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WO2024170691A1 - Composés destinés à être utilisés dans des photocapteurs - Google Patents

Composés destinés à être utilisés dans des photocapteurs Download PDF

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WO2024170691A1
WO2024170691A1 PCT/EP2024/053884 EP2024053884W WO2024170691A1 WO 2024170691 A1 WO2024170691 A1 WO 2024170691A1 EP 2024053884 W EP2024053884 W EP 2024053884W WO 2024170691 A1 WO2024170691 A1 WO 2024170691A1
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group
occurrence
formula
substituent
unsubstituted
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Inventor
Connor PATRICK
Nir YAACOBI-GROSS
Michal MACIEJCZYK
Florence BOURCET
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Cambridge Display Technology Ltd
Sumitomo Chemical Co Ltd
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Cambridge Display Technology Ltd
Sumitomo Chemical Co Ltd
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    • 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
    • C07D495/12—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 three hetero rings
    • C07D495/14—Ortho-condensed systems
    • 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
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains three hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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

Definitions

  • WO2022/129137 discloses compounds of formula each EAG-EDG-EAG wherein EDG is a group of formula (II) and each EAG is independently an electron-accepting group of formula (HI):
  • W02021/079140 discloses a composition comprising an electron acceptor material and an electron donor material wherein the electron-acceptor material is a compound of formula EAG-EDG-EAG wherein each EAG is an electron-accepting group and EDG is a group of formula:
  • X 1 is O, S, Se, NR 2 or PR 2 wherein R 2 in each occurrence is H or a substituent;
  • Y 1 is O, S or Se
  • Ar 1 in each occurrence is independently an unsubstituted or substituted monocyclic or polycyclic aryl or heteroaryl group or is absent;
  • R 1 in each occurrence is independently a substituent
  • B 1 independently in each occurrence is a bridging group; fl and f2 are each 1 ; g is at least 1 ; and
  • a in each occurrence is independently a monovalent electron-accepting group.
  • At least one A is an electron-accepting group of formula (II): wherein:
  • R 3 is H or a substituent
  • Z are each independently CN, CF3 or COOR 40 wherein R 40 in each occurrence is H or a substituent
  • Ar 2 is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic ring.
  • Ar 2 is selected from: benzene substituted with at least one CN substituent; and an unsubstituted or substituted monocyclic or polycyclic heteroaromatic group.
  • the group of formula (II) has formula (Ila): wherein each X 7 -X 10 is independently CR 12 or N wherein R 12 in each occurrence is H or a substituent selected from C1-20 hydrocarbyl and an electron withdrawing group, with the proviso that when each of X 7 -X 10 is CR 12 then at least one R 12 is CN.
  • Ar 3 is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group.
  • Ar 2 is benzene substituted with at least one CN substituent.
  • B 1 is selected from unsubstituted or substituted furan; unsubstituted or substituted thiophene; or a fused analogue thereof.
  • B 1 is a group of formula (III): wherein Y 2 is O, S or Se; and Ar 4 is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group.
  • the group of Formula (III) is a group of formula (Illa): wherein R 8 in each occurrence is H or a substituent.
  • each Ar 1 is absent.
  • the present disclosure provides a composition comprising a compound as described herein and an electron-donating material.
  • 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 an organic photoresponsive device comprising an anode, a cathode and a photoactive layer disposed between the anode and the cathode wherein the photoactive layer comprises a composition as described herein.
  • 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 1000 nm.
  • Figure 1 is a schematic illustration of an organic photoresponsive device according to some embodiments.
  • 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.
  • the compound of formula (I) comprises an electron-donating group D:
  • X 1 is O, S, Se, NR 2 or PR 2 wherein R 2 in each occurrence is H or a substituent.
  • Y 1 is O, S or Se.
  • Ar 1 in each occurrence is independently an unsubstituted or substituted monocyclic or polycyclic aryl or heteroaryl group or is absent.
  • g is at least 1, preferably 1, 2 or 3.
  • R 1 in each occurrence is independently a substituent.
