Active material for organic image sensor

Abstract

The present disclosure relates to active materials for organic image sensors. The present disclosure relates to transparent N materials and / or to transparent P materials and their use in an absorption layer, a photoelectric conversion layer and / or an organic image sensor, as well as their method of synthesis. The present disclosure also relates to a photoelectric conversion layer comprising an active material according to the present disclosure, to a device comprising an active material according to the present disclosure or a photoelectric conversion layer according to the present disclosure. Furthermore, the present disclosure relates to an organic image sensor comprising a photoelectric conversion layer according to the present disclosure.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 201680017925.4, filed March 31, 2016, entitled "N and P Active Materials for Organic Photoelectric Conversion Layers in Organic Photodiodes". TECHNICAL FIELD

[0002] The field of the present disclosure is active materials for organic image sensors.

[0003] The present disclosure relates to transparent N materials and / or to transparent P materials and their use in absorption layers, photoelectric conversion layers and / or organic image sensors, as well as methods for their synthesis.

[0004] The present disclosure also relates to photoelectric conversion layers comprising active materials according to the present disclosure, to devices comprising active materials according to the present disclosure or photoelectric conversion layers according to the present disclosure.

[0005] Furthermore, the present disclosure relates to organic image sensors comprising photoelectric conversion layers according to the present disclosure. BACKGROUND

[0006] The background description provided herein is for the purpose of generally presenting the context of the disclosure. The work of the presently identified inventors, to the extent the work is described in this background section, and the describing of aspects in this background section as it exists at the time of filing, are not, and are not to be construed as, prior art to the disclosure (for purposes of patentability).

[0007] An image sensor, which is a semiconductor device for converting an optical image into an electrical signal, comprises a light sensing unit for sensing light and a logic circuit unit for processing the sensed light into an electrical signal, to store data.

[0008] In the prior art, the light sensing unit comprises a color filter and a photoelectric conversion film, a semiconductor p-n junction, such as silicon. The color filter separates light according to color, but reduces spatial resolution and light collection and utilization efficiency.

[0009] To overcome this problem, geometries were reported, in which photoelectric conversion units capable of detecting light of different wavelengths are stacked in the longitudinal direction. In particular, such photoelectric conversion units are organic photoelectric conversion layers based on p-n junctions or bulk heterojunctions. The photoelectric conversion efficiency of such units depends to a large extent on the type of material used in the layers. With the organic materials available so far, low conversion efficiency and high dark current were reported.

[0010] In another solution, an organic layer is used that absorbs light in the infrared region but not in the visible region. This layer can be combined with a CMOS-based imager portion for the visible range or with an organic-based imager portion that absorbs light in the visible range. In both cases, white light is collected, and filters must be used to achieve BGR pixel resolution. In this case, and in the case of color filters, light is separated according to color but this reduces spatial resolution and light collection and utilization efficiency. Summary of the Invention

[0011] This disclosure provides a transparent nitrogen material,

[0012] When included in a P:N heterojunction or a double-layer or multi-layer junction, preferably a P1:P2:N1:N2 or P1:P2:N or P:N1:N2 heterojunction or multi-layer junction, it has the following characteristics: It effectively dissociates excitons generated on colored P or a mixture of colored P materials (P1:P2) or another colored N or a mixture of colored N and P materials (P:N2 or P1:P2:N2) through a LUMO dissociation process, and receives electrons from the excited state of the donor (the P material or N material absorbs photons).

[0013] Transparency refers to a light density of less than approximately 60,000 cm⁻¹ within the visible light wavelength range (approximately 400 to 700 nm). -1 The absorption coefficient, or a value less than approximately 60,000 MΩ, is the absorption coefficient. -1 cm -1 The extinction coefficient (in toluene),

[0014] And color refers to a wavelength greater than approximately 60,000 cm⁻¹ in the visible light wavelength range from approximately 400 nm to approximately 700 nm. -1 The absorption coefficient (with a maximum value anywhere in this region or absorption in all places in this region).

[0015] This disclosure provides a transparent P material,

[0016] When included in a P:N heterojunction or a P:N bilayer or multilayer junction, preferably a P1:P2:N1:N2 or a P1:P2:N1 or a P:N1:N2 heterojunction or multilayer junction, it has the following characteristics: It effectively dissociates excitons generated on a mixture of colored N or colored N materials (N1:N2) or another colored P or a mixture of colored P and N materials (P2:N or P2:N1:N2) through a HOMO dissociation process.

[0017] Electrons are supplied to excite the HOMO (photon absorption by P or N materials) of the colored material, which is equivalent to receiving holes.

[0018] Transparency refers to a light density of less than approximately 60,000 cm⁻¹ within the visible light wavelength range (approximately 400 to 700 nm). -1 The absorption coefficient, or less than approximately 60,000 MΩ. -1 cm -1 The extinction coefficient (in toluene),

[0019] And color refers to a wavelength greater than approximately 60,000 cm⁻¹ in the visible light wavelength range from approximately 400 nm to approximately 700 nm. -1 The absorption coefficient (with a maximum value anywhere in this region or absorption in all places in this region).

[0020] This disclosure provides a P:N heterojunction, preferably a P1:P2:N1:N2 heterojunction, which includes a transparent N material according to this disclosure and / or a transparent P material according to this disclosure.

[0021] And including other N and / or P materials,

[0022] The additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0023] This disclosure provides the use of transparent N and / or P materials according to this disclosure in absorption layers and / or photoelectric conversion layers and / or in organic and / or hybrid modules for optoelectronic applications.

[0024] This disclosure provides a photoelectric conversion layer comprising a transparent N and / or P material according to this disclosure. This disclosure also provides an absorption layer comprising a transparent N and / or P material according to this disclosure.

[0025] This disclosure provides devices comprising a transparent N and / or P material according to this disclosure or a photoelectric conversion layer according to this disclosure.

[0026] This disclosure provides an organic image sensor including an organic photoelectric conversion unit comprising a photoelectric conversion layer according to this disclosure.

[0027] This disclosure provides a hybrid silicon-organic image sensor, including an organic photoelectric conversion unit comprising a photoelectric conversion layer according to this disclosure.

[0028] The present disclosure provides methods for synthesizing transparent n and p materials, in particular naphthalene monoimide dimer (NMI dimer) based materials, naphthalene diimide (NDI) based materials, naphthalene diimide dimer (NDI dimer) based materials, naphthalene mono-diimide dimer (NMI-NDI) based materials, dithiophene pyrrol dimer (DTP dimer) based materials, and zinc complex based materials.

[0029] The foregoing paragraphs have been presented by way of general introduction, and are not intended to limit the scope of the appended claims. The described embodiments and additional advantages will best be understood by reference to the following detailed description taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0030] The present disclosure, together with its many attendant advantages, will best be understood by reference to the following detailed description, taken in conjunction with the accompanying drawings in which:

[0031] Figure 1 A CMOS image sensor is shown.

[0032] Figure 2 A schematic of a hybrid silicon-organic image sensor is shown.

[0033] Figure 3 A schematic of an organic-based photoelectric conversion unit with different layers is shown.

[0034] Figure 4 HOMO and LUMO dissociation processes are described.

[0035] Figure 5A A general synthetic route for naphthalene monoimide (NMI) based materials is shown. Figure 5B A composite NMI1 of Example 1 is shown along with its TG, DSC, and its absorption (in solution).

