WO2023179986A1

WO2023179986A1 - Aza-boron-diquinomethene-based dyes as photoactive material for organic photoelectric conversion layers in organic photodiodes

Info

Publication number: WO2023179986A1
Application number: PCT/EP2023/054083
Authority: WO
Inventors: Vitor Angelo FONSECA DEICHMANN; Anthony Roberts; Dennis CHERCKA; Silvia Rosselli; Berthold WEGNER; Nikolaus Knorr; Tzenka Miteva; Gabriele Nelles; David Danner; Vladimir Yakutkin
Original assignee: Sony Group Corporation; Sony Europe B.V.
Priority date: 2022-03-24
Filing date: 2023-02-17
Publication date: 2023-09-28

Abstract

The field of the DISCLOSURE lies in active materials for organic image sensors. The present disclosure relates to aza-boron-diquinomethene-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.

Description

AZA-BORON-DIQUINOMETHENE-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 aza-boron-diquinomethene-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 photoelectrical 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/or 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 RGB 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 aza-boron-diquinomethene-based compound represented by formula I

CD wherein

Ri, R2, R4 to R9, R11 and R12 are each independently selected from hydrogen, halogen and linear or branched alkyl (preferably linear or branched Ci-Ce alkyl), Rj and Rio are each independently 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,

RA and RB are each independently selected from 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, NRc, CRD, SIRE, RC,RD and RE 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:

[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 or a photodiode, 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.

[0020] The present disclosure provides an organic material or organic module for an image sensor or a photodiode, 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 600 nm of up to more than 10⁴ cm'¹.

[0021] The present disclosure provides an organic material or organic module for an image sensor or a photodiode, 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 700 nm of up to more than 10⁴ cm'¹.

[0022] The present disclosure provides an organic material or organic module for an image sensor or a photodiode, 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 or a photodiode, 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 or a photodiode, 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 or a photodiode, 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 present disclosure provides the use of an aza-boron-diquinomethene-based compound represented by formula I

wherein

Ri, R2, R4 to R9, R11 and R12 are each independently selected from hydrogen, halogen and linear or branched alkyl (preferably linear or branched Ci-Ce alkyl),

Rj and Rio are each independently 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,

X and Y are each independently selected from O, S, Se, Te, NRc, CRD, SIRE,

RC,RD and RE are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode. [0028] The present disclosure provides an organic module for optoelectronic application, which is an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in [0027],

[0029] The present disclosure provides an organic module for optoelectronic application, which is an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising at least two compounds as defined in [0027],

[0030] The present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in [0027], 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.

[0031] The present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in [0027], 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.

[0032] The present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in [0027], 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.

[0033] The present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in [0027], 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.

[0034] The present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in [0027], 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.

[0035] The present disclosure provides a device, comprising one or more of compound(s) as defined in [0027], organic module(s) according to the present disclosure, organic material(s) or organic module(s) according to the present disclosure, wherein said device is an organic image sensor, a hybrid image sensor or a photodiode. [0036] The present disclosure provides an organic image sensor or a photodiode, comprising

(a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) comprising a compound as defined in [0027], and optionally further compound(s),

(b) at least one electrode,

(c) a substrate,

[0037] The present disclosure provides a hybrid Silicon-organic image sensor or organic image sensor or a photodiode, comprising

(b) optionally, a Si based photoelectric conversion unit,

(c) metal wiring,

(d) a (CMOS) substrate,

(e) insulating layer(s), preferably oxide.

[0038] 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

[0039] 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:

[0040] Figure 1 shows a state of the art CMOS image sensor. [0041] Figure 2 shows a schematic representation of the hybrid silicon-organic image sensor.

[0042] Figure 3 shows a schematic representation of the organic based photoelectrical conversion unit with the different layers.

[0043] Figure 4 shows another schematic representation of the organic based photoelectrical conversion unit with the different layers.

[0044] Figure 5 shows a general synthetic route for the preparation of an aza-boron- diquinomethene- based compound.

