WO2022207312A1 - Indacenetetrone-based dyes as photoactive material for organic photoelectric conversion layers in organic photodiodes - Google Patents

Indacenetetrone-based dyes as photoactive material for organic photoelectric conversion layers in organic photodiodes Download PDF

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Publication number
WO2022207312A1
WO2022207312A1 PCT/EP2022/056719 EP2022056719W WO2022207312A1 WO 2022207312 A1 WO2022207312 A1 WO 2022207312A1 EP 2022056719 W EP2022056719 W EP 2022056719W WO 2022207312 A1 WO2022207312 A1 WO 2022207312A1
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organic
photoelectric conversion
compound
image sensor
conversion layer
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PCT/EP2022/056719
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French (fr)
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David Danner
Vitor Angelo Fonseca DEICHMANN
Anthony Roberts
Dennis CHERCKA
Silvia Rosselli
Berthold WEGNER
Nikolaus Knorr
Vladimir Yakutkin
Tzenka Miteva
Gabriele Nelles
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Sony Group Corporation
Sony Europe B.V.
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Priority to EP22715043.0A priority Critical patent/EP4314166A1/en
Publication of WO2022207312A1 publication Critical patent/WO2022207312A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C07C49/683—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/687—Unsaturated compounds containing a keto groups being part of a ring containing halogen
    • C07C49/697—Unsaturated compounds containing a keto groups being part of a ring containing halogen containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14665—Imagers using a photoconductor layer
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the field of the DISCLOSURE lies in active materials for organic image sensors.
  • the present disclosure relates to indacenetetrone-based active materials and their use in photoelectric conversion layer(s) and/or an organic image sensor and methods for their synthesis.
  • the present disclosure also relates to photoelectric conversion layer(s) comprising an active material according to the present disclosure, to a device, comprising active material(s) according to the present disclosure or photoelectric conversion layer(s) according to the present disclosure.
  • the present disclosure relates to an organic image sensor comprising photoelectric conversion layer(s) according to the present disclosure.
  • Image sensors which are semiconductor devices for converting an optical image into an electric signal, include a light-sensing unit for sensing light and a logic circuit unit for processing the sensed light into an electrical signal to store data.
  • the light-sensing unit includes a color filter and a photoelectric conversion film, a semiconductor p-n junction, such as silicon.
  • the color filter separates light according to colors, but reduces the spatial resolution and light collection and utilization efficiency.
  • photoelectric conversion units capable of detecting light of different wavelengths are stacked in a longitudinal direction.
  • photo electrical conversion unit is an organic photoelectric conversion layer based on p-n junction or bulk heterojunction.
  • the photoelectric conversion efficiency of such a unit depends strongly on the type of material used in the layer. With the organic materials available so far, low conversion efficiencies and high dark currents are reported.
  • an organic layer is used that is capable to absorb in the IR reagion but not in the visible reagion, that could be combined with a complementary metal oxide semiconductor (CMOS) based imager part for the visible range or with an organic based imager part that could absorb in the visible range.
  • CMOS complementary metal oxide semiconductor
  • white ligth is collected and filter have to be used to get the BGR pixel resolution.
  • filter have to be used to get the BGR pixel resolution.
  • light is separated according to colors but the spatial resolution and light collection and utilization efficiency is reduced.
  • R is selected from a linear or branched alkyl, cycloalkyl, aryl, alkylamine, arylamine, biaryl, heteroaryl, furanyl, thienyl, thieno[3,2-b]thienyl, benzo[l,2-b:4,5-b’]dithienyl, selenophenyl, naphthyl, quinolinyl, pyrrolyl, indolyl,
  • Ri and R 2 are each independently selected H, halogen, CF 3 , CN, alkoxy, cycloalkoxy, alkyl (preferably methyl), cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, and can be the same or different from each other,
  • X and Y are each independently selected from O, S, Se, Te, NRA, CRB, SiRc,
  • R 3 , RA, R B and Rc are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, with the proviso that the compound of the present disclosure is not any one of the following structures:
  • the present disclosure provides the use of a compound according to the present disclosure in a photoelectric conversion layer.
  • the present disclosure provides the use of a compound according to the present disclosure in an organic and/or hybrid module for optoelectronic application.
  • the present disclosure provides the use of a compound according to the present disclosure in a buffer layer.
  • the present disclosure provides a photoelectric conversion layer comprising a compound according to the present disclosure.
  • the present disclosure provides a buffer layer comprising a compound according to the present disclosure, wherein said buffer layer is an n-buffer layer and/or p-buffer layer.
  • the present disclosure provides an organic module for optoelectronic application comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure. [0018] The present disclosure provides an organic module for optoelectronic application comprising photoelectric conversion layer(s) comprising at least two compounds according to the present disclosure.
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the green absorption range; with an absorption coefficient between 480 and 600nm of up to more than 10 4 cm 1 .
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the red absorption range; with an absorption coefficient between 580 and 700nm of up to more than 10 4 cm 1 .
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the blue absorption range; with an absorption coefficient between 380 and 500 nm of up to more than 10 4 cm 1 .
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably for visible panchromatic in the range 400 to 700 nm, with an absorption coefficient between 400 and 700 nm of up to more than 10 4 cm 1 .
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the IR absorption range, preferably for IR in the range 700 to 900 nm, with an absorption coefficient between 700 and 900 nm.
  • the present disclosure provides a device, comprising one or more of compound(s) according to the present disclosure, photoelectric conversion layer(s) according to the present disclosure, buffer layer(s) according to the present disclosure, organic material(s) or organic module(s) according to the present disclosure.
  • the present disclosure provides an organic image sensor, comprising (a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) according to the present disclosure,
  • the present disclosure provides a hybrid Silicon-organic image sensor or organic image sensor, comprising
  • Figure 1 shows a state of the art CMOS image sensor.
  • Figure 2 shows a schematic representation of the hybrid silicon-organic image sensor.
  • Figure 3 shows a schematic representation of the organic based photoelectrical conversion unit with the different layers.
  • Figure 4 shows another schematic representation of the organic based photoelectrical conversion unit with the different layers.
  • Figure 5 shows a general synthetic route for the preparation of an indacenetetrone- based compound.
  • Figure 6 shows the indacenetetrone- based compound of Example 2, its synthesis and its absorption in solution.
  • Figure 7 shows the indacenetetrone- based compound of Example 3, its synthesis and its absorption in the solid state.
  • R is selected from a linear or branched alkyl, cycloalkyl, aryl, alkylamine, arylamine, biaryl, heteroaryl, furanyl, thienyl, thieno[3,2-b]thienyl, benzo[l,2-b:4,5-b’]dithienyl, selenophenyl, naphthyl, quinolinyl, pyrrolyl, indolyl, Ri and R2 are each independently selected H, halogen, CF3, CN, alkoxy, cycloalkoxy, alkyl (preferably methyl), cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, and can be the same or different from each other,
  • X and Y are each independently selected from O, S, Se, Te, NRA, CRB, SiRc,
  • R3, RA, RB and Rc are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl.
  • a compound according to the present disclosure is not any one of the following structures:
  • the indacenetetrone-based compound is represented by any of the following structures
  • a indacenetetrone-based compound according to the present disclosure preferably exhibits absorption in the visible absorption range (about 400 to about 700 nm), preferably in the range from 400 nm to 700 nm, or a sub-range thereof, preferably 400 nm to 500 nm, or 500 nm to 600 nm, or 600 nm to 700 nm.