[0036] Figure 6A A synthetic route is shown for preparing two naphthalene monoimide dimer (NMI dimer) based materials, called NMI-B11 and NMI-B15. Figure 6B TG and absorption (in solution) of NMI-B11 and NMI-B15 are shown. Figure 6C An external quantum efficiency (EQE) of a photoelectric conversion layer is shown, where NMI-B11 is used as a transparent n material, and quinacridone (QD) as an absorbing p material.

[0037] Figure 7A A synthetic route is shown for preparing a dithiophene pyrrol (DTP) based material, DTP6. Figure 7BTG, DSC, and its absorption (in solution) of DTP6 are shown. FIG. 7C shows the external quantum efficiency (EQE) of the photoelectric conversion layer, where DTP6 is used as the transparent N material (donor) and SubPcCl (Subphtalocyanine chloride) as the absorbing p material (acceptor).

[0038] Figure 8A The general synthetic route for naphthalene mono-imide dimer (NMI dimer) based materials (general formula II) and naphthalene di-imide (NDI) based materials (general formula III) is shown.

[0039] Figure 8B The UV VIS spectrum of naphthalene di-imide based material NDI1 is shown.

[0040] Figure 8C The electron mobility of NDI1 is shown.

[0041] Figure 8D The PiN junction device of NDI1 with QD is shown.

[0042] Figure 8E The PiN junction device of NDI1 with BQD is shown.

[0043] Figure 8F The PiN junction device of NDI1 with SubPcCl and NMI-NDI1 with SubPcCl is shown.

[0044] Figure 9 The general synthetic route for naphthalene di-imide dimer (NDI dimer) based materials (general formula IV and V) is shown.

[0045] Figures 10A-10C The general synthetic route for naphthalene mono-di-imide dimer (NMI-NDI) based materials (general formula VI— Figure 10A , general formula VII— Figure 10B and general formula VIII— Figure 10C ) is shown.

[0046] Figures 11A-11B The general synthetic route for dithiophene pyrrol dimer (DTP dimer) based materials (general formula XV— Figure 11A and general formula XVI— Figure 11B ) is shown.

[0047] Figure 12 The general synthetic route for zinc complex based materials (general formula XIX to XXI) is shown.

[0048] Figure 13An overview of the synthesis of transparent N materials having the general formula Ia is shown.

[0049] Figure 14 The absorption of NDI materials with the general formula Ia is shown.

[0050] Figure 15 The energy levels of an N-buffered material with the general formula Ia are shown.

[0051] Figure 16 The energy levels of an N-buffered material with the general formula Ia are shown.

[0052] Figure 17A and Figure 17B The energy levels of an N-buffered material with the general formula Ia are shown.

[0053] Figure 18A and Figure 18B An example of a transparent P-type material is shown.

[0054] Figures 19A-19C and Figures 20A-20C The following devices are shown, with NDI35 as an n buffer and DTT2, DTT9, DTT10 or DTT11 as p materials, respectively. Detailed Implementation

[0055] As described above, this disclosure provides transparent N materials.

[0056] When included in a P:N heterojunction or a double or multilayer junction, preferably a P1:P2:N1:N2 or a P1:P2:N or a P:N1:N2 heterojunction or multilayer junction, the transparent N material according to this disclosure has the following characteristics: excitons generated on colored P or a mixture of colored P materials (P1:P2) or another colored N or a mixture of colored N and P materials (P:N2 or P1:P2:N2) are effectively dissociated by a LUMO dissociation process.

[0057] According to this disclosure, the transparent N material receives electrons from the excited state of the donor (the P material or N material absorbs photons).

[0058] Transparency refers to a light density of less than approximately 60,000 cm⁻¹ within the visible light wavelength range (approximately 400 to 700 nm). -1 The absorption coefficient, or less than approximately 60,000 MΩ. -1 cm -1 The extinction coefficient (in toluene),

[0059] And color refers to a wavelength greater than approximately 60,000 cm⁻¹ in the visible light wavelength range from approximately 400 nm to approximately 700 nm. -1The absorption coefficient (with a maximum value anywhere in this region or absorption in all places in this region).

[0060] As described above, this disclosure provides a transparent P material.

[0061] When included in a P:N heterojunction or a P:N bilayer or multilayer junction, preferably a P1:P2:N1:N2 or a P1:P2:N1 or a P:N1:N2 heterojunction or multilayer junction, the transparent P material according to this disclosure has the following characteristics: excitons generated on colored N or a mixture of colored N materials (N1:N2) or another colored P or a mixture of colored P and N materials (P2:N or P2:N1:N2) are effectively dissociated by a HOMO dissociation process.

[0062] According to this disclosure, a transparent P material supplies electrons to excite a HOMO (photon absorption by the P or N material) of a colored material, which is equivalent to receiving holes.

[0063] According to this disclosure, "transparent" means less than about 60,000 cm⁻¹ in the visible light wavelength range (about 400 to about 700 nm). -1 The absorption coefficient, or less than approximately 60,000 MΩ. -1 cm -1 The extinction coefficient (in toluene),

[0064] And "color" refers to a color depth greater than approximately 60,000 cm⁻¹ in the visible light wavelength range from approximately 400 nm to approximately 700 nm. -1 The absorption coefficient (with a maximum value anywhere in this region or absorption in all places in this region).

[0065] In one embodiment, the transparent N and / or P material of this disclosure,

[0066] - It exhibits no or very low absorption in the visible light wavelength range (approximately 400 to 700 nm), i.e., it has an absorption of less than approximately 60,000 cm⁻¹ in the visible light wavelength range (approximately 400 to 700 nm). -1 The absorption coefficient, or has a value less than approximately 60,000 MΩ. -1 cm -1 The extinction coefficient (in toluene),

[0067] - These are organic compounds (organic-based compounds) that, when used in deposition methods (such as vacuum deposition or spin coating), form high-quality homogeneous films.

[0068] In one embodiment, the transparent N and / or P material of this disclosure is selected from the group consisting of:

[0069] -Naphthalenemonimide (NMI),

[0070] -Naphthalimide (NDI),

[0071] - Dimers of naphthalene monoimide and / or naphthalene diimide (NMI-NMI, NDI-NDI, or NMI-NDI),

[0072] - Materials based on thiophene or selenophene

[0073] -Materials based on dithiophenepyrrole (DTP) and DTP dimers,

[0074] -Anthracene-based materials, and

[0075] - Zinc complex (coordination complex).

[0076] In one embodiment, the transparent N and / or P material of this disclosure is a material based on naphthalene monoimide (NMI) represented by general formula I.

[0077]

[0078] in

[0079] R is selected from -C x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 , as well as

[0080] R1 is selected from

[0081] x is an integer from 1 to 10.

[0082] X is a halogen (F, Cl, Br, I),

[0083] Y is selected from CH2, S, O, Se, and N-R2.

[0084] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0085] In a preferred embodiment of the naphthalene monoimide (NMI)-based material represented by general formula I,

[0086] R is selected from

[0087]

[0088] and / or

[0089] R1 is selected from

[0090]

[0091] In one embodiment, the transparent N and / or P material of this disclosure is a material based on naphthalene monoimide dimer (NMI-NMI) represented by general formula II.

[0092]

[0093] in

[0094] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 ,

[0095] as well as

[0096] Bridge foundation selected

[0097] x is an integer from 1 to 10.

[0098] X is a halogen (F, Cl, Br, I),

[0099] Y is selected from CH2, S, O, Se, and N-R2.