  • R 1 in each occurrence is independently selected from:
  • Ci-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 17 wherein R 17 is a Ci-12 hydrocarbyl COO or CO and one or more H atoms of the alkyl may be replaced with F; and an aromatic or heteroaromatic group, preferably a C6-20 aryl, more preferably phenyl, which is unsubstituted or substituted with one or more substituents.
  • substitutents of an aromatic or heteroaromatic group R 1 are preferably selected from substituents R 11 wherein R 11 in each occurrence is independently selected from F, Cl, Br, CN, NO2, and Ci -20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 17 wherein R 17 is a C1-12 hydrocarbyl, COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • Y 1 in each occurrence is independently selected from F, Cl, Br, CN, NO2, and C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, COO, CO or NR 17 wherein R 17 is a C 1-12 hydrocarbyl, and wherein one or more H atoms of the alkyl may be replaced with F.
  • R 17 is optionally a C1-12 alkyl or phenyl which is unsubstituted or substituted with one or more C1-6 alkyl groups.
  • 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.
  • R 2 is preferably H; C1-12 alkyl wherein one or more C atoms of the C1-12 alkyl other than a terminal C atom or the C atom bound to N of NR 2 may be replaced with O, S, CO or COO; or an aromatic or heteroaromatic group, preferably a C6-12 aryl group, more preferably phenyl, which may be unsubstituted or substituted with one or more substituents.
  • substituents of an aromatic or heteroaromatic group R 2 are preferably selected from R 11 as described above.
  • R 2 is H or a C1-20 hydrocarbyl group.
  • a Ci -20 hydrocarbyl group as described anywhere herein may be selected from C1-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 alkyl groups.
  • Each of the electron-accepting groups A of formula (I) has a lowest unoccupied molecular orbital (LUMO) level that is deeper (i.e., further from vacuum) than the donor group D of formula (I), preferably at least 1 eV deeper.
  • the LUMO levels of electron-accepting groups A and electron-donating groups D 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).
  • the compound of formula (I) has a peak absorption wavelength greater than 1000 nm, optionally at least 1200 nm, preferably less than 1800 nm.
  • Each Ar 1 independently may or may not be present.
  • the group D has formula D-l :
  • R 4 in each occurrence is independently H or a substituent, optionally H or a substituent R 11 as described above.
  • each R 4 is H.
  • both Ar 1 groups are present in which case the Ar 1 groups are the same or different.
  • Ar 1 in each occurrence is independently selected from furan; thiophene; furofuran; thienothiophene; and furothiophene.
  • Substituents of Ar 1 are optionally selected from substituents R 11 as described above.
  • Bridging units B 1 are preferably each selected from vinylene, arylene and heteroarylene.
  • the arylene and heteroarylene groups are preferably monocyclic or bicyclic groups, each of which may be unsubstituted or substituted with one or more substituents.
  • each B 1 contains at least one arylene or heteroarylene group, more preferably at least one heteroarylene group.
  • Exemplary monocyclic aromatic and heteroaromatic groups B 1 are benzene, thiophene and furan, each of which may be unsubstituted or substituted with one or more substituents, optionally one or more substituents R 8 as described below.
  • Exemplary bicyclic groups B 1 are selected from formulae (III) and (IV):
  • Ar 4 is an unsubstituted or substituted monocyclic aromatic or heteroaromatic group, preferably benzene; thiophene; furan; pyridine; pyrazine; or piperidine, each of which may be unsubstituted or substituted with one or more substituents, optionally one or more substituents R 8 as described below, and Y 2 is O, S or Se.
  • heteroarylene groups B 1 are selected from units of formulae (Via) - (VIo):
  • R 55 is H or a substituent, optionally H or a C1-20 hydrocarbyl group; and R 8 in each occurrence is independently H or a substituent, preferably H or a substituent selected from:
  • Substituents of a phenyl group R 8 may be selected from substituents R 11 as described above.
  • R 6 is H or a substituent, preferably H or a C1-20 hydrocarbyl group.
  • a Ci -20 hydrocarbyl group as described anywhere herein may be selected from C1-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 alkyl groups.