  • the compounds of the present disclosure absorb in the blue absorption range.
  • the compounds of the present disclosure absorb in the green absorption range.
  • the compounds of the present disclosure absorb in the red absorption range.
  • the compounds of the present disclosure absorb in the IR absorption range, preferably in the range from 700 nm to 900 nm.
  • a compound according to the present disclosure preferably shows an extinction coefficient of > 10 4 LmoHcm 1 , more preferably of > 10 5 LmoHcm 1 .
  • [0049] provide the possibility to adjust the absorption spectrum of an active device via adjusting the absorption spectrum of only one active component.
  • the present disclosure provides the use of a compound according to the present disclosure in a photoelectric conversion layer.
  • the at least two of the compounds according to the present disclosure are used in a photoelectric conversion layer.
  • the present disclosure provides the use of a compound according to the present disclosure in an organic and/or hybrid module for optoelectronic application.
  • Said optoelectronic application can be an image sensor, a photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.
  • the at least two of the compounds according to the present disclosure are used in an organic and/or hybrid module.
  • the present disclosure provides the use of a compound according to the present disclosure in a buffer layer.
  • Said buffer layer can be a hole blocking layer, an electron blocking layer, a hole transport layer, or an electron transport layer.
  • the at least two of the compounds according to the present disclosure are used in a buffer layer.
  • the present disclosure provides a photoelectric conversion layer comprising a compound according to the present disclosure.
  • the photoelectric conversion layer optionally comprises further compound(s).
  • the present disclosure provides a buffer layer comprising a compound according to the present disclosure, wherein said buffer layer is an n-buffer layer and/or p-buffer layer.
  • the buffer layer optionally comprises further compound(s).
  • the present disclosure provides an organic module for optoelectronic application, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure.
  • Said optoelectronic application can be an image sensor, a photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.
  • the present disclosure provides an organic module for optoelectronic application, comprising photoelectric conversion layer(s) comprising at least two compounds according to the present disclosure.
  • Said optoelectronic application can be an image sensor, a photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the green absorption range; with an absorption coefficient between 480 and 600nm of up to more than 10 4 cm 1 ,
  • organic material or organic module optionally comprises further compound(s).
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the red absorption range; with an absorption coefficient between 580 and 700nm of up to more than 10 4 cm 1 ,
  • the organic material or organic module optionally comprises further compound(s).
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the blue absorption range; with an absorption coefficient between 380 and 500 nm of up to more than 10 4 cm 1 ,
  • organic material or organic module optionally comprises further compound(s).
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably for visible panchromatic in the range 400 to 700 nm, with an absorption coefficient between 400 and 700 nm of up to more than 10 4 cm 1 ,
  • the organic material or organic module optionally comprises further compound(s).
  • the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption for IR in the range 700 to 900 nm, with an absorption coefficient between 700 and 900 nm.
  • the organic material or organic module optionally comprises further compound(s).
  • the present disclosure provides a device, comprising one or more of compound(s) according to the present disclosure, photoelectric conversion layer(s) according to the present disclosure, buffer layer(s) according to the present disclosure, organic module(s) according to the present disclosure, organic material(s) or organic module(s) according to the present disclosure.
  • the device is preferably an organic image sensor, an hybrid image sensor, photodiode, organic photovoltaics, organic light-emitting diode (OLED), organic thin-film transistor (OTFT).
  • OLED organic light-emitting diode
  • OTFT organic thin-film transistor
  • said photoelectric conversion layer exhibits photo response in the visible absorption range.
  • the present disclosure provides an organic image sensor, comprising photoelectric conversion layer(s) according to the present disclosure.
  • the organic image sensor of the present disclosure preferably comprises
  • the organic image sensor does not comprise color filter(s).
  • the substrate can be silicon, quartz, glass, polymer, such as PMMA, PC, PS, COP, COP, PVA, PVP, PES, PET, PEN, mica, or combinations thereof.
  • polymer such as PMMA, PC, PS, COP, COP, PVA, PVP, PES, PET, PEN, mica, or combinations thereof.
  • the substrate can also be other photoelectric conversion unit(s) (e.g. blue 400-500nm and red 600-500nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600nm conversion device).
  • photoelectric conversion unit(s) e.g. blue 400-500nm and red 600-500nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600nm conversion device.
  • a device of this disclosure can comprise (i) two inorganic units with one organic unit, (ii) one inorganic unit with two organic units, or (iii) three organic units combined with each other in the organic image sensor. Any of the organic units can contain compounds/layers/devices according to this disclosure.
  • an organic image sensor consists of three organic conversion units containing compounds in layers as of this disclosure (in devices, each with transparent electrodes), combined with each other and operating each in one of the ranges 400nm to 500 nm, 500nm to 600 nm and 600 nm to700nm.
  • Combined units can be realized either by vertical and/or horizontal stacking of the organic-organic or organic-inorganic units.
  • the electrode material can be any organic compound. [0090]
  • ITO indium tin oxide
  • IFO fluorine-doped indium oxide
  • FTO fluorine-doped tin oxide
  • ATO antimonium-doped tin oxide
  • zinc oxide including Al, B and Ga doped zinc Oxide
  • IZO indium oxide-zinc oxide
  • non transparent or semitransparent metal or alloy or conductive polymer such as Au, Ag,
  • the present disclosure provides a hybrid Silicon-organic image sensor or organic image sensor, comprising
  • said organic photoelectric conversion unit of the image sensors of the present disclosure comprises different layers within the organic based photoelectrical conversion unit(s), such as
  • the organic image sensor of the present disclosure can have the structure:
  • the organic image sensor of the present disclosure can comprise different layer structures, in particular regarding the position of the n and p material with respect to the CMOS part.
  • the organic photoconversion unit can be used in combination with a Si based photoelectrical conversion unit where different layers absorb different color (RGB) in a hybrid silicon-organic image sensor (see Figure 2) or can be used without Si based photoelectrical conversion unit. In this case the organic photoconversion unit has the capability of absorbing different color (RGB) (see Figure 3).
  • the p-type material is a transparent P material, which has the quality when comprised in a P:N heterojunction or P:N bilayer or multilayer junction, particularly a P:N1:N2 or aPl:P2:N heterojunction or multilayer junction, to dissociate efficiently the excitons created in colored N, or in a mixture of colored N materials (N1 :N2), or in another colored P or in a mixture of colored P and N materials (P2:N) via a process of HOMO dissociation.
  • the p-type material is a transparent P material, it has the quality to accept hole from the colored N or the mixture of colored N materials, from another colored P material or from a mixture of colored N and another P material.
  • the p-type material is a transparent P material, it has the quality to transport the holes.
  • said organic photoelectric conversion unit comprising photoelectric conversion layer(s) further comprise phthalocyanine (Pc), subphthalocyanine (SubPc), merocyanine (MC), diketopyrrolopyrroles (DPP), borondipyrromethene (BODIPY), isoindigo (ID), perylene diimides (PDI), fulerenes, and naphthalodiimides.
  • Pc phthalocyanine
  • SubPc subphthalocyanine
  • MC merocyanine
  • DPP diketopyrrolopyrroles
  • BODIPY borondipyrromethene
  • ID isoindigo
  • PDI perylene diimides
  • fulerenes fulerenes
  • naphthalodiimides naphthalodiimides.
  • the substrate can also be other photoelectric conversion unit(s) (e.g. blue 400-500nm and red 600-500nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600nm conversion device).