[0100] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0101] In a preferred embodiment of the material based on naphthalene monoimide dimer (NMI-NMI) represented by general formula II,

[0102] R is selected from

[0103]

[0104] and / or

[0105] Bridge foundation selected And none (i.e., no direct connection).

[0106] In one embodiment, the transparent N and / or P material of this disclosure is a naphthalimide (NDI)-based material represented by general formula III.

[0107]

[0108] in

[0109] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 ,

[0110] R1 is selected independently each time it appears.

[0111] x is an integer from 1 to 10.

[0112] X is a halogen (F, Cl, Br, I),

[0113] Y is selected from CH2, S, O, Se, and N-R2.

[0114] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0115] In a preferred embodiment of the naphthalimide (NDI)-based material represented by general formula III,

[0116] R is selected from

[0117] -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0118] and / or

[0119] R1 is selected from

[0120] -OCH2CH3, -Br, -H,

[0121] In one embodiment, the transparent N and / or P material of this disclosure is a naphthalene diimide (NDI)-based material represented by general formula IIIa.

[0122]

[0123] in

[0124] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 ,

[0125] x is an integer from 1 to 10.

[0126] X is a halogen (F, Cl, Br, I),

[0127] Y is selected from CH2, S, O, Se, and N-R2.

[0128] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0129] In a preferred embodiment of the naphthalimide (NDI)-based material represented by general formula IIIa,

[0130] R is specifically selected from -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0131] In one embodiment, the transparent N and / or P material of this disclosure is a material based on naphthalimide dimers (NDI-NDI) represented by general formula IV or V.

[0132]

[0133] In general formula IV

[0134] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 , as well as

[0135] Bridge foundation selected

[0136] x is an integer from 1 to 10.

[0137] X is a halogen (F, Cl, Br, I),

[0138] Y is selected from CH2, S, O, Se, and N-R2.

[0139] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0140] And in the general formula V

[0141] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 , as well as

[0142] R1 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, straight-chain and branched alkoxy, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl, and

[0143] Bridge foundation selected

[0144] x is an integer from 1 to 10.

[0145] X is a halogen (F, Cl, Br, I),

[0146] Y is selected from CH2, S, O, Se, and N-R2.

[0147] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0148] In a preferred embodiment of the material based on naphthalimide dimer (NDI-NDI) represented by general formula IV,

[0149] R is selected from -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0150] and / or

[0151] Bridge foundation selected

[0152] In a preferred embodiment of the material based on naphthalimide dimer (NDI-NDI) represented by general formula V

[0153] R is selected from

[0154] -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0155] R1 is selected from -Br, -H, -OCH2CH3.

[0156] and / or

[0157] Bridge foundation selected

[0158] In one embodiment, the transparent N and / or P material of this disclosure is a material based on naphthalene mono-diimide dimer (NMI-NDI) represented by general formulas selected from general formulas VI to VIII.

[0159]

[0160]

[0161] in

[0162] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 , as well as

[0163] R1 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, straight-chain and branched alkoxy, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl, and

[0164] Bridge foundation selected

[0165] x is an integer from 1 to 10.

[0166] X is a halogen (F, Cl, Br, I),

[0167] Y is selected from CH2, S, O, Se, and N-R2.

[0168] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0169] In one embodiment, the transparent N and / or P material of this disclosure is a thiophene or selenophene-based material represented by a general formula selected from formulas IX to XI.

[0170]

[0171] in

[0172] X and Y are the same or different and are independently selected from CH2, S, O, Se, NR and Si-R2 each time they appear.

[0173] Z is selected from CH and N.

[0174] R and R1 are the same or different and are independently selected from H, straight-chain and branched alkyl, cycloalkyl, straight-chain and branched alkoxy, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, halogenated aryl, biaryl, haloalkyl, heteroaryl and fluorenyl.

[0175] In preferred embodiments of the thiophene or selenophene-based materials of general formulas IX to XI,

[0176] X is selected from S and Se.

[0177] Y is selected from S and Se.

[0178] Z is selected from CH and N.

[0179] R is selected from and / or

[0180] R1 is selected from

[0181] In one embodiment, the transparent N and / or P material of this disclosure is a thiophene or selenophene-based material represented by the general formula XII or XIIb.

[0182]

[0183] in

[0184] R is selected independently each time it appears.

[0185]

[0186] In one embodiment, the transparent N and / or P material of this disclosure is a thiophene or selenophene-based material represented by general formulas XXII to XXXVIII.

[0187]

[0188]

[0189] in

[0190] X and Y are the same or different and are independently selected from CH2, S, O, Se, NR and Si-R2 each time they appear.

[0191] Z is selected from CH and N.

[0192] R and R1 are the same or different and are independently selected from H, straight-chain and branched alkyl, cycloalkyl, straight-chain and branched alkoxy, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloaryl, biaryl, haloalkyl, heteroaryl and fluorenyl.

[0193] In preferred embodiments of thiophene or selenophene-based materials of general formulas XXII to XXXVIII, X is selected from S and Se.

[0194] Y is selected from S and Se.

[0195] Z is selected from CH and N.

[0196] R is selected from

[0197]

[0198] R2 and R3 are either the same or different and are independently selected from H, CH3, alkyl, and aryl each time they appear.

[0199] In one embodiment, the transparent N and / or P material of this disclosure is a thiophene or selenophene-based material represented by the general formula XXXIX or XL:

[0200] T—B—T

[0201] XXXIX

[0202] in

[0203] T is selected from structures having one of the general formulas IX, X, XI or XXII to XXXVIII, as defined herein.

[0204] in

[0205] X and Y are the same or different and are independently selected from CH2, S, O, Se, NR and Si-R2 each time they appear.

[0206] Z is selected from CH and N.

[0207] B is selected from any of the following:

[0208]

[0209] R2 and R3 are either the same or different and are independently selected from H, CH3, alkyl, and aryl each time they appear.

[0210] Each time R appears, it is independently selected from H, alkyl, aryl, ...

[0211] T—H

[0212] XL

[0213] in

[0214] T is selected from structures having one of the general formulas IX, X, XI or XXII to XXXVIII, as defined herein.

[0215] in

[0216] X and Y are the same or different and are independently selected from CH2, S, O, Se, NR and Si-R2 each time they appear.

[0217] Z is selected from CH and N.

[0218] H is selected from any of the following:

[0219]

[0220] In one embodiment, the transparent N and / or P material of this disclosure is a dithiophenepyrrole (DTP)-based material represented by general formula XIII.

[0221]

[0222] in

[0223] R is selected from -C x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 ,

[0224] R1 is selected from

[0225] R3 is selected from straight-chain and branched alkyl groups, cycloalkyl groups, haloalkyl groups, and halogen atoms.

[0226] x is an integer from 1 to 10.

[0227] X is a halogen (F, Cl, Br, I),

[0228] Y is selected from CH2, S, O, Se, and N-R2.

[0229] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0230] In a preferred embodiment of the material based on dithiophenepyrrole (DTP), represented by general formula XIII,

[0231] R is selected from

[0232] R1 is selected from

[0233] and / or

[0234] R2 is selected from straight-chain and branched alkyl groups.

[0235] In one embodiment, the transparent N and / or P material of this disclosure is a material based on dithiophenepyrrole dimer (DTP dimer) represented by general formulas selected from XIV to XVI.

[0236]

[0237] in

[0238] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 ,

[0239] R1 is selected independently each time it appears.

[0240] R3 is selected from straight-chain and branched alkyl groups, cycloalkyl groups, haloalkyl groups, and halogen atoms.

[0241] n is 0 or 1,

[0242] x is an integer from 1 to 10.