[0045] Figure 6 shows the aza-boron-diquinomethene- based compound of Example 1, its absorption spectra in solution and solid state.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0046] As discussed above, the present disclosure provides an aza-boron-diquinomethene- based compound represented by formula I

wherein

X and Y are each independently selected from O, S, Se, Te, NRc, CRD, SIRE,

RC,RD and RE are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl. [0047] A compound according to the present disclosure is not any one of the following structures:

[0048] In one embodiment, the aza-boron-diquinomethene-based compound is represented by any of the following structures

[0049] An aza-boron-diquinomethene-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.

[0050] In one embodiment, the compounds of the present disclosure absorb in the blue absorption range.

[0051] In one embodiment, the compounds of the present disclosure absorb in the green absorption range.

[0052] In one embodiment, the compounds of the present disclosure absorb in the red absorption range.

[0053] In one embodiment, the compounds of the present disclosure absorb in the IR range, preferably in the range from 700 nm-900 nm.

[0054] In one embodiment, the compounds of the present disclosure absorb in the visible panchromatic, preferably in the range from 400 to 700 nm.

[0055] A compound according to the present disclosure preferably shows an extinction coefficient of > 10⁴ Lmol^cm'¹, more preferably of > 10⁵ Lmol^cm'¹.

[0056] The compounds according to the present disclosure preferably:

[0057] exhibit good photo- and thermal stability (up to 300°C),

[0058] allow tuning of HOMO and LUMO energies, [0059] allow tuning of the absorption maximum (optical band gap) and shape over a broad range,

[0060] provide the possibility to adjust the absorption spectrum of an active device via adjusting the absorption spectrum of only one active component.

[0061] exhibit high electrons and holes mobilities,

[0062] exhibit high exciton diffusion efficiencies.

[0063] Their processability is already proven for OPV.

[0064] As discussed above, the present disclosure provides the use of a compound according to the present disclosure in a photoelectric conversion layer.

[0065] In one embodiment, at least two of the compounds according to the present disclosure are used in a photoelectric conversion layer.

[0066] 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.

[0067] Said optoelectronic application can be an image sensor, a photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.

[0068] In one embodiment, at least two of the compounds according to the present disclosure are used in an organic and/or hybrid module.

[0069] As discussed above, the present disclosure provides the use of a compound according to the present disclosure in a buffer layer.

[0070] Said buffer layer can be a hole blocking layer, an electron blocking layer, a hole transport layer, or an electron transport layer.

[0071] In one embodiment, at least two of the compounds according to the present disclosure are used in a buffer layer.

[0072] As discussed above, the present disclosure provides a photoelectric conversion layer comprising a compound according to the present disclosure.

[0073] The photoelectric conversion layer optionally comprises further compound(s).

[0074] 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. [0075] The buffer layer optionally comprises further compound(s).

[0076] 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.

[0077] Said optoelectronic application can be an image sensor, a photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.

[0078] 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.

[0079] Said optoelectronic application can be an image sensor, a photodiode, organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.

[0080] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, 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 600 nm of up to more than 10⁴ cm'¹,

[0081] The organic material or organic module optionally comprises further compound(s).

[0082] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, 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 700 nm of up to more than 10⁴ cm'¹,

[0083] The organic material or organic module optionally comprises further compound(s).

[0084] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, 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, [0085] The organic material or organic module optionally comprises further compound(s).

[0086] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, 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,

[0087] The organic material or organic module optionally comprises further compound(s).

[0088] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, 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,

[0089] The organic material or organic module optionally comprises further compound(s).

[0090] 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.

[0091] The device is preferably an organic image sensor, a hybrid image sensor, photodiode, organic photovoltaics, organic light-emitting diode (OLED), organic thin-film transistor (OTFT).

[0092] In one embodiment, said photoelectric conversion layer exhibits photo response in the visible absorption range.

[0093] As discussed above, the present disclosure provides an organic image sensor or a photodiode, comprising photoelectric conversion layer(s) according to the present disclosure.

[0094] 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). [0095] In a preferred embodiment, the organic image sensor or a photodiode does not comprise color filter(s).

[0096] The substrate can be silicon, quartz, glass, polymer, such as PMMA, PC, PS, COP, COP, PVA, PVP, PES, PET, PEN, mica, or combinations thereof.

[0097] The substrate can also be other photoelectric conversion unit(s) (e.g. blue 400-500 nm and red 600-500 nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600 nm conversion device).

