 )2 wherein R 14 in each occurrence is a substituent, optionally a Ci-2ohydrocarbyl group; — is a bond to the boron atom -B(R 14 )2; and — is a C-C bond between formula (IXo) and the bridging group.
  • R 14 is selected from Ci-12 alkyl; unsubstituted phenyl; and phenyl substituted with one or more Ci-12 alkyl groups.
  • the group of formula (IXo), the B 1 group and the B(R 14 )2 substituent of B 1 may be linked together to form a 5- or 6-membered ring.
  • groups of formula (IXo) are selected from:
  • a 2 is a group represented by formula (II)
  • R 3 , Y and R 4 are each independently the same as defined in relation to formula (II) of A 1 .
  • a 1 and A 2 may be the same or different.
  • R 4 in each occurrence is H or an electron withdrawing group, with the proviso that at least one R 4 is CN.
  • R 4 in each occurrence is an electron withdrawing group selected from the group consisting of halogen, NO2, and CN, with the proviso that at least one R 4 is CN.
  • two R 4 s are a substituent, optionally wherein the two R 4 s are CN.
  • each R 4 is an electron withdrawing group selected from the group consisting of halogen, NO2, and CN, with the proviso that at least one R 4 is CN.
  • each R 4 is a halogen or CN, with the proviso that at least one R 4 is CN. More preferably, when one or more R 4 is a substituent, each R 4 is CN.
  • any substituent described herein may be independently selected from the group consisting of Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; and an aromatic group, optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO; and wherein NR 6 is as described herein.
  • R 40 as described herein may be a substituent as described herein.
  • the replaced C atom may be a terminal C atom of the alkyl group or a non-terminal C- atom.
  • non-terminal C atom of an alkyl group as used anywhere herein means a C atom other than the C atom of the methyl group at the end of an n-alkyl chain or the C atoms of the methyl groups at the ends of a branched alkyl chain.
  • the resulting group may be an anionic group comprising a countercation, e.g., an ammonium or metal countercation, preferably an ammonium or alkali metal cation.
  • a countercation e.g., an ammonium or metal countercation, preferably an ammonium or alkali metal cation.
  • a C atom of an alkyl substituent group which is replaced with another atom or group as described anywhere herein is preferably a non-terminal C atom, and the resultant substituent group is preferably non-ionic.
  • Bridging units B 1 are preferably each selected from arylene or heteroarylene wherein the arylene and heteroarylene groups are monocyclic or bicyclic groups, each of which may be unsubstituted or substituted with one or more substituents.
  • B 1 is selected from units of formulae (Via) - (VIo): (Via) (VIb) (Vic) wherein R 55 is H or a substituent, optionally H or a Ci-20 hydrocarbyl group; and R 8 in each occurrence is independently H or a substituent, preferably H or a substituent selected from F; CN; NO 2 ; Ci -20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; phenyl which is unsubstituted or substituted with one or more substituents; and -B(R 14 )2 wherein R 14 in each occurrence is a substituent, optionally a C 1-20 hydrocarbyl group.
  • R 8 groups of formulae (Via), (VIb) and (Vic) may be linked to form a bicyclic ring which may be substituted with one or more substituents, optionally one or more substituents selected from F; CN; NO 2 ; Ci -20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • R 8 is preferably H, Ci-20 alkyl or Ci-19 alkoxy.
  • R 8 groups of formulae (Via), (VIb) and (Vic) may be linked to form an optionally substituted bicyclic ring.
  • Electron-donating groups preferably are fused aromatic or heteroaromatic groups, more preferably fused heteroaromatic groups containing three or more rings.
  • Particularly preferred electron-donating groups comprise fused thiophene or furan rings, optionally fused rings containing thiophene or furan rings and one or more rings selected from benzene, cyclopentadiene, tetrahydropyran, tetrahydrothiopyran and piperidine rings, each of said rings being unsubstituted or substituted with one or more substituents.
  • Exemplary electron-donating groups D include groups of formulae (Vlla)-(VIIm): wherein Y A in each occurrence is independently O, S or NR 55 , Y A1 in each occurrence is independently O or S; Z A in each occurrence is O, CO, S, NR 55 or C(R 54 ; R 51 , R 52 R 54 and R 55 independently in each occurrence is H or a substituent; R 53 independently in each occurrence is a substituent; and Ar 4 is an optionally substituted monocyclic or fused heteroaromatic group.
  • R 51 and R 52 independently in each occurrence are selected from H; F; Ci-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; and an aromatic or heteroaromatic group Ar 3 which is unsubstituted or substituted with one or more substituents.
  • Ar 3 may be an aromatic group, e.g., phenyl.