[0243] X is a halogen (F, Cl, Br, I),

[0244] Y is selected from CH2, S, O, Se, and N-R2.

[0245] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0246] In a preferred embodiment of the material based on dithiophenepyrrole dimer (DTP dimer), represented by general formulas XIV to XVI,

[0247] R is selected from

[0248] R1 is selected from

[0249] and / or

[0250] R2 is selected from straight-chain and branched alkyl groups.

[0251] In one embodiment, the transparent N and / or P material of this disclosure is an anthracene or anthracene dimer-based material represented by general formula XVII or XVIII.

[0252]

[0253] in

[0254] R is selected independently each time it appears.

[0255] R1 is selected from straight-chain and branched alkyl groups, cycloalkyl groups, haloalkyl groups, and halogen atoms.

[0256] Y is selected from CH2, S, O, Se, and N-R2.

[0257] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0258] In a preferred embodiment of the material based on anthracene or anthracene dimer, represented by general formula XVII or XVIII,

[0259] R is selected from and / or

[0260] R1 is selected from straight-chain and branched alkyl groups.

[0261] In one embodiment, the transparent N and / or P material of this disclosure is a zinc complex-based material.

[0262] Zinc complexes are characterized by the presence of Zn-N bonds or combinations of Zn-N and Zn-O bonds, where the N and O atoms are elements of the organic ligands, and the absence of Zn-C bonds. Materials based on zinc coordination complexes or zinc coordination compounds are represented by general formulas selected from XIX to XXI.

[0263]

[0264] in

[0265] ORN is selected independently each time it appears.

[0266]

[0267] NRN is selected independently each time it appears.

[0268]

[0269] L is selected independently each time it appears.

[0270]

[0271] X is selected from halogens (F, Cl, Br, I), CN, CF3, COOH, NH2.

[0272] R is selected from alkyl and aryl groups.

[0273] As described above, this disclosure provides a P:N heterojunction, preferably a P1:P2:N1:N2 heterojunction, which includes a transparent N material according to this disclosure and / or a transparent P material according to this disclosure.

[0274] In one embodiment, in a P:N heterojunction, the transparent P material according to this disclosure is a donor and the transparent N material according to this disclosure is an acceptor. For example, see... Figure 4 .

[0275] In one embodiment of the P1:P2:N1:N2 heterojunction, one of the P materials may be a transparent P material and a donor according to the present disclosure, and one of the N materials may be a transparent N material and an acceptor according to the present disclosure.

[0276] In one embodiment, the P:N heterojunction, preferably a P1:P2:N1:N2 heterojunction, includes additional N and / or P materials.

[0277] The additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0278] As described above, this disclosure provides a transparent N and / or P material for use in an absorber layer according to this disclosure.

[0279] In one embodiment, the absorbent layer comprises additional N and / or P material.

[0280] The additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0281] As described above, this disclosure provides for the use of transparent N and / or P materials according to this disclosure.

[0282] -In the photoelectric conversion layer, and / or

[0283] -In organic and / or hybrid modules

[0284] Used in optoelectronic applications, such as image sensors, photodiodes, organic photovoltaic devices, including organic photoelectric conversion layers, OLEDs, and OTFT organic modules.

[0285] In one embodiment, the photoelectric conversion layer and / or organic and / or hybrid module (hybrid module) includes additional N and / or P materials.

[0286] The additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0287] As described above, this disclosure provides a photoelectric conversion layer comprising a transparent N and / or P material according to this disclosure.

[0288] In one embodiment, the photoelectric conversion layer includes additional N and / or P materials, wherein the additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0289] In one embodiment, the photoelectric conversion layer includes additional molecules.

[0290] As described above, this disclosure provides an absorbent layer comprising a transparent N and / or P material according to this disclosure.

[0291] In one embodiment, the absorption layer includes additional N and / or P materials, wherein the additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0292] In one embodiment, the absorber layer includes additional molecules.

[0293] As described above, this disclosure provides a device comprising a transparent N and / or P material according to this disclosure or a photoelectric conversion layer according to this disclosure.

[0294] The device may be an organic image sensor, a hybrid image sensor, a photodiode, an organic photovoltaic device, an organic light-emitting diode (OLED), or an organic thin-film transistor (OTFT).

[0295] In one embodiment, the photoelectric conversion layer exhibits a light response within the visible light absorption range.

[0296] In this embodiment, the photoelectric conversion layer of the device includes a transparent N and / or P material according to the present disclosure and additional N and / or P materials, which preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0297] According to this disclosure, when one of the active substances is transparent, the following possibilities are provided:

[0298] The total absorption spectrum can be adjusted by regulating the absorption of only one active substance;

[0299] Only the exciton diffusion efficiency of the partner (absorber) material is adjusted;

[0300] The charge generation efficiency can be adjusted independently via HOMO or LUMO;

[0301] Adjust only the electron mobility (for transparent N) or hole mobility (for transparent P);

[0302] Typically: decoupling absorption and migration properties of electron / hole transfer in the visible range.

[0303] In one embodiment, the photoelectric conversion layer of the device includes additional molecules.

[0304] The photoelectric conversion layer may include different components (dyes) and combinations thereof.

[0305] In one embodiment, the photoelectric conversion layer and / or absorption layer includes further n- and p-type materials (molecules) and their derivatives, which can be used together with the materials disclosed herein, such as...

[0306] Phthalocyanine (Pc), sub-phthalocyanine (SubPc), methyl cyanide (MC), diketopyrrole (DPP), borondipyrrolemethenes (BODIPY), iso-indigo (ID), perylene diimide (PDI) and perylene monoimide (PMI), as well as quinacridone (QD), fused acenes, such as pentaphenylene and tetraphenylene, and triphenylamine and its derivatives (TPA), as donors;

[0307] and / or

[0308] Fullerenes, aryl diimides and monoimides (e.g., but not limited to PDI and PMI), phthalocyanines and phthalocyanines, borodipyrrole methylene (BODIPY), and cyanopentene are used as acceptors.

[0309] As described above, this disclosure provides an organic image sensor that includes a photoelectric conversion layer according to this disclosure.

[0310] The organic image sensor disclosed herein preferably includes:

[0311] (a) An organic photoelectric conversion unit, comprising a photoelectric conversion layer according to the present disclosure,

[0312] (b) At least one electrode,

[0313] (c) substrate,

[0314] (d) Optionally, a second electrode on the photoelectric conversion layer.

[0315] The substrate can be silicon, quartz, glass, polymers such as PMMA, PC, PS, COP, PVA, PVP, PES, PET, PEN, mica, or combinations thereof.

[0316] The substrate can also be other photoelectric conversion units.

[0317] This means that the device of this disclosure may include (i) two inorganic units and one organic unit, (ii) one inorganic unit and two organic units, or (iii) three organic units combined with each other in an organic image sensor. Any organic unit may contain molecules / layers / devices according to this disclosure.

[0318] In a preferred embodiment, the organic image sensor comprises three organic conversion units containing molecules in the layers of this disclosure (each having a transparent electrode in the device), which are combined with each other and each operate in one of the ranges of 400 nm to 500 nm, 500 nm to 600 nm, and 600 nm to 700 nm.

[0319] Combinatorial units can be achieved by vertical and / or horizontal stacking of organic-organic or organic-inorganic units.