[0098] 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 or a photodiode. Any of the organic units can contain compounds/layers/devices according to this disclosure.

[0099] 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 400 nm to 500 nm, 500 nm to 600 nm and 600 nm to 700 nm.

[00100] Combined units can be realized either by vertical and/or horizontal stacking of the organic-organic or organic-inorganic units.

[00101] 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), TiO2,

- nontransparent 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 work function; PEDOT/PSS, PANI or PANI/PSS, graphene.

[00102] As discussed above, the present disclosure provides a hybrid Silicon-organic image sensor or organic image sensor or a photodiode, 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.

[00103] In one embodiment, said organic photoelectric conversion unit of the image sensors or a photodiode 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.

[00104] In one embodiment, said n-type material can be comprised of two or more n-type materials co-deposited as an n-type material.

[00105] In one embodiment, said p-type material can be comprised of two or more p-type materials co-deposited as a p-type material.

[00106] In one embodiment, said n-buffer layer can be comprised of two or more n-buffer layers co-deposited as an n-buffer layer.

[00107] In one embodiment, said p-buffer layer can be comprised of two or more p-buffer layers co-deposited as a p-buffer layer.

[00108] For example, the organic image sensor or a photodiode 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.

[00109] 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.

[00110] 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 or a photodiode (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).

[00111] 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 a Pl :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.

[00112] 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.

[00113] In one embodiment, where the p-type material is a transparent P material, it has the quality to transport the holes.

[00114] 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.

[00115] As discussed above, the substrate can also be other photoelectric conversion unit(s) (e.g. blue 400-500 nm and red 600-500 nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600 nm conversion device).

[00116] 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.

[00117] The deposition methods to produce the organic photoelectrical conversion layer are PVD, C VD, spin coating, dipping coating, casting process, inkj et printing, screen printing, spray coating, offset printing.

[00118] Different process temperatures for processing devices with the photoelectrical conversion layer are possible, up to 200°Celsius.

[00119] As discussed above, the present disclosure provides the use of an aza-boron- diquinomethene-based compound represented by formula I

wherein

X and Y are each independently selected from O, S, Se, Te, NRc, CRD, SIRE,

RC,RD and RE are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode. [00120] In one embodiment, the aza-boron-diquinom ethene-based compound used in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode is represented by any of the following structures

[00121] In one embodiment, the aza-boron-diquinom ethene-based compound used in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode 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.

[00122] In one embodiment, the aza-boron-diquinom ethene-based compound used in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode absorb in the blue absorption range.

[00123] In one embodiment, the compounds of the present disclosure absorb in the green absorption range.

[00124] In one embodiment, the aza-boron-diquinom ethene-based compound used in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode absorb in the red absorption range.

[00125] In one embodiment, the aza-boron-diquinomethene-based compound used in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode absorb in the IR range, preferably in the range from 700 nm-900 nm. [00126] In one embodiment, the aza-boron-diquinom ethene-based compound used in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode absorb in the visible panchromatic, preferably in the range from 400 to 700 nm.

[00127] The aza-boron-diquinomethene-based compound used in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode preferably shows an extinction coefficient of > 10⁴ Lmol^cm’¹, more preferably of > 10⁵ Lmol^cm'¹.

[00128] Said aza-boron-diquinomethene-based compounds preferably:

[00129] exhibit good photo- and thermal stability (up to 300°C),

[00130] allow tuning of HOMO and LUMO energies,

[00131] allow tuning of the absorption maximum (optical band gap) and shape over a broad range,

[00132] provide the possibility to adjust the absorption spectrum of an active device via adjusting the absorption spectrum of only one active component.

[00133] exhibit high electrons and holes mobilities,

[00134] exhibit high exciton diffusion efficiencies.

[00135] Their processability is already proven for OPV.

[00136] As discussed above, the present disclosure provides an organic module for optoelectronic application, which is an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound of the present disclosure, in particular as defined herein above in [0119] to [0135],

[00137] As discussed above, the present disclosure provides an organic module for optoelectronic application, which is an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising at least two compounds of the present disclosure, in particular as defined herein above in [0119] to [0135],

[00138] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound of the present disclosure, in particular as defined herein above in [0119] to [0135], 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 cm⁴. [00139] The organic material or organic module optionally comprises further compound(s).