  • photoelectric conversion unit(s) e.g. blue 400-500nm and red 600-500nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600nm conversion device.
  • a device of this disclosure can comprise (i) two inorganic units with one organic unit, (ii) one inorganic unit with two organic units, or (iii) three organic units combined with each other in the organic image sensor. Any of the organic units can contain compounds/layers/devices according to this disclosure.
  • the deposition methods to produce the organic photoelectrical conversion layer are PVD, CVD, spin coating, dipping coating, casting process, inkjet printing, screen printing, spray coating, offset printing.
  • R is selected from a linear or branched alkyl, cycloalkyl, aryl, alkylamine, arylamine, biaryl, heteroaryl, furanyl, thienyl, thieno[3,2-b]thienyl, benzo[l,2-b:4,5-b’]dithienyl, selenophenyl, naphthyl, quinolinyl, pyrrolyl, indolyl,
  • Ri and R2 are each independently selected H, halogen, CF 3 , CN, alkoxy, cycloalkoxy, alkyl (preferably methyl), cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, and can be the same or different from each other,
  • X and Y are each independently selected from O, S, Se, Te, NRA, CRB, SiRc,
  • R3, RA, RB and Rc are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, with the proviso that the compound is not any one of the following structures:
  • - preferably shows an extinction coefficient of > 10 4 LmoHcm 1 .
  • a buffer layer such as a hole blocking layer, an electron blocking layer, a hole transport layer, or an electron transport layer.
  • a photoelectric conversion layer comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s).
  • a buffer layer comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein said buffer layer is an n-buffer layer and/or p-buffer layer.
  • An organic module for optoelectronic application such as image sensor, photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules, comprising photoelectric conversion layer(s) comprising a compound according to any of embodiments (1) to (3).
  • An organic module for optoelectronic application such as image sensor, photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules, comprising photoelectric conversion layer(s) comprising at least two compounds according to any of embodiments (1) to (3).
  • An organic material or organic module for an image sensor comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably in the green absorption range; with an absorption coefficient between 480 and 600nm of up to more than 10 4 cm 1 .
  • An organic material or organic module for an image sensor comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably in the red absorption range; with an absorption coefficient between 580 and 700nm of up to more than 10 4 cm 1 .
  • An organic material or organic module for an image sensor comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably in the blue absorption range; with an absorption coefficient between 380 and 500 nm of up to more than 10 4 cm 1 .
  • An organic module for an image sensor comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably for visible panchromatic in the range 400 to 700 nm, with an absorption coefficient between 400 and 700 nm of up to more than 10 4 cm 1 .
  • An organic module for an image sensor comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the IR absorption range, preferably in the range 700 to 900 nm, with an absorption coefficient between 700 and 900 nm.
  • a device comprising one or more of compound(s) according to any one of embodiments (1) to (3), photoelectric conversion layer(s) according to embodiment (8), buffer layer(s) according to embodiment (9), organic module(s) according to any of embodiments (10), (11), (15) or (16), organic material(s) or organic module(s) according to any of embodiments (12) to (14), wherein said device is preferably an organic image sensor, an hybrid image sensor, photodiode, organic photovoltaic s, organic light-emitting diode (OLED), organic thin-film transistor (OTFT).
  • OLED organic light-emitting diode
  • OFT organic thin-film transistor
  • a hybrid Silicon-organic image sensor or organic image sensor comprising
  • the p-type material is a transparent P material, which has the quality when comprised in a P:N heterojunction or P:N bilayer or multilayer junction, particularly a P:N1:N2 or aPl:P2:N heterojunction or multilayer junction, to dissociate efficiently the excitons created in colored N, or in a mixture of colored N materials (N1 :N2), or in another colored P or in a mixture of colored P and N materials (P2:N) via a process of HOMO dissociation, and/or has the quality to accept hole from the colored N or the mixture of colored N materials, from another colored P material or from a mixture of colored N and another P material, and/or has the quality to transport the holes.
  • the p-type material is a transparent P material, which has the quality when comprised in a P:N heterojunction or P:N bilayer or multilayer junction, particularly a P:N1:N2 or aPl:P2:N heterojunction or multilayer junction, to
  • absorption in the visible wavelength range or “dye exhibiting absorption in the visible wavelength range”, as used herein, is meant to refer to a compound/dye that is able to absorb light in only one or several parts of the entire range indicated or over the total range.
  • a compound may only absorb in the range of from 500 - 700 nm, whereas another compound may absorb in the range of from 400 - 700 nm or 500 - 600 nm, whereas a third compound may absorb over the range of from 400 - 500 nm (or the above described sub-ranges of preferably 400 nm to 500 nm, or 500 nm to 600 nm, or 600 nm to 700 nm). All these scenarios are meant to be encompassed by such wording.
  • absorption in the IR range or “dye exhibiting absorption in the IR range”, as used herein, is meant to refer to a compound/dye that is able to absorb light in wavelength ranges above 700 nm, preferably between 700 and 900 nm.
  • Electrode refers to an electrical lead to apply voltage.
  • An electrode may be "interdigitated", meaning that it has a comb-like shape with two combs lying opposite each other and the respective figures of the combs engaging with each other.
  • an electrode may be a non-interdigitated.
  • An electrode may be transparent or non-transparent.
  • a transparent electrode may, for example, be formed from indium tin oxide (ITO) or from fluorinated tin oxide (FTO).
  • a non-transparent electrode may be reflective and may, for example, be formed from silver (Ag) or gold (Au).
  • the present inventors have found novel indacenetetrone based dyes / compounds which are highly suitable as active materials for organic photoelectric conversion layers with improved conversion efficiency and response speed in organic photodiodes for vertically- integrated (VI) CMOS image sensors application.
  • V vertically- integrated
  • the present disclosure relates to indacenetetrone based dyes / compounds as active materials for the organic photoconversion unit.
  • the organic photoconversion unit can be used in combination with a Si based photoelectrical conversion unit where different layer absorbed different colour (RGB and/or Visible Panchromatic) in a hybrid Silicon-organic image sensor or can be used without Si based photoelectrical conversion unit. In this case the organic photoconversion unit having the capability of absorbing different colour (RGB and/or Visible Panchromatic).
  • different molecular dye / compound structures, different components and combination of the photoelectric conversion layer (list of possible electrodes, list of other possible n and p type materials that could be used together with the IT dyes, list of different n and p type buffer layer), different layer structures (position of the n and p material with respect to the electrodes) and different process temperature for processing the layer (from 150 to 245°Celsius) are described herein.
  • the present disclosure further relates to indacenetetrone based dyes / compounds of the present disclosure which are used in a bulk heterojunction (mixed p-n layer) or PN heterojunction (formed between a p layer and n layer or PiN junction (p layer - mixed layer as p-n bulk heterojunction - n-layer) in the photoelectric conversion material layer.
  • IT-MeTh presents an absorption maximum at 464 nm in solution (Toluene, concentration 10 5 M and 10 6 M), see Figure 6B.
  • IT-TPA presents an absorption maximum at 597 nm in solid state (vacuum deposited film), see Figure 6B.

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Abstract

The field of the disclosure lies in active materials for organic image sensors. The present disclosure relates to indacenetetrone-based active materials and their use in photoelectric conversion layer(s) and/or an organic image sensor and methods for their synthesis. The present disclosure also relates to photoelectric conversion layer(s) comprising an active material according to the present disclosure, to a device, comprising active material(s) according to the present disclosure or photoelectric conversion layer(s) according to the present disclosure. Moreover, the present disclosure relates to an organic image sensor comprising photoelectric conversion layer(s) according to the present disclosure. The indacenetetrone compounds have the following formula (I).