[0320] Electrode materials can be

[0321] - Transparent metal oxides, such as indium tin oxide (ITO), fluorine-doped indium oxide (IFO), tin oxide, fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), zinc oxide (including Al, B, and Ga-doped zinc oxide), indium-zinc oxide (IZO), TiO2,

[0322] - Non-transparent or semi-transparent metals or alloys or conductive polymers, such as Au, Ag, Cr, Ni, Pd, AlSiCu, or any metal or metal alloy or metal combination (with appropriate work function); PEDOT / PSS, PANI or PANI / PSS, graphene.

[0323] As described above, this disclosure provides a hybrid silicon-organic image sensor or an organic image sensor, comprising:

[0324] (a) An organic photoelectric conversion unit, comprising a photoelectric conversion layer according to the present disclosure,

[0325] (b) Optionally, a Si-based photoelectric conversion unit,

[0326] (c) Metal wire,

[0327] (d) (CMOS) substrate,

[0328] (e) Insulating layer, preferably oxide.

[0329] In one embodiment, the organic photoelectric conversion unit of the image sensor of this disclosure includes different layers within an organic-based photoelectric conversion unit, such as...

[0330] -n type materials,

[0331] -p type materials,

[0332] -n buffer layer,

[0333] -p buffer layer,

[0334] Or combinations and / or mixtures thereof (e.g., n-material and p-material co-deposited in a single layer).

[0335] For example, the organic image sensor disclosed herein may have the following structure:

[0336] -Substrate / First Electrode / nBuffer Layer / n Material / p Material / pBuffer Layer / Second Electrode;

[0337] -Substrate / First Electrode / nBuffer Layer / n Material / Mix of n and p Materials / p Material / p Buffer Layer / Second Electrode;

[0338] -Substrate / First Electrode / nBuffer Layer / n Material / Mix of n and p Materials / pBuffer Layer / Second Electrode;

[0339] -Substrate / First Electrode / pBuffer Layer / p Material / n Material / n Buffer Layer / Second Electrode;

[0340] -Substrate / First Electrode / pBuffer Layer / p Material / Mix of n and p Materials / n Material / n Buffer Layer / Second Electrode;

[0341] -Substrate / First Electrode / p Buffer Layer / p Material / Mixture of n and p Materials / n Buffer Layer / Second Electrode.

[0342] The organic image sensor disclosed herein may include different layer structures, particularly regarding the positions of n and p materials relative to the CMOS portion.

[0343] Organic light conversion units can be used in conjunction with Si-based photoelectric conversion units, where different layers in a hybrid silicon-organic image sensor absorb different colors (BGR) (see...). Figure 2 Alternatively, it can be used without a Si-based photoelectric conversion unit. In this case, the organic photoelectric conversion unit has the ability to absorb different colors (BGR) (see...). Figure 3 ).

[0344] The absorption rate (BGR) in the range of 400-500 nm, 500-600 nm, and 600-700 nm, and outside the ranges mentioned above, is preferably less than 20%, more preferably less than 10% and 5%.

[0345] As mentioned above, the substrate can also be other photoelectric conversion units.

[0346] As described above, the device of the present invention may include (i) two inorganic units and one organic unit, (ii) one inorganic unit and two organic units, or (iii) three organic units combined with each other in an organic image sensor. Any organic unit may contain molecules / layers / devices according to this disclosure.

[0347] The deposition methods used to produce organic photoelectric conversion layers include PVD, CVD, spin coating, dip coating, casting, inkjet printing, screen printing, spraying, and offset printing.

[0348] Different process temperatures are possible for treating the layers, ranging from 50 to 245 degrees Celsius. The layer treatment (annealing) can be performed before and / or after the deposition of the top electrode.

[0349] As described above, this disclosure provides a method for synthesizing materials based on naphthalene monoimide (NMI) (represented by general formula I) and materials based on naphthalene monoimide dimers (NMI-NMI) (represented by general formula II), comprising the following steps:

[0350] -Imine 4-bromo-1,8-naphthalenedicarboxylic anhydride derivatives in the presence of primary amines and acids.

[0351] - Subsequently, palladium-catalyzed Suzuki coupling is performed with a specific boronic ester or "bridging group"-boronic ester.

[0352] This disclosure also provides a method for synthesizing naphthalimide (NDI)-based materials (represented by general formula III), comprising the following steps:

[0353] -Imine 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic acid dianhydride derivatives in the presence of R-primary amines and acids.

[0354] - Subsequently coupled with palladium-catalyzed Suzuki coupling of a specific R1-boronate.

[0355] This disclosure also provides a method for synthesizing materials based on naphthalimide dimers (NDI-NDI) (represented by general formula IV or V), comprising:

[0356] (i) In the case of general formula IV, the following steps are taken:

[0357] - Monoimideation of 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic acid dianhydride derivatives in the presence of R-primary amines and acids.

[0358] -Subsequently, a second imine is formed in the presence of a "bridging group"-diamine and an acid, and

[0359] (ii) In the case of general formula V, the following steps are taken:

[0360] -Imine 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic acid dianhydride derivatives in the presence of R-primary amines and acids.

[0361] -Subsequently coupled with a specific R1-boron ester via a single palladium-catalyzed Suzuki coupling,

[0362] - Subsequently coupled with a second palladium catalyst Suzuki for a specific bridged-diboron ester.

[0363] This disclosure also provides a method for synthesizing materials based on naphthalene mono-diimide dimers (NMI-NDI) (represented by general formulas selected from general formulas VI to VIII), comprising the following steps:

[0364] -Imine the corresponding 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride using a suitable amine derivative.

[0365] - Subsequently coupled with one or more palladium-catalyzed Suzukis of a specific diboronate.

[0366] This disclosure also provides a method for synthesizing materials based on dithiophenepyrrole dimers (DTP dimers) (represented by general formulas selected from general formulas XIV and XV), comprising the following steps:

[0367] -3,3'-dibromo-2,2'-bisthiophene is coupled to the corresponding R-amine via palladium-catalyzed Buchwald-Hartwig coupling to receive an N-substituted dithiophenepyrrole (DTP) core unit.

[0368] Further steps include:

[0369] - Utilizing N-bromo-succinimide bromination

[0370] -Subsequently coupled with a single palladium-catalyzed Suzuki coupling of R1-boronate, and

[0371] - Subsequently, it is further palladium-catalyzed Suzuki coupling with a specific R2-phenyl-substituted diboronate.

[0372] This disclosure also provides a method for synthesizing materials based on dithiophenepyrrole dimers (DTP dimers) (represented by general formula XVI), comprising the following steps:

[0373] -3,3'-dibromo-2,2'-bisthiophene is coupled to the corresponding R2-phenyl-substituted diamine via palladium-catalyzed Buchwald-Hartwig coupling to receive the N-substituted dithiophene-pyrrole (DTP) dimer core unit.

[0374] Further steps include:

[0375] - Utilizing N-bromo-succinimide bromination

[0376] -Subsequently coupled with a single palladium-catalyzed Suzuki coupling of R1-boronate, and

[0377] - Subsequently, it is further palladium-catalyzed Suzuki coupling with a specific R2-phenyl-substituted diboronate.

[0378] This disclosure also provides a method for synthesizing zinc-based materials (represented by general formulas selected from XIX, XX, and XI), comprising the following steps:

[0379] -Ligands of the (HO-RN) and (HN-RN) types are combined using dehydrated zinc acetate and base in refluxed methanol.

[0380] Note that this technology can also be configured as described below.