  • Ar 4 is preferably selected from optionally substituted oxadiazole, thiadiazole, triazole, and 1,4- diazine.
  • the 1,4-diazine may be fused to a further heterocyclic group, optionally a group selected from optionally substituted oxadiazole, thiadiazole, triazole, 1,4-diazine and succinimide.
  • the one or more substituents of Ar 3 may be selected from Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • each R 54 is selected from the group consisting of:
  • Ci-20 alkyl wherein one or more non-adjacent C atoms may be replaced by O, S, NR 17 , CO or COO wherein R 17 is a C1-12 hydrocarbyl and one or more H atoms of the Ci-20 alkyl may be replaced with F; and a group of formula (Ak)u-(Ar 7 )v wherein Ak is a Ci-20 alkylene chain in which one or more non-adjacent C atoms may be replaced with O, S, NR 6 , CO or COO; u is 0 or 1; Ar 7 in each occurrence is independently an aromatic or heteroaromatic group which is unsubstituted or substituted with one or more substituents; and v is at least 1, optionally 1, 2 or 3.
  • Substituents of Ar 7 are preferably selected from F; Cl; NO2; CN; and Ci-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , CO or COO and one or more H atoms may be replaced with F.
  • Ar 7 is phenyl.
  • R 53 independently in each occurrence is selected from Ci-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; and phenyl which is unsubstituted or substituted with one or more substituents, optionally one or more Ci-12 alkyl groups wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • R 55 as described anywhere herein is H or Ci-3ohydrocarbyl group.
  • D 1 of the compound of formula (I) is a group of formula (Vile).
  • Exemplary compounds of formula (I) include, without limitation:
  • R in each occurrence is independently a Ci-12 alkyl group or Ci-12 alkoxy group.
  • a photoactive layer as described herein comprises an electron-donating material.
  • the photoactive layer may be a bulk heterojunction layer comprising an electron-donating material and a compound of formula (I) as described herein.
  • the photoactive layer may comprise two or more sub-layers including an electron-donating sub-layer comprising or consisting of an electron-donating material.
  • Exemplary donor materials are disclosed in, for example, WO2013/051676, the contents of which are incorporated herein by reference.
  • the electron-donating material may be a non-poly meric or polymeric material.
  • the electron-donating material is an organic conjugated polymer, which can be a homopolymer or copolymer including alternating, random or block copolymers.
  • the conjugated polymer is preferably a donor- acceptor polymer comprising alternating electron-donating repeat units and electron- accepting repeat units.
  • the electron-donating polymer is a conjugated organic polymer with a low bandgap, typically between 2.5 eV and 1.5 eV, preferably between 2.3 eV and 1.8 eV.
  • the electron-donating polymer has a HOMO level no more than 5.5 eV from vacuum level.
  • the electron-donating polymer has a HOMO level at least 4.1 eV from vacuum level.
  • polymers selected from conjugated hydrocarbon or heterocyclic polymers including polyacene, polyaniline, polyazulene, polybenzofuran, polyfluorene, polyfuran, polyindenofluorene, polyindole, polyphenylene, polypyrazoline, polypyrene, polypyridazine, polypyridine, polytriarylamine, poly(phenylene vinylene), poly(3-substituted thiophene), poly(3,4-bisubstituted thiophene), polyselenophene, poly(3-substituted selenophene), poly(3,4- bisubstituted selenophene), poly(bisthiophene), poly(terthiophen
  • donor polymers are copolymers of polyfluorenes and poly thiophenes, each of which may be substituted, and polymers comprising benzothiadiazole-based and thiophene-based repeating units, each of which may be substituted.
  • a particularly preferred donor polymer comprises a repeat unit of formula (X): wherein Y A , Z A , R 51 and R 54 are as described above.
  • Another particularly preferred donor polymer comprises repeat units of formula (XI): wherein R 18 and R 19 are each independently selected from H; F; Ci-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO and one or more H atoms of the alkyl may be replaced with F; or an aromatic or heteroaromatic group Ar 6 which is unsubstituted or substituted with one or more substituents selected from F and Ci-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO.
  • R 18 and R 19 are each independently selected from H; F; Ci-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO and one or more H atoms of the alkyl may be replaced with F; or an aromatic or heteroaromatic group Ar 6 which is unsubstituted or substituted with
  • the donor polymer is preferably a donor-acceptor (DA) copolymer comprising a donor repeat unit, for example a repeat unit of formula (X) or (XI), and an acceptor repeat unit, for example divalent electron- accepting units A 2 as described herein provided as polymeric repeat units.
  • DA donor-acceptor