Description

INDACENETETRONE-BASED DYES AS PHOTOACTIVE MATERIAL FOR ORGANIC PHOTOELECTRIC CONVERSION LAYERS IN ORGANIC PHOTODIODES
BACKGROUND
[0001] The field of the DISCLOSURE lies in active materials for organic image sensors. [0002] The present disclosure relates to indacenetetrone-based active materials and their use in photoelectric conversion layer(s) and/or an organic image sensor and methods for their synthesis.
[0003] The present disclosure also relates to photoelectric conversion layer(s) comprising an active material according to the present disclosure, to a device, comprising active material(s) according to the present disclosure or photoelectric conversion layer(s) according to the present disclosure.
[0004] Moreover, the present disclosure relates to an organic image sensor comprising photoelectric conversion layer(s) according to the present disclosure.
DESCRIPTION OF THE RELATED ART [0005] The “background” description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against the present disclosure.
[0006] Image sensors, which are semiconductor devices for converting an optical image into an electric signal, include a light-sensing unit for sensing light and a logic circuit unit for processing the sensed light into an electrical signal to store data.
[0007] In the state of the art, the light-sensing unit includes a color filter and a photoelectric conversion film, a semiconductor p-n junction, such as silicon. The color filter separates light according to colors, but reduces the spatial resolution and light collection and utilization efficiency.
[0008] In order to overcome this problem geometries are reported where photoelectric conversion units capable of detecting light of different wavelengths are stacked in a longitudinal direction. In particular such photo electrical conversion unit is an organic photoelectric conversion layer based on p-n junction or bulk heterojunction. The photoelectric conversion efficiency of such a unit depends strongly on the type of material used in the layer. With the organic materials available so far, low conversion efficiencies and high dark currents are reported.
[0009] In another solution, an organic layer is used that is capable to absorb in the IR reagion but not in the visible reagion, that could be combined with a complementary metal oxide semiconductor (CMOS) based imager part for the visible range or with an organic based imager part that could absorb in the visible range. In both cases white ligth is collected and filter have to be used to get the BGR pixel resolution. In this case, as well as in the case of color filter, light is separated according to colors but the spatial resolution and light collection and utilization efficiency is reduced.
SUMMARY
[0010] In the following, the elements of the invention will be described. These elements are listed with specific embodiments, however, it should be understood that they may be combined in any manner and in any number to create additional embodiments. The variously described examples and preferred embodiments should not be construed to limit the present invention to only the explicitly described embodiments. This description should be understood to support and encompass embodiments which combine two or more of the explicitly described embodiments or which combine the one or more of the explicitly described embodiments with any number of the disclosed and/or preferred elements. Furthermore, any permutations and combinations of all described elements in this application should be considered disclosed by the description of the present application unless the context indicates otherwise.
[0011] The present disclosure provides an indacenetetrone-based compound represented by formula I
Figure imgf000004_0001
wherein
R is selected from a linear or branched alkyl, cycloalkyl, aryl, alkylamine, arylamine, biaryl, heteroaryl, furanyl, thienyl, thieno[3,2-b]thienyl, benzo[l,2-b:4,5-b’]dithienyl, selenophenyl, naphthyl, quinolinyl, pyrrolyl, indolyl,
Figure imgf000005_0001
Ri and R2 are each independently selected H, halogen, CF3, CN, alkoxy, cycloalkoxy, alkyl (preferably methyl), cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, and can be the same or different from each other,
X and Y are each independently selected from O, S, Se, Te, NRA, CRB, SiRc,
R3, RA, RB and Rc are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, with the proviso that the compound of the present disclosure is not any one of the following structures:
Figure imgf000006_0001
[0012] The present disclosure provides the use of a compound according to the present disclosure in a photoelectric conversion layer.
[0013] The present disclosure provides the use of a compound according to the present disclosure in an organic and/or hybrid module for optoelectronic application.
[0014] The present disclosure provides the use of a compound according to the present disclosure in a buffer layer.
[0015] The present disclosure provides a photoelectric conversion layer comprising a compound according to the present disclosure.
[0016] The present disclosure provides a buffer layer comprising a compound according to the present disclosure, wherein said buffer layer is an n-buffer layer and/or p-buffer layer.
[0017] The present disclosure provides an organic module for optoelectronic application comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure. [0018] The present disclosure provides an organic module for optoelectronic application comprising photoelectric conversion layer(s) comprising at least two compounds according to the present disclosure.
[0019] The present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the green absorption range; with an absorption coefficient between 480 and 600nm of up to more than 104 cm 1.
[0020] The present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the red absorption range; with an absorption coefficient between 580 and 700nm of up to more than 104 cm 1.
[0021] The present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the blue absorption range; with an absorption coefficient between 380 and 500 nm of up to more than 104 cm 1.
[0022] The present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably for visible panchromatic in the range 400 to 700 nm, with an absorption coefficient between 400 and 700 nm of up to more than 104 cm 1.
[0023] The present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the IR absorption range, preferably for IR in the range 700 to 900 nm, with an absorption coefficient between 700 and 900 nm.
[0024] The present disclosure provides a device, comprising one or more of compound(s) according to the present disclosure, photoelectric conversion layer(s) according to the present disclosure, buffer layer(s) according to the present disclosure, organic material(s) or organic module(s) according to the present disclosure.
[0025] The present disclosure provides an organic image sensor, comprising (a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) according to the present disclosure,
(b) at least one electrode,
(c) a substrate,
(d) optionally, a second electrode on top of said photoelectric conversion layer(s), preferably not comprising color filter(s).
[0026] The present disclosure provides a hybrid Silicon-organic image sensor or organic image sensor, comprising
(a) an organic photoelectric conversion unit or units comprising photoelectric conversion layer(s) according to the present disclosure,
(b) optionally, a Si based photoelectric conversion unit,
(c) metal wiring,
(d) a (CMOS) substrate,
(e) insulating layer(s), preferably oxide.
[0027] The foregoing paragraphs have been provided by way of general introduction and are not intended to limit the scope of the following claims. The described embodiments, together with further advantages, will be best understood by reference to the following detailed description taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS [0028] A more complete appreciation of the disclosure and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
[0029] Figure 1 shows a state of the art CMOS image sensor.
[0030] Figure 2 shows a schematic representation of the hybrid silicon-organic image sensor. [0031] Figure 3 shows a schematic representation of the organic based photoelectrical conversion unit with the different layers.
[0032] Figure 4 shows another schematic representation of the organic based photoelectrical conversion unit with the different layers.
[0033] Figure 5 shows a general synthetic route for the preparation of an indacenetetrone- based compound.
[0034] Figure 6 shows the indacenetetrone- based compound of Example 2, its synthesis and its absorption in solution. [0035] Figure 7 shows the indacenetetrone- based compound of Example 3, its synthesis and its absorption in the solid state.