[0381] (1) A transparent nitrogen material,

[0382] When included in a P:N heterojunction or a double or multilayer junction, preferably a P1:P2:N1:N2 or a P1:P2:N or a P:N1:N2 heterojunction or multilayer junction, it has the following characteristics: excitons generated on colored P or a mixture of colored P materials (P1:P2) or another colored N or a mixture of colored N and P materials (P:N2 or P1:P2:N2) are effectively dissociated through the LUMO dissociation process.

[0383] Transparency refers to a light density of less than approximately 60,000 cm⁻¹ within the visible light wavelength range (approximately 400 to 700 nm). -1 The absorption coefficient, or less than approximately 60,000 MΩ. -1 cm -1 The extinction coefficient (in toluene),

[0384] And color refers to a wavelength greater than approximately 60,000 cm⁻¹ in the visible light wavelength range from approximately 400 nm to approximately 700 nm. -1 The absorption coefficient (with a maximum value anywhere in this region or absorption in all places in this region).

[0385] (2) A transparent P material,

[0386] When included in a P:N heterojunction or P:N bilayer or multilayer junction, preferably a P1:P2:N1:N2 or P1:P2:N1 or P:N1:N2 heterojunction or multilayer junction, it has the following characteristics: It effectively dissociates excitons generated on colored N or a mixture of colored N materials (N1:N2) or another colored P or a mixture of colored P and N materials (P2:N or P2:N1:N2) through a HOMO dissociation process.

[0387] Transparency refers to a light density of less than approximately 60,000 cm⁻¹ within the visible light wavelength range (approximately 400 to 700 nm). -1 The absorption coefficient, or less than approximately 60,000 MΩ. -1 cm -1 The extinction coefficient (in toluene),

[0388] And color refers to a wavelength greater than approximately 60,000 cm⁻¹ in the visible light wavelength range from approximately 400 nm to approximately 700 nm. -1 The absorption coefficient (with a maximum value anywhere in this region or absorption in all places in this region).

[0389] (3) or (1) or (2) of a transparent N or P material, wherein the above material,

[0390] -Having a wavelength of less than approximately 60,000 cm⁻¹ in the visible light wavelength range (approximately 400 to approximately 700 nm).-1 The absorption coefficient is less than approximately 60,000 M. -1 cm -1 The extinction coefficient (in toluene),

[0391] - It is an organic compound that forms a high-quality homogeneous film when deposited using methods such as vacuum deposition or spin coating.

[0392] (4) Any of the transparent N or P materials from (1) to (3), selected from the group consisting of:

[0393] -Naphthalenemonimide (NMI),

[0394] -Naphthalimide (NDI),

[0395] - Dimers of naphthalene monoimide and / or naphthalene diimide (NMI-NMI, NDI-NDI, or NMI-NDI),

[0396] - Materials based on thiophene or selenophene

[0397] -Based on dithiophenepyrrole (DTP) and DTP dimer materials,

[0398] -Anthracene-based materials, and

[0399] - Zinc complex.

[0400] (5)(4) transparent N or P materials, wherein the material is a naphthalene monoimide (NMI) based material represented by general formula I.

[0401]

[0402] in

[0403] R is selected from -C x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 , as well as

[0404] R1 is selected from

[0405] x is an integer from 1 to 10.

[0406] X is a halogen (F, Cl, Br, I),

[0407] Y is selected from CH2, S, O, Se, and N-R2.

[0408] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0409] Preferably

[0410] R is preferred to be selected from

[0411] -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0412] R1 is preferred to be selected

[0413]

[0414] (6)(4) or (5) transparent N or P materials, wherein the above materials are materials based on naphthalene monoimide dimers (NMI-NMI) represented by general formula II.

[0415]

[0416] in

[0417] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 , as well as

[0418] Bridge foundation selected

[0419] x is an integer from 1 to 10.

[0420] X is a halogen (F, Cl, Br, I),

[0421] Y is selected from CH2, S, O, Se, and N-R2.

[0422] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0423] Preferably

[0424] R is preferred to be selected from

[0425] -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0426] Bridge foundations are preferred And none (i.e., no direct connection).

[0427] (7)(4) transparent N or P materials, wherein the above materials are naphthalimide (NDI) based materials represented by general formula III.

[0428]

[0429] in

[0430] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 ,

[0431] R1 is selected independently each time it appears.

[0432] x is an integer from 1 to 10.

[0433] X is a halogen (F, Cl, Br, I),

[0434] Y is selected from CH2, S, O, Se, and N-R2.

[0435] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0436] Preferably

[0437] R is preferred to be selected from

[0438] -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0439] R1 is preferred to be selected

[0440]

[0441] Or, the above-mentioned materials are materials based on naphthalimide (NDI) represented by general formula IIIa.

[0442]

[0443] in

[0444] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 ,

[0445] x is an integer from 1 to 10.

[0446] X is a halogen (F, Cl, Br, I),

[0447] Y is selected from CH2, S, O, Se, and N-R2.

[0448] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0449] Preferably

[0450] R is preferred to be selected from -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0451] (8)(4) or (7) transparent N or P materials, wherein the above materials are materials based on naphthalimide dimers (NDI-NDI) represented by general formula IV or V.

[0452]

[0453] In general formula IV

[0454] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 , as well as

[0455] Bridge foundation selected

[0456] x is an integer from 1 to 10.

[0457] X is a halogen (F, Cl, Br, I),

[0458] Y is selected from CH2, S, O, Se, and N-R2.

[0459] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0460] Among them, in general formula IV, preferably

[0461] R is preferred to be selected from -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0462] Bridge foundations are preferred

[0463] In the general formula V

[0464] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 , as well as

[0465] R1 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, straight-chain and branched alkoxy, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl, and

[0466] Bridge foundation selected

[0467] x is an integer from 1 to 10.

[0468] X is a halogen (F, Cl, Br, I),

[0469] Y is selected from CH2, S, O, Se, and N-R2.

[0470] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0471] In general formula V, preferably

[0472] R is preferred to be selected from

[0473] -(CF2)5CF3, -(CH2)5CH3, -CH2-(CF2)3-CF3,

[0474] R1 is preferably selected from -Br, -H, -OCH2CH3.

[0475] Bridge foundations are preferred

[0476] A transparent N or P material of any one of (9)(4) to (8), wherein the above materials are materials based on naphthalene mono-diimide dimers (NMI-NDI) represented by general formulas selected from general formulas VI to VIII.

[0477]

[0478]

[0479] in

[0480] R is selected independently from -C each time it appears. x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 , as well as

[0481] R1 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, straight-chain and branched alkoxy, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl, and

[0482] Bridge foundation selected

[0483] x is an integer from 1 to 10.

[0484] X is a halogen (F, Cl, Br, I),

[0485] Y is selected from CH2, S, O, Se, and N-R2.

[0486] R2 is selected independently each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0487] (10)(4) transparent N or P materials, wherein the above materials are thiophene or selenophene-based materials represented by general formulas selected from general formulas IX to XI.

[0488]

[0489] in

[0490] X and Y are the same or different and are independently selected from CH2, S, O, Se, NR and Si-R2 each time they appear.

[0491] Z is selected from CH and N.

[0492] R and R1 are the same or different and are independently selected from H, straight-chain and branched alkyl, cycloalkyl, straight-chain and branched alkoxy, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloaryl, biaryl, haloalkyl, heteroaryl, and fluorenyl in each occurrence.

[0493] Preferably

[0494] X is preferred from S and Se.

[0495] Y is preferred to be selected from S and Se.

[0496] Z is preferred to be selected from CH and N.