  • a compound of formula (I) may be provided as an active layer of an organic electronic device.
  • a photoactive layer of an organic photoresponsive device more preferably an organic photodetector, comprises a compound of formula (I).
  • the photoactive layer is a bulk heterojunction layer comprising or consisting of an electron-donating material and an electron-accepting compound of formula (I) as described herein.
  • the bulk heterojunction layer contains two or more electron-donating materials and / or two or more electron- accepting materials.
  • the weight of the electron-donating material(s) to the electron- accepting material(s) is from about 1:0.5 to about 1:2, preferably about 1:1.1 to about 1:2.
  • the electron-donating material has a type II interface with the electron-accepting material, i.e. the electron-donating material has a shallower HOMO and LUMO that the corresponding HOMO and LUMO levels of the electron- accepting material.
  • the compound of formula (I) has a HOMO level that is at least 0.05 eV deeper, optionally at least 0.10 eV deeper, than the HOMO of the electron-donating material.
  • the gap between the HOMO level of the electron-donating material and the LUMO level of the electron- accepting compound of formula (I) is less than 1.4 eV.
  • HOMO and LUMO levels of materials as described herein are as measured by square wave voltammetry (SWV).
  • the current at a working electrode is measured while the potential between the working electrode and a reference electrode is swept linearly in time.
  • the difference current between a forward and reverse pulse is plotted as a function of potential to yield a voltammogram. Measurement may be with a CHI 660D Potentiostat.
  • the apparatus to measure HOMO or LUMO energy levels by SWV may comprise a cell containing 0.1 M tertiary butyl ammonium hexafluorophosphate in acetonitrile; a 3 mm diameter glassy carbon working electrode; a platinum counter electrode and a leak free Ag/AgCl reference electrode. Ferrocene is added directly to the existing cell at the end of the experiment for calculation purposes where the potentials are determined for the oxidation and reduction of ferrocene versus Ag/AgCl using cyclic voltammetry (CV).
  • CV cyclic voltammetry
  • the sample is dissolved in toluene (3 mg / ml) and spun at 3000 rpm directly on to the glassy carbon working electrode.
  • LUMO 4.8-E ferrocene (peak to peak average) - E reduction of sample (peak maximum).
  • HOMO 4.8-E ferrocene (peak to peak average) + E oxidation of sample (peak maximum).
  • FIG. 1 illustrates an organic photoresponsive device according to some embodiments of the present disclosure.
  • the organic photoresponsive device comprises a cathode 103, an anode 107 and a bulk heterojunction layer 105 disposed between the anode and the cathode.
  • the organic photoresponsive device may be supported on a substrate 101, optionally a glass or plastic substrate.
  • Each of the anode and cathode may independently be a single conductive layer or may comprise a plurality of layers.
  • At least one of the anode and cathode is transparent so that light incident on the device may reach the bulk heterojunction layer.
  • both of the anode and cathode are transparent.
  • the transmittance of a transparent electrode may be selected according to an emission wavelength of a light source for use with the organic photodetector.
  • Figure 1 illustrates an arrangement in which the cathode is disposed between the substrate and the anode.
  • the anode may be disposed between the cathode and the substrate.
  • the organic photoresponsive device may comprise layers other than the anode, cathode and bulk heterojunction layer shown in Figure 1.
  • a hole-transporting layer is disposed between the anode and the bulk heterojunction layer.
  • an electron-transporting layer is disposed between the cathode and the bulk heterojunction layer.
  • a work function modification layer is disposed between the bulk heterojunction layer and the anode, and/or between the bulk heterojunction layer and the cathode.
  • Photoactive layer 105 of Figure 1 is a bulk heterojunction layer.
  • the photoactive layer comprises or consists of an electron-accepting sub-layer comprising or consisting of a compound of formula (I) and an electron-donating sub-layer comprising an electron-donating material.
  • the area of the OPD may be less than about 3 cm 2 , less than about 2 cm 2 , less than about 1 cm 2 , less than about 0.75 cm 2 , less than about 0.5 cm 2 or less than about 0.25 cm 2 .
  • each OPD may be part of an OPD array wherein each OPD is a pixel of the array having an area as described herein, optionally an area of less than 1 mm 2 , optionally in the range of 0.5 micron 2 - 900 micron 2 .
  • the substrate may be, without limitation, a glass or plastic substrate.
  • the substrate can be an inorganic semiconductor.
  • the substrate may be silicon.
  • the substrate can be a wafer of silicon.