DETAILED DESCRIPTION OF THE EMBODIMENTS [0036] As discussed above, the present disclosure provides an indacenetetrone-based compound represented by formula I
Figure imgf000009_0001
wherein
R is selected from a linear or branched alkyl, cycloalkyl, aryl, alkylamine, arylamine, biaryl, heteroaryl, furanyl, thienyl, thieno[3,2-b]thienyl, benzo[l,2-b:4,5-b’]dithienyl, selenophenyl, naphthyl, quinolinyl, pyrrolyl, indolyl,
Figure imgf000009_0002
Ri and R2 are each independently selected H, halogen, CF3, CN, alkoxy, cycloalkoxy, alkyl (preferably methyl), cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, and can be the same or different from each other,
X and Y are each independently selected from O, S, Se, Te, NRA, CRB, SiRc,
R3, RA, RB and Rc are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl.
[0037] A compound according to the present disclosure is not any one of the following structures:
Figure imgf000010_0001
[0038] In one embodiment, the indacenetetrone-based compound is represented by any of the following structures
Figure imgf000011_0001
[0039] A indacenetetrone-based compound according to the present disclosure preferably exhibits absorption in the visible absorption range (about 400 to about 700 nm), preferably in the range from 400 nm to 700 nm, or a sub-range thereof, preferably 400 nm to 500 nm, or 500 nm to 600 nm, or 600 nm to 700 nm.
[0040] In one embodiment, the compounds of the present disclosure absorb in the blue absorption range.
[0041] In one embodiment, the compounds of the present disclosure absorb in the green absorption range.
[0042] In one embodiment, the compounds of the present disclosure absorb in the red absorption range.
[0043] In one embodiment, the compounds of the present disclosure absorb in the IR absorption range, preferably in the range from 700 nm to 900 nm. [0044] A compound according to the present disclosure preferably shows an extinction coefficient of > 104 LmoHcm 1, more preferably of > 105 LmoHcm 1.
[0045] The compounds according to the present disclosure preferably:
[0046] exhibit good photo- and thermal stability (up to 300°C),
[0047] allow tuning of HOMO and LUMO energies,
[0048] allow tuning of the absorption maximum (optical band gap) and shape over a broad range,
[0049] provide the possibility to adjust the absorption spectrum of an active device via adjusting the absorption spectrum of only one active component.
[0050] exhibit high electrons and holes mobilities,
[0051] exhibit high exciton diffusion efficiencies.
[0052] Their processability is already proven for OPV.
[0053] As discussed above, the present disclosure provides the use of a compound according to the present disclosure in a photoelectric conversion layer.
[0054] In one embodiment, the at least two of the compounds according to the present disclosure are used in a photoelectric conversion layer.
[0055] As discussed above, the present disclosure provides the use of a compound according to the present disclosure in an organic and/or hybrid module for optoelectronic application. [0056] Said optoelectronic application can be an image sensor, a photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.
[0057] In one embodiment, the at least two of the compounds according to the present disclosure are used in an organic and/or hybrid module.
[0058] As discussed above, the present disclosure provides the use of a compound according to the present disclosure in a buffer layer.
[0059] Said buffer layer can be a hole blocking layer, an electron blocking layer, a hole transport layer, or an electron transport layer.
[0060] In one embodiment, the at least two of the compounds according to the present disclosure are used in a buffer layer. [0061] As discussed above, the present disclosure provides a photoelectric conversion layer comprising a compound according to the present disclosure.
[0062] The photoelectric conversion layer optionally comprises further compound(s).
[0063] As discussed above, the present disclosure provides a buffer layer comprising a compound according to the present disclosure, wherein said buffer layer is an n-buffer layer and/or p-buffer layer.
[0064] The buffer layer optionally comprises further compound(s).
[0065] As discussed above, the present disclosure provides an organic module for optoelectronic application, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure.
[0066] Said optoelectronic application can be an image sensor, a photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.
[0067] As discussed above, the present disclosure provides an organic module for optoelectronic application, comprising photoelectric conversion layer(s) comprising at least two compounds according to the present disclosure.
[0068] Said optoelectronic application can be an image sensor, a photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.
[0069] As discussed above, the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the green absorption range; with an absorption coefficient between 480 and 600nm of up to more than 104 cm 1,
[0070] The organic material or organic module optionally comprises further compound(s).
[0071] As discussed above, the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the red absorption range; with an absorption coefficient between 580 and 700nm of up to more than 104 cm 1,
[0072] The organic material or organic module optionally comprises further compound(s). [0073] As discussed above, the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably in the blue absorption range; with an absorption coefficient between 380 and 500 nm of up to more than 104 cm 1,
[0074] The organic material or organic module optionally comprises further compound(s).
[0075] As discussed above, the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption in the visible absorption range, preferably for visible panchromatic in the range 400 to 700 nm, with an absorption coefficient between 400 and 700 nm of up to more than 104 cm 1,
[0076] The organic material or organic module optionally comprises further compound(s).
[0077] As discussed above, the present disclosure provides an organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to the present disclosure, wherein the compound exhibits absorption for IR in the range 700 to 900 nm, with an absorption coefficient between 700 and 900 nm.,
[0078] The organic material or organic module optionally comprises further compound(s).
[0079] As discussed above, the present disclosure provides a device, comprising one or more of compound(s) according to the present disclosure, photoelectric conversion layer(s) according to the present disclosure, buffer layer(s) according to the present disclosure, organic module(s) according to the present disclosure, organic material(s) or organic module(s) according to the present disclosure.
[0080] The device is preferably an organic image sensor, an hybrid image sensor, photodiode, organic photovoltaics, organic light-emitting diode (OLED), organic thin-film transistor (OTFT).
[0081] In one embodiment, said photoelectric conversion layer exhibits photo response in the visible absorption range.
[0082] As discussed above, the present disclosure provides an organic image sensor, comprising photoelectric conversion layer(s) according to the present disclosure. [0083] The organic image sensor of the present disclosure preferably comprises
(a) an organic photoconversion unit comprising photoelectric conversion layer(s) according to the present disclosure,
(b) at least one electrode,
(c) a substrate,
(d) optionally, a second electrode on top of said photoelectric conversion layer(s).
[0084] In a preferred embodiment, the organic image sensor does not comprise color filter(s).
[0085] The substrate can be silicon, quartz, glass, polymer, such as PMMA, PC, PS, COP, COP, PVA, PVP, PES, PET, PEN, mica, or combinations thereof.
[0086] The substrate can also be other photoelectric conversion unit(s) (e.g. blue 400-500nm and red 600-500nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600nm conversion device).
[0087] This means, a device of this disclosure can comprise (i) two inorganic units with one organic unit, (ii) one inorganic unit with two organic units, or (iii) three organic units combined with each other in the organic image sensor. Any of the organic units can contain compounds/layers/devices according to this disclosure.
[0088] In a preferred embodiment, an organic image sensor consists of three organic conversion units containing compounds in layers as of this disclosure (in devices, each with transparent electrodes), combined with each other and operating each in one of the ranges 400nm to 500 nm, 500nm to 600 nm and 600 nm to700nm.
[0089] Combined units can be realized either by vertical and/or horizontal stacking of the organic-organic or organic-inorganic units.
[0090] The electrode material can be
- transparent metal oxide, such as indium tin oxide (ITO), fluorine-doped indium oxide (IFO), tin oxide, fluorine-doped tin oxide (FTO), antimonium-doped tin oxide (ATO), zinc oxide (including Al, B and Ga doped zinc Oxide), indium oxide-zinc oxide (IZO), T1O2,
- non transparent or semitransparent metal or alloy or conductive polymer, such as Au, Ag,
Cr, Ni, Pd, AlSiCu, or any metal or metal alloy or metal combination with a suitable workfunction; PEDOT/PSS, PAN! or PANI/PSS, graphene. [0091] As discussed above, the present disclosure provides a hybrid Silicon-organic image sensor or organic image sensor, comprising
(a) an organic photoelectric conversion unit or units comprising photoelectric conversion layer(s) according to the present disclosure (comprising the compound(s) of the present disclosure),
(b) optionally, a Si based photoelectric conversion unit,
(c) metal wiring,
(d) a (CMOS) substrate,
(e) insulating layer(s), preferably oxide.