[0497] R is preferred to be selected from

[0498] R1 is preferred to be selected

[0499] (11)(4) or (10) transparent N or P materials, wherein the above materials are thiophene or selenophene-based materials represented by general formula XII or XIIb.

[0500]

[0501] in

[0502] R is selected independently each time it appears.

[0503]

[0504] (12)(4) transparent N or P materials, wherein the above materials are thiophene or selenophene-based materials represented by general formulas XXII to XXXIII:

[0505]

[0506]

[0507] in

[0508] X and Y are the same or different and are independently selected from CH2, S, O, Se, NR and Si-R2 each time they appear.

[0509] Z is selected from CH and N.

[0510] R and R1 are the same or different and are independently selected from H, straight-chain and branched alkyl, cycloalkyl, straight-chain and branched alkoxy, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloaryl, biaryl, haloalkyl, heteroaryl, and fluorenyl in each occurrence.

[0511] Preferably

[0512] X is preferred from S and Se.

[0513] Y is preferred to be selected from S and Se.

[0514] Z is preferred to be selected from CH and N.

[0515] R is preferred to be selected from

[0516]

[0517] R2 and R3 are either the same or different and are independently selected from H, CH3, alkyl, and aryl each time they appear.

[0518] (13)(10) or (12) transparent N or P materials, wherein the above materials are thiophene or selenophene-based materials represented by the general formula XXXIX or XL:

[0519] T—B—T

[0520] XXXIX

[0521] in

[0522] T is selected from structures having one of the general formulas IX, X, XI or XXII to XXXVIII, as defined in (10) or (12).

[0523] in

[0524] X and Y are the same or different and are independently selected from CH2, S, O, Se, NR and Si-R2 each time they appear.

[0525] Z is selected from CH and N.

[0526] B is selected from any of the following:

[0527]

[0528] R2 and R3 are either the same or different and are independently selected from H, CH3, alkyl, and aryl each time they appear.

[0529] R is independently selected from H, alkyl, aryl, ... each time it appears.

[0530]

[0531] T—H

[0532] XL

[0533] in

[0534] T is selected from structures having one of the general formulas IX, X, XI or XXII to XXXVIII, as defined in (10) or (12).

[0535] in

[0536] X and Y are the same or different and are independently selected from CH2, S, O, Se, NR and Si-R2 each time they appear.

[0537] Z is selected from CH and N.

[0538] H is selected from any of the following:

[0539]

[0540] (14)(4) transparent N or P materials, wherein the above materials are thiophene-pyrrole (DTP) based materials represented by general formula XIII.

[0541]

[0542] in

[0543] R is selected from -C x H 2x+1 -C x X 2x+1 -C x H2X 2x-1 ,

[0544] R1 is selected from

[0545] R3 is selected from straight-chain and branched alkyl groups, cycloalkyl groups, haloalkyl groups, and halogen atoms.

[0546] x is an integer from 1 to 10.

[0547] X is a halogen (F, Cl, Br, I),

[0548] Y is selected from CH2, S, O, Se, and N-R2.

[0549] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0550] Preferably

[0551] R is preferred to be selected from

[0552] R1 is preferred to be selected

[0553]

[0554] R2 is preferably selected from straight-chain and branched alkyl groups.

[0555] (15)(4) or (14) transparent N or P material, wherein the above material is a material based on dithiophenepyrrole dimer (DTP dimer) represented by a general formula selected from general formulas XIV to XVI.

[0556]

[0557] in

[0558] R is selected independently each time it appears.

[0559] -C x H 2x-1 -C x X 2x+1 -C x H2X 2x-1 ,

[0560] R1 is selected independently each time it appears.

[0561] R3 is selected from straight-chain and branched alkyl groups, cycloalkyl groups, haloalkyl groups, and halogen atoms.

[0562] n is 0 or 1,

[0563] x is an integer from 1 to 10.

[0564] X is a halogen (F, Cl, Br, I),

[0565] Y is selected from CH2, S, O, Se, and N-R2.

[0566] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0567] Preferably

[0568] R is preferred to be selected from

[0569] R1 is preferred to be selected

[0570]

[0571] R2 is preferably selected from straight-chain and branched alkyl groups.

[0572] (16)(4) transparent N or P materials, wherein the above materials are materials based on anthracene or anthracene dimers represented by general formula XVII or XVIII.

[0573]

[0574] in

[0575] R is selected independently each time it appears.

[0576] R1 is selected from straight-chain and branched alkyl groups, cycloalkyl groups, haloalkyl groups, and halogen atoms.

[0577] Y is selected from CH2, S, O, Se, and N-R2.

[0578] R2 is independently selected each time it appears from H, straight-chain and branched alkyl, cycloalkyl, haloalkyl, halogen atom, alkyl or arylthioalkyl, alkyl or arylamine, aryl, haloalkyl, heteroaryl, fluorenyl.

[0579] Preferably

[0580] R is preferred to be selected from

[0581] R1 is preferably selected from straight-chain and branched alkyl groups.

[0582] (17)(4) transparent N or P materials, wherein the above materials are zinc-based materials represented by general formulas selected from general formulas XIX to XXI.

[0583]

[0584] in

[0585] ORN is selected independently each time it appears.

[0586]

[0587] NRN is selected independently each time it appears.

[0588]

[0589] L is selected independently each time it appears.

[0590]

[0591] X is selected from halogens (F, Cl, Br, I), CN, CF3, COOH, NH2.

[0592] R is selected from alkyl and aryl groups.

[0593] (18) A P:N heterojunction, preferably a P1:P2:N1:N2 heterojunction, comprising a transparent N material according to any one of (1) to (17) and / or a transparent P material according to any one of (1) to (17),

[0594] And including other N and / or P materials,

[0595] The additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0596] (19) The use of any of the transparent N and / or P materials in the absorbing layer according to (1) to (17),

[0597] And including other N and / or P materials,

[0598] The additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0599] (20) The use of any of the transparent N and / or P materials according to (1) to (17) in photoelectric conversion layers and / or organic and / or hybrid modules for optoelectronic applications such as image sensors, photodiodes, organic photovoltaic devices, including organic photoelectric conversion layers, OLEDs and OTFT organic modules.

[0600] And including other N and / or P materials,

[0601] The additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0602] (21) A photoelectric conversion layer comprising a transparent N and / or P material according to any one of (1) to (17),

[0603] And including other N and / or P materials,

[0604] The other N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0605] And optionally include other molecules.

[0606] (22) An absorbent layer comprising a transparent N and / or P material according to any one of (1) to (17),

[0607] And including other N and / or P materials, and

[0608] Optionally, additional molecules may be included.

[0609] The additional N and / or P materials preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0610] (23) A device comprising a transparent N and / or P material according to any one of (1) to (17) or a photoelectric conversion layer according to (21),

[0611] The device is preferably an organic image sensor, a hybrid image sensor, a photodiode, an organic photovoltaic device, an organic light-emitting diode (OLED), or an organic thin-film transistor (OTFT).

[0612] (24) According to the device of (23), the photoelectric conversion layer exhibits a light response in the visible light absorption range.

[0613] (25) The device according to (23) or (24), including a transparent N and / or P material according to any one of (1) to (17) or a photoelectric conversion layer according to (21),

[0614] And / or includes additional N and / or P materials, which preferably exhibit absorption in the visible light wavelength range (about 400 to about 700 nm).

[0615] And / or include other molecules.