  • the substrate is transparent if, in use, incident light is to be transmitted through the substrate and the electrode supported by the substrate.
  • a compound of formula (I) is the only electron- accepting material of a bulk heterojunction layer as described herein.
  • a bulk heterojuction layer contains a compound of formula (I) and one or more further electron-accepting materials.
  • Preferred further electron-accepting materials are fullerenes.
  • the compound of formula (I) : fullerene acceptor weight ratio may be in the range of about 1 : 0.1 - 1 : 1, preferably in the range of about 1 : 0.1 - 1 : 0.5.
  • Fullerenes may be selected from, without limitation, Ceo, C70, C76, C78 and Cs4 fullerenes or a derivative thereof, including, without limitation, PCBM-type fullerene derivatives including phenyl-Cei-butyric acid methyl ester (CeoPCBM), TCBM-type fullerene derivatives (e.g. tolyl- Cei-butyric acid methyl ester (CeoTCBM)), and ThCBM-type fullerene derivatives (e.g. thienyl-Cei -butyric acid methyl ester (CeoThCBM).
  • Fullerene derivatives may have formula (V): wherein A, together with the C-C group of the fullerene, forms a monocyclic or fused ring group which may be unsubstituted or substituted with one or more substituents.
  • Exemplary fullerene derivatives include formulae (Va), (Vb) and (Vc): wherein R 20 -R 32 are each independently H or a substituent.
  • Substituents R 20 -R 32 are optionally and independently in each occurrence selected from the group consisting of aryl or heteroaryl, optionally phenyl, which may be unsubstituted or substituted with one or more substituents; and Ci-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , CO or COO and one or more H atoms may be replaced with F.
  • Substituents of aryl or heteroaryl, where present, are optionally selected from Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , CO or COO and one or more H atoms may be replaced with F.
  • the photoactive layer may be formed by any process including, without limitation, thermal evaporation and solution deposition methods.
  • the photoactive layer comprising the compound of formula (I) or (II) is formed by depositing a formulation comprising or consisting of the electron-accepting material(s) and, in the case of a the bulk heterojunction layer, the electron-donating materials dissolved or dispersed in a solvent or a mixture of two or more solvents.
  • the formulation may be deposited by any coating or printing method including, without limitation, spin-coating, dip-coating, rollcoating, spray coating, doctor blade coating, wire bar coating, slit coating, ink jet printing, screen printing, gravure printing and flexographic printing.
  • the one or more solvents of the formulation may optionally comprise or consist of benzene or naphthalene substituted with one or more substituents selected from fluorine, chlorine, Ci-10 alkyl and Ci-10 alkoxy wherein two or more substituents may be linked to form a ring which may be unsubstituted or substituted with one or more C1-6 alkyl groups, optionally toluene, xylenes, trimethylbenzenes, tetramethylbenzenes, anisole, indane and its alkyl-substituted derivatives, and tetralin and its alkyl-substituted derivatives.
  • substituents selected from fluorine, chlorine, Ci-10 alkyl and Ci-10 alkoxy wherein two or more substituents may be linked to form a ring which may be unsubstituted or substituted with one or more C1-6 alkyl groups, optionally toluene, xylenes, trimethylbenzenes, te
  • the formulation may comprise a mixture of two or more solvents, preferably a mixture comprising at least one benzene substituted with one or more substituents as described above and one or more further solvents.
  • the one or more further solvents may be selected from esters, optionally alkyl or aryl esters of alkyl or aryl carboxylic acids, optionally a Ci-10 alkyl benzoate, benzyl benzoate or dimethoxybenzene.
  • a mixture of trimethylbenzene and benzyl benzoate is used as the solvent.
  • a mixture of trimethylbenzene and dimethoxybenzene is used as the solvent.
  • the formulation may comprise further components in addition to the electron- accepting material, the electron-donating material (in the case of a bulk heterojunction layer) and the one or more solvents.
  • adhesive agents defoaming agents, deaerators, viscosity enhancers, diluents, auxiliaries, flow improvers colourants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface-active compounds, lubricating agents, wetting agents, dispersing agents and inhibitors may be mentioned.
  • a circuit may comprise the OPD connected to one or more of a voltage source for applying a reverse bias to the device; a device configured to measure photocurrent; and an amplifier configured to amplify an output signal of the OPD.
  • the voltage applied to the photodetector may be variable.
  • the photodetector may be continuously biased when in use.
  • a photodetector system comprises a plurality of photodetectors as described herein, such as an image sensor of a camera.