  • 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; NO2; 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, C1-20 alkyl or C1-19 alkoxy.
  • R 8 groups of formulae (Via), (VIb) and (Vic) may be linked to form an optionally substituted bicyclic ring.
  • the monovalent acceptor groups A may each independently be selected from any such units known to the skilled person.
  • the A groups of the compound of formula (I) may be the same or different, preferably the same.
  • Exemplary monovalent acceptor groups include, without limitation, groups of formulae (IXa)- (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.
  • the N atom of formula (IXe) may be unsubstituted or substituted.
  • R 3 is H or a substituent, preferably H or 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 3 is H.
  • J is O or S, preferably O.
  • R 13 in each occurrence is a substituent, optionally 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.
  • R 15 in each occurrence is independently H; F; 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; 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; or a group selected from:
  • R 16 is H or a substituent, preferably a substituent selected from:
  • Ar 5 in each occurrence is independently an unsubstituted or substituted aryl or heteroaryl group, preferably thiophene, and w is 1, 2 or 3;
  • 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.
  • 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 5 and Ar 6 are optionally selected from 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.
  • 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 , where present, are optionally selected from non-H groups of R 25 .
  • T 3 is benzothiadi azole.
  • 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 3 , and which is bound to an aromatic C atom of B 1 or B 2 and to a boron substituent of B 1 or B 2 .
  • Preferred groups A are groups having a non-aromatic carbon-carbon bond which is bound directly to B 1 .
  • At least one A preferably both groups A, are a group of formula (II): wherein:
  • R 3 is as described above;
  • Ar 2 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, for example quinoxaline; and each Z is independently CN, CFs or COOR 40 wherein R 40 in each occurrence is H or a substituent, preferably H or a C1-20 hydrocarbyl group.
  • each Z is the same.
  • each Z is CN.
  • Ar 2 may be unsubstituted or substituted with one or more substituents.
  • Substituents of Ar 2 are preferably selected from groups R 11 as described above.
  • each X 7 -X 10 is independently CR 12 or N wherein R 12 in each occurrence is H or a substituent selected from C1-20 hydrocarbyl and an electron withdrawing group.
  • the electron withdrawing group is F, Cl, Br or CN, more preferably F, Cl or CN; and most preferably CN.
  • the Ci -20 hydrocarbyl group R 12 may be selected from C1-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 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.
  • Ar 3 is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group.
  • Ar 3 is benzene which is unsubstituted or substituted with one or more substituents.
  • Substituents of Ar 3 may be selected from R 11 as described above, more preferably R 12 as described above.
  • Exemplary groups of formula (IXd) include:
  • Exemplary groups of formula (IXe) include:
  • An exemplary group of formula (IXj) is: wherein Ak is a C1-12 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 -SOs'; and each benzene ring is independently unsubstituted or substituted with one or more substituents selected from substituents described with reference to R 3 .
  • Exemplary groups of formula (IXm) are:
  • An exemplary group of formula (IXn) is:
  • Groups of formula (IXo) are bound directly to a bridging group B 1 or B 2 substituted with a group of formula -B(R 14 )2 wherein R 14 in each occurrence is a substituent, optionally a C1-20 hydrocarbyl 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 C1-12 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 alkyl groups.
  • the group of formula (IXo), the B 1 or B 2 group and the B(R 14 )2 substituent of B 1 or B 2 may be linked together to form a 5- or 6-membered ring.
  • groups of formula (IXo) are selected from:
  • FIG. 1 illustrates an organic photoresponsive device, preferably an organic photodetector, 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.
  • the bulk heterojunction layer comprises or consists of the compound of formula (I) and an electron-donating compound.
  • the bulk heterojuction layer comprise one or more further materials, for example one or more further electron-donating materials and / or one or more further 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, or each, electron-donating material has a type II interface with the, or each, electron-accepting material, i.e. the or each electron-donating material has a shallower HOMO and LUMO that the corresponding HOMO and LUMO levels of the or each electronaccepting material.