[00140] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound of the present disclosure, in particular as defined herein above in [0119] to [0135], 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.

[00141] The organic material or organic module optionally comprises further compound(s).

[00142] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound of the present disclosure, in particular as defined herein above in [0119] to [0135], 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.

[00143] The organic material or organic module optionally comprises further compound(s).

[00144] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound of the present disclosure, in particular as defined herein above in [0119] to [0135], 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.

[00145] The organic material or organic module optionally comprises further compound(s).

[00146] As discussed above, the present disclosure provides an organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound of the present disclosure, in particular as defined herein above in [0119] to [0135], 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.

[00147] The organic material or organic module optionally comprises further compound(s).

[00148] As discussed above, the present disclosure provides a device, comprising one or more of compound(s) of the present disclosure, in particular as defined herein above in [0119] to [0135], organic module(s) according to the present disclosure, organic material(s) or organic module(s) according to the present disclosure, wherein said device is an organic image sensor, a hybrid image sensor or a photodiode.

[00149] As discussed above, the present disclosure provides an organic image sensor or a photodiode, comprising

(a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) comprising a compound of the present disclosure, in particular as defined herein above in [0119] to [0135], and optionally further compound(s),

(b) at least one electrode,

(c) a substrate,

(d) optionally, a second electrode on top of said photoelectric conversion layer(s), [00150] In a preferred embodiment, the organic image sensor or a photodiode does not comprise color filter(s).

[00151] As discussed above, the substrate can be silicon, quartz, glass, polymer, such as PMMA, PC, PS, COP, COP, PVA, PVP, PES, PET, PEN, mica, or combinations thereof. [00152] The substrate can also be other photoelectric conversion unit(s) (e.g. blue 400-500 nm and red 600-500 nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600 nm conversion device).

[00153] 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.

[00154] In a preferred embodiment, an organic image sensor or a photodiode 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 400 nm to 500 nm, 500 nm to 600 nm and 600 nm to700 nm. [00155] Combined units can be realized either by vertical and/or horizontal stacking of the organic-organic or organic-inorganic units.

[00156] As discussed above, the electrode material can be

[00157] As discussed above, the present disclosure provides a hybrid Silicon-organic image sensor or organic image sensor or a photodiode, comprising

(b) optionally, a Si based photoelectric conversion unit,

(c) metal wiring,

(d) a (CMOS) substrate,

(e) insulating layer(s), preferably oxide.

[00158] In one embodiment of the organic image sensor or a photodiode, said organic photoelectric conversion unit comprises different layers, such as

- n-type material,

- p-type material,

- n-buffer layer,

[00159] In one embodiment, said n-type material can be comprised of two or more n-type materials co-deposited as an n-type material.

[00160] In one embodiment, said p-type material can be comprised of two or more p-type materials co-deposited as a p-type material. [00161] In one embodiment, said n-buffer layer can be comprised of two or more n-buffer layers co-deposited as an n-buffer layer.

[00162] In one embodiment, said p-buffer layer can be comprised of two or more p-buffer layers co-deposited as a p-buffer layer.

[00163] For example, the organic image sensor or a photodiode of the present disclosure can have the structure:

- 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.

[00164] The organic image sensor or a photodiode 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.

[00165] 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).

[00166] 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 a P1 :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. [00167] 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.

[00168] In one embodiment, where the p-type material is a transparent P material, it has the quality to transport the holes.

[00169] 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.

[00170] As discussed above, the substrate can also be other photoelectric conversion unit(s) (e.g. blue 400-500 nm and red 600-500 nm conversion devices in case the organic conversion layer according to this disclosure is green 500-600 nm conversion device).

[00171] 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 or a photodiode. Any of the organic units can contain compounds/layers/devices according to this disclosure.

[00172] The deposition methods to produce the organic photoelectrical conversion layer are PVD, C VD, spin coating, dipping coating, casting process, inkj et printing, screen printing, spray coating, offset printing.

[00173] Different process temperatures for processing devices with the photoelectrical conversion layer are possible, up to 200°Celsius.

[00174] Note that the present technology can also be configured as described below.