  • a sensor may comprise an OPD as described herein and a light source wherein the OPD is configured to receive light emitted from the light source.
  • the light source has a peak wavelength of at least 900 nm or at least 1000 nm, optionally in the range of 900-1500 nm.
  • the light from the light source may or may not be changed before reaching the OPD.
  • the light may be reflected, filtered, down-converted or up- converted before it reaches the OPD.
  • the organic photoresponsive device as described herein may be an organic photovoltaic device or an organic photodetector.
  • An organic photodetector as described herein may be used in a wide range of applications including, without limitation, detecting the presence and / or brightness of ambient light and in a sensor comprising the organic photodetector and a light source.
  • the photodetector may be configured such that light emitted from the light source is incident on the photodetector and changes in wavelength and/or brightness of the light may be detected, e.g., due to absorption by, reflection by and/or emission of light from an object, e.g. a target material in a sample disposed in a light path between the light source and the organic photodetector.
  • the sample may be a non-biological sample, e.g. a water sample, or a biological sample taken from a human or animal subject.
  • the sensor may be, without limitation, a gas sensor, a biosensor, an X-ray imaging device, an image sensor such as a camera image sensor, a motion sensor (for example for use in security applications) a proximity sensor or a fingerprint sensor.
  • a ID or 2D photosensor array may comprise a plurality of photodetectors as described herein in an image sensor.
  • the photodetector may be configured to detect light emitted from a target analyte which emits light upon irradiation by the light source or which is bound to a luminescent tag which emits light upon irradiation by the light source.
  • the photodetector may be configured to detect a wavelength of light emitted by the target analyte or a luminescent tag bound thereto.
  • Comparative Compound 1 Comparative Compound 1 was synthesised according to the method described in WO2022/129137, which is incorporated in its entirety herein.
  • Absorption data are obtained by measuring the intensity of transmitted radiation through a solution sample. Absorption intensity is plotted vs. incident wavelength to generate an absorption spectrum.
  • a method for measuring absorption may comprise measuring a 15 mg / ml solution in a quartz cuvette and comparing to a cuvette containing the solvent only.
  • An organic electronic device was manufactured using the following method.
  • a glass substrate coated with a 150 nm thick layer of indium-tin oxide (ITO) was coated with a 0.2 % polyethyleneimine (PEIE) solution in water to form a ⁇ 5 nm film modifying the work function of the ITO.
  • PEIE polyethyleneimine
  • a ca. 200-330 nm thick bulk heterojunction layer of a mixture of Donor Polymer 2 : Compound 1 (1 : 1.5 by weight) was deposited over the modified ITO layer by bar coating from a 15 mg/ml 1,2,4 trimethylbenzene; dimethoxybenzene 95:5 v/v solvent mixture.
  • Donor Polymer 2 may be prepared as described in W02013/051676, the contents of which are incorporated herein by reference.
  • An organic electronic device was manufactured using the same method described for Eample Device 1, except that a ca. 200-330 nm thick bulk heterojunction layer of a mixture of Donor Polymer 2 : Compound 1 (1 : 1 by weight) was deposited over the modified ITO layer by bar coating from a 24 mg/ml chloroform; chloronapthalene 98:2 v/v solvent mixture.
  • devices comprising a compound according to the present disclosure exhibits surprisingly good characteristics. For example, absorption at long wavelengths, high external quantum efficiency (EQE) (in particular from 1470 nm to 1800 nm), and excellent dark current and current density.
  • EQE external quantum efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electromagnetism (AREA)
  • Light Receiving Elements (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un composé de formule (I), dans laquelle : D est un groupe donneur d'électrons; B1 à chaque occurrence est indépendamment un groupe de pontage; n est au moins 1; m est 0 ou au moins 1; p est 0 ou 1; q est 0 ou 1; A1 est un groupe représenté par la formule (II) dans laquelle : R3 est indépendamment H ou un substituant; Y est C=O, C=S SO, SO2, NR33 ou C(R33)2, R33 est CN ou COOR40; R40 à chaque occurrence est H ou un substituant; et R4 à chaque occurrence est H ou un substituant choisi dans le groupe constitué par hydrocarbyle en C1-20 et un groupe attracteur d'électrons, à condition qu'au moins un R4 soit CN.
PCT/EP2023/083051 2022-11-28 2023-11-24 Composés utiles dans la préparation d'un dispositif photosensible Ceased WO2024115329A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB2217856.0 2022-11-28
GB2217856.0A GB2624716A (en) 2022-11-28 2022-11-28 Compound