[0092] In one embodiment, said organic photoelectric conversion unit of the image sensors of the present disclosure comprises different layers within the organic based photoelectrical conversion unit(s), such as
- n-type material,
- p-type material,
- n-buffer layer,
- p-buffer layer, or combinations and/or mixtures (e.g. n material and p material co-deposited in one layer) thereof.
[0093] For example, the organic image sensor of the present disclosure can have the structure:
- substrate/first electrode/n-buffer layer/n-material/p-material/p buffer layer/second electrode;
- substrate/first electrode/n-buffer layer/n-material/mixture of n- and p- material/ p-material/p buffer layer/second electrode;
- substrate/first electrode/n-buffer layer/n-material/mixture of n- and p- material/ p buffer layer/second electrode;
- substrate/first electrode/p-buffer layer/p-material/n-material/n buffer layer/second electrode.
- substrate/first electrode/p-buffer layer/p-material/ mixture of n- and p- material /n-material/n buffer layer/second electrode.
- substrate/first electrode/p-buffer layer/p-material/ mixture of n- and p- material /n buffer layer/second electrode. [0094] The organic image sensor of the present disclosure can comprise different layer structures, in particular regarding the position of the n and p material with respect to the CMOS part.
[0095] The organic photoconversion unit can be used in combination with a Si based photoelectrical conversion unit where different layers absorb different color (RGB) in a hybrid silicon-organic image sensor (see Figure 2) or can be used without Si based photoelectrical conversion unit. In this case the organic photoconversion unit has the capability of absorbing different color (RGB) (see Figure 3).
[0096] In one embodiment, the p-type material is a transparent P material, which has the quality when comprised in a P:N heterojunction or P:N bilayer or multilayer junction, particularly a P:N1:N2 or aPl:P2:N heterojunction or multilayer junction, to dissociate efficiently the excitons created in colored N, or in a mixture of colored N materials (N1 :N2), or in another colored P or in a mixture of colored P and N materials (P2:N) via a process of HOMO dissociation.
[0097] In one embodiment, where the p-type material is a transparent P material, it has the quality to accept hole from the colored N or the mixture of colored N materials, from another colored P material or from a mixture of colored N and another P material.
[0098] In one embodiment, where the p-type material is a transparent P material, it has the quality to transport the holes.
[0099] In one embodiment, said organic photoelectric conversion unit comprising photoelectric conversion layer(s) further comprise phthalocyanine (Pc), subphthalocyanine (SubPc), merocyanine (MC), diketopyrrolopyrroles (DPP), borondipyrromethene (BODIPY), isoindigo (ID), perylene diimides (PDI), fulerenes, and naphthalodiimides.
[00100] As discussed above, the substrate can also be other photoelectric conversion unit(s) (e.g. blue 400-500nm and red 600-500nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600nm conversion device).
[00101] As discussed above, a device of this disclosure can comprise (i) two inorganic units with one organic unit, (ii) one inorganic unit with two organic units, or (iii) three organic units combined with each other in the organic image sensor. Any of the organic units can contain compounds/layers/devices according to this disclosure. [00102] The deposition methods to produce the organic photoelectrical conversion layer are PVD, CVD, spin coating, dipping coating, casting process, inkjet printing, screen printing, spray coating, offset printing.
[00103] Different process temperatures for processing the layer are possible, namely from 150 to 245°Celsius.
[00104] Note that the present technology can also be configured as described below.
(1) An indacenetetrone compound represented by formula I
Figure imgf000018_0001
wherein
R is selected from a linear or branched alkyl, cycloalkyl, aryl, alkylamine, arylamine, biaryl, heteroaryl, furanyl, thienyl, thieno[3,2-b]thienyl, benzo[l,2-b:4,5-b’]dithienyl, selenophenyl, naphthyl, quinolinyl, pyrrolyl, indolyl,
Figure imgf000019_0001
Ri and R2 are each independently selected H, halogen, CF3, CN, alkoxy, cycloalkoxy, alkyl (preferably methyl), cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, and can be the same or different from each other,
X and Y are each independently selected from O, S, Se, Te, NRA, CRB, SiRc,
R3, RA, RB and Rc are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, with the proviso that the compound is not any one of the following structures:
Figure imgf000020_0001
(2) The compound according to embodiment (1), represented by any of structures
Figure imgf000020_0002
(3) The compound according to any one of embodiments (1) to (2), wherein the compound
- exhibits absorption in the visible absorption range (about 400 to about 700 nm)
- absorbs in the blue absorption range or absorbs in the green absorption range or absorbs in the red absorption range,
- preferably shows an extinction coefficient of > 104 LmoHcm 1.
(4) Use of a compound according to any of embodiments (1) to (3) in a photoelectric conversion layer.
(5) Use of a compound according to any of embodiments (1) to (3) in an organic and/or hybrid module for optoelectronic application, such as image sensor, photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.
(6) Use of a compound according to any of embodiments (1) to (3) in a buffer layer, such as a hole blocking layer, an electron blocking layer, a hole transport layer, or an electron transport layer.
(7) Use according to any of embodiments (4) to (6), wherein at least two of the compounds according to any of embodiments (1) to (3) are used.
(8) A photoelectric conversion layer comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s).
(9) A buffer layer comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein said buffer layer is an n-buffer layer and/or p-buffer layer.
(10) An organic module for optoelectronic application such as image sensor, photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules, comprising photoelectric conversion layer(s) comprising a compound according to any of embodiments (1) to (3). (11) An organic module for optoelectronic application such as image sensor, photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules, comprising photoelectric conversion layer(s) comprising at least two compounds according to any of embodiments (1) to (3).
(12) An organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably in the green absorption range; with an absorption coefficient between 480 and 600nm of up to more than 104 cm 1.
(13) An organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably in the red absorption range; with an absorption coefficient between 580 and 700nm of up to more than 104 cm 1.
(14) An organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably in the blue absorption range; with an absorption coefficient between 380 and 500 nm of up to more than 104 cm 1.
(15) An organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably for visible panchromatic in the range 400 to 700 nm, with an absorption coefficient between 400 and 700 nm of up to more than 104 cm 1.
(16) An organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of embodiments (1) to (3), optionally comprising further compound(s), wherein the compound exhibits absorption in the IR absorption range, preferably in the range 700 to 900 nm, with an absorption coefficient between 700 and 900 nm.
(17) A device, comprising one or more of compound(s) according to any one of embodiments (1) to (3), photoelectric conversion layer(s) according to embodiment (8), buffer layer(s) according to embodiment (9), organic module(s) according to any of embodiments (10), (11), (15) or (16), organic material(s) or organic module(s) according to any of embodiments (12) to (14), wherein said device is preferably an organic image sensor, an hybrid image sensor, photodiode, organic photovoltaic s, organic light-emitting diode (OLED), organic thin-film transistor (OTFT).
(18) The device according to embodiment (17), wherein said photoelectric conversion layer exhibits photo response in the visible absorption range.