  • the compound of formula (I) has 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 compound of formula (I) is less than 1.4 eV.
  • 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 photoresponsive device comprises a bulk heterojunction photoactive layer 105.
  • the photoactive layer comprises an electron-accepting sub-layer comprising or consisting of the compound of formula (I) disposed between the anode and cathode; and an electron-donating sub-layer comprising or consisting of one or more electron-donating materials disposed between the anode and the electron-accepting layer and in direct contact with the electron-accepting layer.
  • 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 the photoactive layer.
  • a hole-transporting layer and / or an electron- blocking layer is disposed between the anode and the photoactive layer.
  • an electron-transporting layer and / or a hole-blocking layer is disposed between the cathode and the photoactive layer.
  • a work function modification layer is disposed between the photoactive layer and the anode, and/or between the photoactive layer and the cathode.
  • 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.
  • Exemplary electron-donating materials of a photoactive layer as described herein are disclosed in, for example, WO2013/051676, the contents of which are incorporated herein by reference.
  • the electron-donating material may be a non-polymeric 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.
  • exemplary electron-donating polymers polymers selected from conjugated hydrocarbon or heterocyclic polymers including poly acene, poly aniline, 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(terthioph
  • donor polymers are copolymers of polyfluorenes and polythiophenes, each of which may be substituted, and polymers comprising benzothiadiazole-based and thiophene-based repeating units, each of which may be substituted.
  • the donor polymer is preferably a donor-acceptor (DA) copolymer comprising a donor repeat unit and an acceptor repeat unit.
  • DA donor-acceptor
  • Preferred donor units are selected from thiophene which is optionally substituted with one or more substituents R 11 as described above; and repeat units of formulae (X), (XII) and (XII): wherein:
  • Y A in each occurrence is independently O, S or NR 55 ;
  • Z A in each occurrence is O, CO, S, NR 55 or C(R 54 )2; and
  • R 51 , R 54 and R 55 independently in each occurrence is H or a substituent.
  • R 51 independently in each occurrence is selected firomH; F; C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 2 , 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.
  • the one or more substituents of Ar 3 may be selected from 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.
  • each R 51 is H.
  • each R 54 is selected from the group consisting of:
  • Substituents of Ar 7 are preferably selected from F; Cl; NO2; CN; and C1-20 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 55 is H or C 1-20 hydrocarbyl group.
  • R 18 and R 19 are each independently selected from H; F; C1-12 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 C1-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO.
  • Y 3 is O, S or Se, preferably S;
  • R 5 in each occurrence is H or a substituent, more preferably H or a substituent R 11 as described above, most preferably H;
  • Q is C(R 21 )2 or Si(R 21 )2 wherein R 21 in each occurrence is a substituent, preferably a substituent selected from: Ci-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 17 wherein R 17 is a Ci-nhydrocarbyl, COO or CO and one or more H atoms of the alkyl may be replaced with F; and an aromatic or heteroaromatic group, preferably a C6-20 aryl, more preferably phenyl, which is unsubstituted or substituted with one or more substituents.
  • Substituents of an aromatic or heteroaromatic group R 21 may be selected from R 11 as described above.
  • Preferred acceptor units include benzothiadiazole which is optionally substituted with one or more substituents R 11 ; and repeat units of formula (XIII): wherein R 2 is as described above; and Y 4 is O, S or Se, preferably S.
  • the compound of formula (I) is the only electron-accepting material of an electron-accepting sub-layer or a bulk heterojunction layer as described herein.
  • an electron-accepting layer or a bulk heterojunction 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 Csr 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)
  • ThCBM-type fullerene derivatives e.g. thienyl-Cei-butyric acid methyl ester (CeoThCBM).
  • Fullerene derivatives may have formul 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):
  • 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 C1-20 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 C1-12 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.
  • an electron-accepting sub-layer or a bulk heterojunction layer is formed by depositing a formulation comprising the compound of formula (I) and any other components of the layer, including one or more electron-donating materials in the case of a bulk heterojunction layer, dissolved or dispersed in a solvent or a mixture of two or more solvents followed by evaporation of the one 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 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 C1-10 alkyl benzoate, benzyl benzoate or dimethoxybenzene.