Publications (1)

Publication Number Publication Date
WO2024115329A1 true WO2024115329A1 (fr) 2024-06-06

Family

ID=84889504

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/083051 Ceased WO2024115329A1 (fr) 2022-11-28 2023-11-24 Composés utiles dans la préparation d'un dispositif photosensible

Country Status (2)

Country Link
GB (1) GB2624716A (fr)
WO (1) WO2024115329A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013051676A1 (fr) 2011-10-07 2013-04-11 住友化学株式会社 Composé polymère et élément électronique
WO2015044377A1 (fr) 2013-09-27 2015-04-02 Heliatek Gmbh Matériau organique photoactif pour composants optoélectroniques
CN110028488A (zh) 2019-05-15 2019-07-19 杭州师范大学 以茚并[1,2-b]芴为核的A-D-A型光伏小分子受体及其制备方法和应用
WO2019185578A1 (fr) 2018-03-28 2019-10-03 Merck Patent Gmbh Composés semi-conducteurs organiques
WO2019185580A1 (fr) 2018-03-28 2019-10-03 Merck Patent Gmbh Composés semi-conducteurs organiques
WO2020109823A1 (fr) * 2018-11-30 2020-06-04 Sumitomo Chemical Co., Ltd Composé photoactif
US20210336148A1 (en) 2020-04-28 2021-10-28 Raynergy Tek Incorporation Semiconductor mixed material and application thereof
CN111978335B (zh) 2020-08-24 2022-04-26 中国科学院化学研究所 一种带二乙烯基pi-桥的窄带隙有机受体光伏材料及其制备方法与应用
WO2022129137A1 (fr) 2020-12-15 2022-06-23 Cambridge Display Technology Ltd. Composé

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013051676A1 (fr) 2011-10-07 2013-04-11 住友化学株式会社 Composé polymère et élément électronique
WO2015044377A1 (fr) 2013-09-27 2015-04-02 Heliatek Gmbh Matériau organique photoactif pour composants optoélectroniques
WO2019185578A1 (fr) 2018-03-28 2019-10-03 Merck Patent Gmbh Composés semi-conducteurs organiques
WO2019185580A1 (fr) 2018-03-28 2019-10-03 Merck Patent Gmbh Composés semi-conducteurs organiques
WO2020109823A1 (fr) * 2018-11-30 2020-06-04 Sumitomo Chemical Co., Ltd Composé photoactif
CN110028488A (zh) 2019-05-15 2019-07-19 杭州师范大学 以茚并[1,2-b]芴为核的A-D-A型光伏小分子受体及其制备方法和应用
US20210336148A1 (en) 2020-04-28 2021-10-28 Raynergy Tek Incorporation Semiconductor mixed material and application thereof
CN111978335B (zh) 2020-08-24 2022-04-26 中国科学院化学研究所 一种带二乙烯基pi-桥的窄带隙有机受体光伏材料及其制备方法与应用
WO2022129137A1 (fr) 2020-12-15 2022-06-23 Cambridge Display Technology Ltd. Composé