(19) An organic image sensor, comprising
(a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) according to embodiment (8),
(b) at least one electrode,
(c) a substrate,
(d) optionally, a second electrode on top of said photoelectric conversion layer(s), preferably not comprising color filter(s). (20) A hybrid Silicon-organic image sensor or organic image sensor, comprising
(a) an organic photoelectric conversion unit or units comprising photoelectric conversion layer(s) according to embodiment (8),
(b) optionally, a Si based photoelectric conversion unit,
(c) metal wiring,
(d) a (CMOS) substrate,
(e) insulating layer(s), preferably oxide.
(21) The organic image sensor according to embodiment (19) or (20), wherein said organic photoelectric conversion unit comprises different layers, such as n-type material, p-type material, n-buffer layer and/or p-buffer layer or combinations or mixtures thereof.
(22) The organic image sensor according to embodiment (21), wherein the p-type material is a transparent P material, which has the quality when comprised in a P:N heterojunction or P:N bilayer or multilayer junction, particularly a P:N1:N2 or aPl:P2:N heterojunction or multilayer junction, to dissociate efficiently the excitons created in colored N, or in a mixture of colored N materials (N1 :N2), or in another colored P or in a mixture of colored P and N materials (P2:N) via a process of HOMO dissociation, and/or has the quality to accept hole from the colored N or the mixture of colored N materials, from another colored P material or from a mixture of colored N and another P material, and/or has the quality to transport the holes.
[00105] The term “indacenetetrone compound” or “indacenetetrone -based compound”, as used herein, refers to a compound having a central benzene ring fused with two five- membered rings each of these five-membered rings having two =0, shown below. See also Figure 5.
Figure imgf000024_0001
[00106] The term “absorption in the visible wavelength range” or “dye exhibiting absorption in the visible wavelength range”, as used herein, is meant to refer to a compound/dye that is able to absorb light in only one or several parts of the entire range indicated or over the total range. For example a compound may only absorb in the range of from 500 - 700 nm, whereas another compound may absorb in the range of from 400 - 700 nm or 500 - 600 nm, whereas a third compound may absorb over the range of from 400 - 500 nm (or the above described sub-ranges of preferably 400 nm to 500 nm, or 500 nm to 600 nm, or 600 nm to 700 nm). All these scenarios are meant to be encompassed by such wording.
[00107] The term “absorption in the IR range” or “dye exhibiting absorption in the IR range”, as used herein, is meant to refer to a compound/dye that is able to absorb light in wavelength ranges above 700 nm, preferably between 700 and 900 nm.
[00108] In accordance with the present disclosure, the term "electrode" refers to an electrical lead to apply voltage. An electrode may be "interdigitated", meaning that it has a comb-like shape with two combs lying opposite each other and the respective figures of the combs engaging with each other. Alternatively, an electrode may be a non-interdigitated. An electrode may be transparent or non-transparent. A transparent electrode may, for example, be formed from indium tin oxide (ITO) or from fluorinated tin oxide (FTO). A non-transparent electrode may be reflective and may, for example, be formed from silver (Ag) or gold (Au).
[00109] The requirements of a photoelectric conversion layer to be used in image sensors are demanding and can be summarised as followed:
(1) up to 4 materials can be used together in the active layer,
(2) narrow absorption band of at least one active material for RGB pixel resolution;
(3) broad absorption band of at least one active material for visible panchromatic light;
(4) high extinction coefficient, e > 104 Lmol^cm 1 - correspondingly high absorption coefficient of at least one active material;
(5) Good hole transport for at least one material in the active layer,
(6) Good electron transport for at least one material in the layer,
(7) Optimal phase formation within the active layer- to ensure high charge generation and extraction efficiencies,
(8) Heat resistivity (preservation of all properties upon annealing of the devices up to 200° for longer times); (9) high photoelectric conversion efficiency (EQE);
(10) Fast response/short decay times of the photocurrent;
(11) low dark-current in device;
(12) thin film formation by vapour deposition (Tvp < Tdec) for all materials in the layer.
[00110] The present inventors have found novel indacenetetrone based dyes / compounds which are highly suitable as active materials for organic photoelectric conversion layers with improved conversion efficiency and response speed in organic photodiodes for vertically- integrated (VI) CMOS image sensors application. The advantages of those materials with respect to the requirements, the different type of possible molecular structures and example of compounds for use as photoelectrical conversion layer are reported herein.
[00111] The present disclosure relates to indacenetetrone based dyes / compounds as active materials for the organic photoconversion unit.
[00112] The organic photoconversion unit can be used in combination with a Si based photoelectrical conversion unit where different layer absorbed different colour (RGB and/or Visible Panchromatic) in a hybrid Silicon-organic image sensor or can be used without Si based photoelectrical conversion unit. In this case the organic photoconversion unit having the capability of absorbing different colour (RGB and/or Visible Panchromatic).
[00113] The general structure of the resulting hybrid image sensor device as well as the details of the organic based photoelectrical conversion unit are schematic represented in the Figure 2 and 3.
[00114] The absorption, energy levels and the morphology in thin film are tunable by the type of substituent R. This makes the IT based compounds very versatile compounds to be used in the organic photoelectric conversion layer (as depicted for example in figures 2 and
3)·
[00115] The main advantages of the IT based compounds of the present disclosure for the application in photoelectrical conversion layers are as follows:
- Exhibit good photo- and thermal stability (up to 300°C);
Tuning of HOMO and LUMO energies is possible;
Tuning of the absorption maximum (optical band gap) and shape over a broad range is possible; The possibility to adjust the absorption spectrum of the active device via adjusting the absorption spectrum of only one active component;
Good extinction coefficients ( e > 104 Lmol^cm 1 )
Good electrons and holes mobilities;
Good exciton diffution efficiencies;
- Processability already proven for organic photovoltaics (OPV).
[00116] In specific embodiments, different molecular dye / compound structures, different components and combination of the photoelectric conversion layer (list of possible electrodes, list of other possible n and p type materials that could be used together with the IT dyes, list of different n and p type buffer layer), different layer structures (position of the n and p material with respect to the electrodes) and different process temperature for processing the layer (from 150 to 245°Celsius) are described herein.
[00117] The present disclosure further relates to indacenetetrone based dyes / compounds of the present disclosure which are used in a bulk heterojunction (mixed p-n layer) or PN heterojunction (formed between a p layer and n layer or PiN junction (p layer - mixed layer as p-n bulk heterojunction - n-layer) in the photoelectric conversion material layer.
[00118] The dyes / compounds of the present disclosure and their use in photoelectric conversion layers have the following advantages:
High extinction coefficients ( e > 104 Lmol^cm 1).
- High thermal stability (300 to 400 °C depending on substitients but at least 300°C).
- High photostability.
- Possibility for tuning of the absorption spectrum of the device via absorption maximum (optical band gap) and shape over a broad range.
Tuning of HOMO and LUMO energy levels is possible.
- Processability already proven for OPV.
- High holes and electron mobilities high charge generation efficiencies of the devices - high charge transfer efficiency and charge separation efficiency.
- Especially independent tuning of the charge generation efficiency - through the HOMO level. EXAMPLES
EXAMPLE 1: Synthesis of indacenetetrone based dyes
[00119] In the scheme shown in Figure 5, the general synthetic route for the preparation of an indacenetetrone based compound according to the present disclosure is depicted, which starts from indacenetetrone.