(1) An aza-boron-diquinom ethene-based compound represented by formula I

wherein Ri, R2, R4 to R9, R11 and R12 are each independently selected from hydrogen, halogen and linear or branched alkyl (preferably linear or branched Ci-Ce alkyl),

RA and RB are each independently selected from 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, NRc, CRD, SIRE,

RC,RD and RE 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:

(2) The compound according to (1), represented by any of structures

(3) The compound according to (1) or (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 Lmol^cm'¹.

(4) Use of a compound according to any of (1) to (3) in a photoelectric conversion layer.

(5) Use of a compound according to any of (1) to (3) in an organic and/or hybrid module for optoelectronic application, such as organic photovoltaics, comprising organic photoelectric conversion layer(s), OLED and OTFT organic modules.

(6) Use of a compound according to any of (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 any of (4) to (6), wherein at least two of the compounds according to any of (1) to (3) are used. (8) A photoelectric conversion layer comprising a compound according to any of (1) to (3), optionally comprising further compound(s).

(9) A buffer layer comprising a compound according to any of (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 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 (1) to (3).

(11) An organic module for optoelectronic application, such as 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 (1) to (3).

(12) An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound according to any of (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 or a photodiode, comprising photoelectric conversion layer(s) comprising a compound according to any of (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 or a photodiode, comprising photoelectric conversion layer(s) comprising a compound according to any of (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 material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound according to any of (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 material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound according to any of (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 any of (1) to (3), photoelectric conversion layer(s) according to (8), buffer layer(s) according to (9), organic module(s) according to any of (10), (11), (15) or (16), organic material(s) or organic module(s) according to any of (12) to (14), wherein said device is preferably organic photovoltaics, organic light-emitting diode (OLED), organic thin-film transistor (OTFT). (18) The device according to (17), wherein said photoelectric conversion layer exhibits photo response in the visible absorption range.

(19) An organic image sensor or a photodiode, comprising

(a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) according to (8),

(b) at least one electrode,

(c) a substrate,

(20) A hybrid Silicon-organic image sensor or organic image sensor or a photodiode, comprising

(a) an organic photoelectric conversion unit or units comprising photoelectric conversion layer(s) according to (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 or a photodiode according to (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 or a photodiode according to (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 a Pl :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) Use of an aza-boron-diquinomethene-based compound represented by formula I

wherein

X and Y are each independently selected from O, S, Se, Te, NRc, CRD, SIRE,

RC,RD and RE are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl or of a compound according to (2) or (3) in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode. (24) An organic module for optoelectronic application, which is an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in (23).

(25) An organic module for optoelectronic application, which is an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising at least two compounds as defined in (23).

(26) An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in (23), 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.

(27) An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in (23), 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.

(28) An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in (23), 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.

(29) An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in (23), 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.

(30) An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in (23), 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.

(31) A device, comprising one or more of compound(s) as defined in (23), organic module(s) according to any of (24) to (30), organic material(s) or organic module(s) according to any of (26) to (30), wherein said device is an organic image sensor, a hybrid image sensor or a photodiode.

(32) An organic image sensor or a photodiode, comprising

(a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) comprising a compound as defined in (23), and optionally further compound(s),

(b) at least one electrode,

(c) a substrate,

(33) A hybrid Silicon-organic image sensor or organic image sensor or a photodiode, comprising

(b) optionally, a Si based photoelectric conversion unit,

(c) metal wiring,

(d) a (CMOS) substrate,

(e) insulating layer(s), preferably oxide. (34) The organic image sensor or a photodiode according to (32) or (33), 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.

(35) The organic image sensor or a photodiode according to claim (34), 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 a Pl :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.

[00175] The term “aza-boron-diquinomethene compound” or “aza-boron-diquinomethene- based compound”, as used herein, refers to a compound having a boron-difluoride complex with a planar aza-boron-diquinomethene (BDQ) core structure, shown below. See also Figure 5.

[00176] 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. [00177] 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.

[00178] 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).

[00179] The requirements of a photoelectric conversion layer to be used in image sensors or a photodiode 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 vacuum deposition (Td < Tdec) for all materials in the layer.

[00180] The present inventors have found novel aza-boron-diquinom ethene 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.

[00181] The present disclosure relates to aza-boron-diquinomethene based dyes / compounds as active materials for the organic photoconversion unit.