  • a mixture of trimethylbenzene and benzyl benzoate is used as the solvent.
  • a mixture of trimethylbenzene and dimethoxy benzene is used as the solvent.
  • the formulation may comprise further components in addition to the electron-accepting material, the electron-donating material 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.
  • the photoactive layer is formed over one of the anode and cathode of the organic photoresponsive device and the other of the anode and cathode is formed over the photoactive layer.
  • 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 1000 nm or at least 1200 nm, optionally in the range of 1000-1500 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 anon-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.
  • the detection surface area of an OPD as described herein may be selected according to the desired application.
  • an OPD as described herein has a detection surface area of 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 .
  • 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).
  • absorption spectra were measured using a Cary 5000 UV-VIS-NIR Spectrometer. Measurements were taken from 175 nm to 3300 nm using a PbSmart NIR detector for extended photometric range with variable slit widths (down to 0.01 nm) for optimum control over data resolution.
  • absorption values are of a solution.
  • 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.
  • solution absorption data as provided herein is as measured in toluene solution.
  • Donor groups D in which at least one Ar 1 is present may be prepared according to General
  • a compound of formula (I) containing both a heteroaromatic and a vinylene bridge may be prepared according to General Scheme 4.
  • Table 4 shows modeled band gaps for compounds containing a thienopyrazine bridge.
  • Table 5 shows modeled band gaps for compounds in which only one Ar 1 group is present.
  • Table 6 shows modeled band gaps for compounds in which two Ar 1 groups are present.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Composé représenté par la formule (I) dans laquelle X1 désigne O, S, Se, NR2 ou PR2, où R2 désigne à chaque occurrence H ou un substituant; Y1 représente O, S ou Se; Ar1 représente indépendamment à chaque occurrence un groupe aryle ou hétéroaryle monocyclique ou polycyclique substitué ou non substitué ou est absent; R1 désigne indépendamment à chaque occurrence un substituant; B1 désigne indépendamment à chaque occurrence un groupe de pontage; f1 et f2 valent chacun 1; g vaut au moins 1; et A désigne indépendamment à chaque occurrence un groupe accepteur d'électrons monovalent.
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Citations (6)

* 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
CN111018884A (zh) * 2019-12-17 2020-04-17 河南大学 一种基于二（并二噻吩）并六元杂环的受体材料及其制备方法和应用
WO2021079140A1 (fr) 2019-10-24 2021-04-29 Sumitomo Chemical Co., Ltd Matériaux moléculaires à base de noyau de phénoxyazine pour cellules solaires organiques à hétérojonction
WO2022019300A1 (fr) * 2020-07-22 2022-01-27 住友化学株式会社 Composé et élément de conversion photoélectrique l'utilisant
WO2022129137A1 (fr) 2020-12-15 2022-06-23 Cambridge Display Technology Ltd. Composé
WO2023172010A1 (fr) * 2022-03-07 2023-09-14 한국화학연구원 Matériau semi-conducteur organique de type n absorbant dans le proche infrarouge et photodétecteur organique le comprenant

Patent Citations (6)

* 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
WO2021079140A1 (fr) 2019-10-24 2021-04-29 Sumitomo Chemical Co., Ltd Matériaux moléculaires à base de noyau de phénoxyazine pour cellules solaires organiques à hétérojonction
CN111018884A (zh) * 2019-12-17 2020-04-17 河南大学 一种基于二（并二噻吩）并六元杂环的受体材料及其制备方法和应用
WO2022019300A1 (fr) * 2020-07-22 2022-01-27 住友化学株式会社 Composé et élément de conversion photoélectrique l'utilisant
WO2022129137A1 (fr) 2020-12-15 2022-06-23 Cambridge Display Technology Ltd. Composé
WO2023172010A1 (fr) * 2022-03-07 2023-09-14 한국화학연구원 Matériau semi-conducteur organique de type n absorbant dans le proche infrarouge et photodétecteur organique le comprenant

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