EXAMPLE 2: IT-MeTh
[00120] Following the synthesis scheme of Example 1, an indacenetetrone derivative named IT-MeTh was synthesized. For details see Figure 6A.
Figure imgf000028_0001
[00121] IT-MeTh presents an absorption maximum at 464 nm in solution (Toluene, concentration 105M and 106M), see Figure 6B.
EXAMPLE 3:
[00122] Following the synthesis scheme of Example 1, an indacenetetrone derivative named IT-TPA was synthesized. For details see Figure 7A.
Figure imgf000028_0002
[00123] IT-TPA presents an absorption maximum at 597 nm in solid state (vacuum deposited film), see Figure 6B.

Claims

1. An indacenetetrone compound represented by formula I
Figure imgf000029_0001
wherein
R is selected from a linear or branched alkyl, cycloalkyl, aryl, alkylamine, arylamine, biaryl, heteroaryl, furanyl, thienyl, thieno[3,2-b]thienyl, benzo[l,2-b:4,5-b’]dithienyl, selenophenyl, naphthyl, quinolinyl, pyrrolyl, indolyl,
Figure imgf000029_0002
Ri and R2 are each independently selected H, halogen, CF3, CN, alkoxy, cycloalkoxy, alkyl (preferably methyl), cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, and can be the same or different from each other, X and Y are each independently selected from O, S, Se, Te, NRA, CRB, SiRc,
R3, RA, RB and Rc are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl, with the proviso that the compound is not any one of the following structures:
Figure imgf000030_0001
2. The compound according to claim 1, represented by any of structures
3. The compound according to any one of claims 1 to 2, wherein the compound
- exhibits absorption in the visible absorption range (about 400 to about 700 nm)
- absorbs in the blue absorption range or absorbs in the green absorption range or absorbs in the red absorption range,
- preferably shows an extinction coefficient of > 104 LmoHcm 1.
4. Use of a compound according to any of claims 1 to 3 in a photoelectric conversion layer.
5. Use of a compound according to any of claims 1 to 3 in an organic and/or hybrid module for optoelectronic application, such as image sensor, photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.
6. Use of a compound according to any of claims 1 to 3 in a buffer layer, such as a hole blocking layer, an electron blocking layer, a hole transport layer, or an electron transport layer.
7. Use according to any of claims 4 to 6, wherein at least two of the compounds according to any of claims 1 to 3 are used.
8. A photoelectric conversion layer comprising a compound according to any one of claims 1 to 3, optionally comprising further compound(s).
9. A buffer layer comprising a compound according to any one of claims 1 to 3, optionally comprising further compound(s), wherein said buffer layer is an n-buffer layer and/or p-buffer layer.
10. An organic module for optoelectronic application such as image sensor, photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules, comprising photoelectric conversion layer(s) comprising a compound according to any of claims 1 to 3.
11. An organic module for optoelectronic application such as image sensor, photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules, comprising photoelectric conversion layer(s) comprising at least two compounds according to any of claims 1 to 3.
12. An organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of claims 1 to 3, optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably in the green absorption range; with an absorption coefficient between 480 and 600nm of up to more than 104 cm 1.
13. An organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of claims 1 to 3, optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably in the red absorption range; with an absorption coefficient between 580 and 700nm of up to more than 104 cm 1.
14. An organic material or organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of claims 1 to 3, optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably in the blue absorption range; with an absorption coefficient between 380 and 500 nm of up to more than 104 cm 1.
15. An organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of claims 1 to 3, optionally comprising further compound(s), wherein the compound exhibits absorption in the visible absorption range, preferably for visible panchromatic in the range 400 to 700 nm, with an absorption coefficient between 400 and 700 nm of up to more than 104 cm 1.
16. An organic module for an image sensor, comprising photoelectric conversion layer(s) comprising a compound according to any one of claims 1 to 3, optionally comprising further compound(s), wherein the compound exhibits absorption in the IR absorption range, preferably in the range 700 to 900 nm, with an absorption coefficient between 700 and 900 nm.
17. A device, comprising one or more of compound(s) according to any one of claims 1 to 3, photoelectric conversion layer(s) according to claim 8, buffer layer(s) according to claim 9, organic module(s) according to any of claims 10, 11, 15 or 16, organic material(s) or organic module(s) according to any of claims 12 to 14, wherein said device is preferably an organic image sensor, an hybrid image sensor, photodiode, organic photovoltaics, organic light-emitting diode (OLED), organic thin-film transistor (OTFT).
18. The device according to claim 17, wherein said photoelectric conversion layer exhibits photo response in the visible absorption range.
19. An organic image sensor, comprising
(a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) according to claim 8,
(b) at least one electrode,
(c) a substrate,
(d) optionally, a second electrode on top of said photoelectric conversion layer(s), preferably not comprising color filter(s).
20. A hybrid Silicon-organic image sensor or organic image sensor, comprising
(a) an organic photoelectric conversion unit or units comprising photoelectric conversion layer(s) according to claim 8,
(b) optionally, a Si based photoelectric conversion unit,
(c) metal wiring,
(d) a (CMOS) substrate,
(e) insulating layer(s), preferably oxide.
21. The organic image sensor according to claim 19 or 20, wherein said organic photoelectric conversion unit comprises different layers, such as n-type material, p-type material, n-buffer layer and/or p-buffer layer or combinations or mixtures thereof.
22. The organic image sensor according to claim 21, wherein the p-type material is a transparent P material, which has the quality when comprised in a P:N heterojunction or P:N bilayer or multilayer junction, particularly a P:N1:N2 or aPl:P2:N heterojunction or multilayer junction, to dissociate efficiently the excitons created in colored N, or in a mixture of colored N materials (N1 :N2), or in another colored P or in a mixture of colored P and N materials (P2:N) via a process of HOMO dissociation, and/or has the quality to accept hole from the colored N or the mixture of colored N materials, from another colored P material or from a mixture of colored N and another P material, and/or has the quality to transport the holes.
23. The organic image sensor according to any one of claim 19 or 22, wherein said organic photoelectric conversion unit comprising photoelectric conversion layer(s) further comprise phthalocyanine (Pc), subphthalocyanine (SubPc), merocyanine (MC), diketopyrrolopyrroles (DPP), borondipyrromethene (BODIPY), isoindigo (ID), perylene diimides (PDI), fulerenes, and naphthalodiimides.
24. The organic image sensor according to any one of claims 19 to 23, wherein the substrate is silicon, quartz, glass, polymer, such as PMMA, PC, PS, COP, COP, PVA, PVP, PES, PET, PEN, mica, or combinations thereof.
25. The organic image sensor according to any one of claims 19 to 24, wherein the electrode material is selected from
- transparent metal oxide, such as indium tin oxide (ITO), fluorine-doped indium oxide (IFO), tin oxide, fluorine-doped tin oxide (FTO), antimonium-doped tin oxide (ATO), zinc oxide (including Al, B and Ga doped zinc Oxide), indium oxide-zinc oxide (IZO), T1O2,
- non transparent or semitransparent metal or alloy or conductive polymer, such as Au, Ag, Cr, Ni, Pd, AlSiCu, or any metal or metal alloy or metal combination with suitable workfunction; PEDOT/PSS, PANI or PANI/PSS, graphene.
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WO2011105624A1 (en) * 2010-02-25 2011-09-01 Fujifilm Corporation Photoelectric conversion device, imaging device and production methods thereof

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