[00182] 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 a photodiode 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).

[00183] The general structure of the resulting hybrid image sensor or a photodiode device as well as the details of the organic based photoelectrical conversion unit are schematic represented in the Figure 2 and 3.

[00184] The absorption, energy levels and the morphology in thin film are tunable, preferably by the type of substituent R3 and Rio. This makes the aza-boron-diquinomethene based compounds very versatile compounds to be used in the organic photoelectric conversion layer (as depicted for example in Figures 2 and 3).

[00185] The main advantages of the aza-boron-diquinomethene 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 absorbion 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).

[00186] 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 aza-boron- diquinomethene based 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.

[00187] The present disclosure further relates to aza-boron-diquinomethene 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.

[00188] 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 absorbion spectrum of the device via absorbion 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 :

[00189] In the scheme shown in Figure 5, the general synthetic route for the preparation of an aza-boron-diquinomethene based compound according to the present disclosure is depicted, which starts from aza-boron-diquinomethene.

EXAMPLE 2: BDQ-1 [00190] Use of the aza-boron-diquinomethene based dye BDQ-1 in a photoconversion layer as shown in Figure 4.

[00191] Figure 6 shows a typical absorption spectrum of a BDQ dye both in solution and in the solid state (thin film deposition).

[00192] Thus, the foregoing discussion discloses and describes merely exemplary embodiments of the present disclosure. As will be understood by those skilled in the art, the present disclosure may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. Accordingly, the disclosure of the present disclosure is intended to be illustrative, but not limiting of the scope of the disclosure, as well as other claims. The disclosure, including any readily discernible variants of the teachings herein, define, in part, the scope of the foregoing claim terminology such that no inventive subject matter is dedicated to the public.

Claims

Sony Group Corporation et al. CLAIMS

1. An aza-boron-diquinomethene-based compound represented by formula I

wherein

X and Y are each independently selected from O, S, Se, Te, NRc, CRD, SIRE,

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

- preferably shows an extinction coefficient of > 10⁴ Lmol^cm'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 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 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 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 or a photodiode, 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 or a photodiode, 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 or a photodiode, 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 material or organic module for an image sensor or a photodiode, 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 material or organic module for an image sensor or a photodiode, 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 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 or a photodiode, comprising

(a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) according to claim 8,

(b) at least one electrode,

(c) a substrate,

20. A hybrid Silicon-organic image sensor or organic image sensor or a photodiode, 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 or a photodiode 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 or a photodiode 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 a Pl :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. Use of an aza-boron-diquinomethene-based compound represented by formula I

wherein

X and Y are each independently selected from O, S, Se, Te, NRc, CRD, SIRE,

RC,RD and RE are each independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, amino, benzyl, heteroaryl or aryl or of a compound according to claim 2 or 3 in an organic and/or hybrid module for optoelectronic application, which is an image sensor or a photodiode.

24. An organic module for optoelectronic application, which is an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in claim 23.

25. An organic module for optoelectronic application, which is an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising at least two compounds as defined in claim 23.

26. An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in claim 23, 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.

27. An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in claim 23, 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.

28. An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in claim 23, 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.

29. An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in claim 23, 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.

30. An organic material or organic module for an image sensor or a photodiode, comprising photoelectric conversion layer(s) comprising a compound as defined in claim 23, 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.

31. A device, comprising one or more of compound(s) as defined in claim 23, organic module(s) according to any of claims 24 to 30, organic material(s) or organic module(s) according to any of claims 26 to 30, wherein said device is an organic image sensor, a hybrid image sensor or a photodiode.

32. An organic image sensor or a photodiode, comprising

(a) an organic photoelectric conversion unit comprising photoelectric conversion layer(s) comprising a compound as defined in claim 23, and optionally further compound(s),

(b) at least one electrode,

(c) a substrate,

33. A hybrid Silicon-organic image sensor or organic image sensor or a photodiode, comprising

(b) optionally, a Si based photoelectric conversion unit,

(c) metal wiring,

(d) a (CMOS) substrate,

(e) insulating layer(s), preferably oxide.

34. The organic image sensor or a photodiode according to claim 32 or 33, 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.

35. The organic image sensor or a photodiode according to claim 34, 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 a Pl :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.