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
JIA ZHENRONG ET AL: "High performance tandem organic solar cells via a strongly infrared-absorbing narrow bandgap acceptor", NATURE COMMUNICATIONS, vol. 12, no. 1, 8 January 2021 (2021-01-08), UK, XP093124673, ISSN: 2041-1723, Retrieved from the Internet <URL:https://www.nature.com/articles/s41467-020-20431-6> DOI: 10.1038/s41467-020-20431-6 *
JIA, Z ET AL.: "High performance tandem organic solar cells via a strongly infrared-absorbing narrow bandgap acceptor", NAT COMMUN, vol. 12, 2021, pages 178
JIEFENG HAI ET AL.: "Vinylene r-bridge: A simple building block for ultra-narrow bandgap nonfullerene acceptors enable 14.2% efficiency in binary organic solar cells", DYES AND PIGMENTS, vol. 188, 2021, pages 109171
QIAN ZHANG ET AL.: "Effect of r-bridges on the performance of indeno[1,2-b]fluorene-based non-fullerene small molecular acceptors", DYES AND PIGMENTS, vol. 169, 2019, pages 22 - 28, XP085710169, DOI: 10.1016/j.dyepig.2019.05.009
QUNPING FAN ET AL.: "Vinylene-Inserted Asymmetric Polymer Acceptor with Absorption Approaching 1000 nm for Versatile Applications in All-Polymer Solar Cells and Photomultiplication-Type Polymeric Photodetectors", ACS APPLIED MATERIALS & INTERFACES, vol. 14, no. 23, 2022, pages 26970 - 26977
XIAOJUN LI ET AL.: "Synthesis and Photovoltaic Properties of a Series of Narrow Bandgap Organic Semiconductor Acceptors with Their Absorption Edge Reaching 900 nm", CHEMISTRY OF MATERIALS, vol. 29, no. 23, 2017, pages 10130 - 10138, XP055594901, DOI: 10.1021/acs.chemmater.7b03928

Also Published As

Publication number Publication date
GB202217856D0 (en) 2023-01-11
GB2624716A (en) 2024-05-29

Similar Documents

Publication Publication Date Title
WO2023012365A1 (fr) Accepteurs non-fullerènes asymétriques photosensibles de type a-d-a&#39;-d-a destinés à être utilisés dans des dispositifs optoélectroniques
US12082426B2 (en) Photodetector composition
GB2572573A (en) Organic photodetector
US20200194684A1 (en) Photoactive compound
US20210175426A1 (en) Organic photodetector
US11968885B2 (en) Organic photodetector
TWI865736B (zh) 光活性組合物、調配物、有機光響應器件及形成其之方法、光感測器、以及使用該有機光響應器件之測定方法
GB2624715A (en) Composition
GB2627286A (en) Compound
WO2024115329A1 (fr) Composés utiles dans la préparation d&#39;un dispositif photosensible
CN117813310A (zh) 用于光电子装置中的a-d-a&#39;-d-a型的光响应性不对称非富勒烯受体
US20240196744A1 (en) Compound
WO2024170691A1 (fr) Composés destinés à être utilisés dans des photocapteurs
WO2024115333A1 (fr) Procédé et composé
US20250282793A1 (en) Compound
US20240206336A1 (en) Compound
WO2025186103A1 (fr) Composé
US20240206310A1 (en) Compound and device
WO2024115338A1 (fr) Dérivés de fullerène dans un dispositif photosensible
WO2024115332A1 (fr) Composés pour dispositifs électroniques organiques
WO2022129595A1 (fr) Matériau photoactif
GB2624717A (en) Formulation
GB2639045A (en) Compound

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23813656

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23813656

Country of ref document: EP

Kind code of ref document: A1