[0616] (26) An organic image sensor, comprising:

[0617] (a) An organic photoelectric conversion unit comprising a photoelectric conversion layer according to (21),

[0618] (b) At least one electrode,

[0619] (c) substrate,

[0620] (d) Optionally, a second electrode above the photoelectric conversion layer.

[0621] (27) A hybrid silicon-organic image sensor or an organic image sensor, comprising:

[0622] (a) An organic photoelectric conversion unit comprising a photoelectric conversion layer according to (21),

[0623] (b) Optionally, a Si-based photoelectric conversion unit,

[0624] (c) Metal wire,

[0625] (d) (CMOS) substrate,

[0626] (e) Insulating layer, preferably oxide.

[0627] (28) The organic image sensor according to (26) or (27), wherein the organic photoelectric conversion unit comprises different layers,

[0628] Such as n-type materials, p-type materials, n-buffered layers and / or p-buffered layers, or combinations or mixtures thereof.

[0629] (29) A method for synthesizing a material based on naphthalene monoimide (NMI) (represented by general formula I) and a material based on naphthalene monoimide dimer (NMI-NMI) (represented by general formula II), comprising the following steps:

[0630] -Imine 4-bromo-1,8-naphthalenedicarboxylic anhydride derivatives in the presence of primary amines and acids.

[0631] - Subsequently, palladium-catalyzed Suzuki coupling is performed with a specific boronic ester or "bridging group"-boronic ester.

[0632] (30) A method for synthesizing a naphthalimide (NDI)-based material (represented by general formula III), comprising the following steps:

[0633] -Imine 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic acid dianhydride derivatives in the presence of R-primary amines and acids.

[0634] - Subsequently coupled with palladium-catalyzed Suzuki coupling of a specific R1-boronate.

[0635] (31) A method for synthesizing a material based on naphthalimide dimer (NDI-NDI) (represented by general formula IV), comprising the following steps:

[0636] - Monoimideation of 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic acid dianhydride derivatives in the presence of R-primary amines and acids.

[0637] - Subsequently, in the presence of a "bridging group"-diamine and an acid, a second imine is formed.

[0638] (32) A method for synthesizing a material based on naphthalimide dimer (NDI-NDI) (represented by general formula V), comprising the following steps:

[0639] -Imine 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic acid dianhydride derivatives in the presence of R-primary amines and acids.

[0640] -Subsequently coupled with a specific R1-boron ester via a single palladium-catalyzed Suzuki coupling,

[0641] - Subsequently coupled with a second palladium-catalyzed Suzuki coupling with a specific bridged diboronate.

[0642] (33) A method for synthesizing a material based on naphthalene mono-diimide dimer (NMI-NDI) (represented by a general formula selected from general formulas VI to VIII), comprising the following steps:

[0643] -Imine the corresponding 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride using a suitable amine derivative.

[0644] - Subsequently coupled with one or more palladium-catalyzed Suzukis of a specific diboronate.

[0645] (34) A method for synthesizing a material based on dithiophenepyrrole dimer (DTP dimer) (represented by a general formula selected from general formulas XIV and XV), comprising the following steps:

[0646] -3,3'-dibromo-2,2'-bisthiophene was coupled to the corresponding R-amine via palladium-catalyzed Buchwald-Hartwig coupling to receive an N-substituted dithiophenepyrrole (DTP) core unit.

[0647] - Utilizing N-bromo-succinimide bromination

[0648] -Subsequently coupled with a single palladium-catalyzed Suzuki coupling of R1-boronate, and

[0649] - Subsequently, it is further palladium-catalyzed Suzuki coupling with a specific R2-phenyl-substituted diboronate.

[0650] (35) A method for synthesizing a material based on dithiophenepyrrole dimer (DTP dimer) (represented by general formula XVI), comprising the following steps:

[0651] -3,3'-dibromo-2,2'-bisthiophene is coupled to the corresponding R2-phenyl-substituted diamine via palladium-catalyzed Buchwald-Hartwig coupling to receive the N-substituted dithiophenepyrrole (DTP) dimer core unit.

[0652] - Utilizing N-bromo-succinimide bromination

[0653] -Subsequently coupled with a single palladium-catalyzed Suzuki coupling of R1-boronate, and

[0654] - Subsequently, it is further palladium-catalyzed Suzuki coupling with a specific R2-phenyl-substituted diboronate.

[0655] (36) A method for synthesizing zinc-based materials (represented by a general formula selected from general formulas XIX, XX and XI), comprising the following steps:

[0656] -Ligands of the (HO-RN) and (HN-RN) types are bound with dehydrated zinc acetate and base (in refluxed methanol).

[0657] As used herein, the term "N material" refers to a material that receives electrons.

[0658] As used herein, the term "P material" refers to a material that is given electrons.

[0659] As used herein, the terms “naphthalene monoimide” or “NMI” or “naphthalene monoimide-based material” refer to molecules based on the 1,4-naphthalene monoimide structure.

[0660] As used herein, the terms “naphthalimide” or “NDI” or “naphthalimide-based material” refer to molecules based on the 1,4,5,8-naphthalimide structure.

[0661] As used herein, the term "thiophene material" or "thiophene-based material" refers to a molecule in which at least thiophene or a thiophene derivative is present in the molecular structure.

[0662] As used herein, the terms "selenophene material" or "selenophene-based material" refer to molecules in which at least selenophene or a selenophene derivative is present in the molecular structure.

[0663] As used herein, the term "anthracene material" or "anthracene-based material" refers to a molecule that contains at least anthracene molecules in its molecular structure.

[0664] As used herein, the terms “zinc complex material,” “zinc complex,” or “zinc complex-based material” refer to a molecule containing zinc atoms, wherein the zinc atoms are coordinated to bidentate ligands of nitrogen-containing heterocycles.

[0665] As used herein, the terms "absorption in the visible light wavelength range" or "molecule exhibiting absorption in the visible light wavelength range" refer to a molecule / dye that is able to absorb light in only one or more portions of the indicated full range or in the entire range. For example, one molecule may absorb only in the 500-700 nm range, while another molecule may absorb in the 400-700 nm or 500-600 nm range, and a third molecule may absorb in the 400-500 nm range (or preferably the aforementioned subranges of 400 nm to 500 nm, 500 nm to 600 nm, or 600 nm to 700 nm). Such wording encompasses all these cases.

[0666] As used herein, the term “narrow absorption band” means an absorption band width of 200 nm, more preferably 150 nm, and more preferably 100 nm at 0 intensity.

[0667] As used herein, the term "transparent" or "transparent material" refers to a material having a density of less than about 60,000 cm⁻¹ in the visible light wavelength range (about 400 to about 700 nm). -1 The absorption coefficient is less than approximately 60,000 M. -1 cm -1 The extinction coefficient (in toluene).

[0668] As used herein, the term "colored" or "colored material" refers to a material that exhibits a color intensity greater than approximately 60,000 cm⁻¹ in the visible light wavelength range. -1 The absorption coefficient has a blue, green, or red maximum value, especially in the region from about 400 nm to about 700 nm (with a maximum value anywhere in this region or absorption in all places in this region).

[0669] According to this disclosure, the term "electrode" refers to an electrical lead used to apply a voltage. An electrode can be "interdigitated," meaning it has a comb-like shape, wherein two combs are opposite each other and their respective contours interlock. Alternatively, an electrode can be non-interdigitated. Electrodes can be transparent or opaque. Transparent electrodes can, for example, be formed from indium tin oxide (ITO) or from tin oxide fluoride (FTO). Optical electrodes can be reflective and can, for example, be formed from silver (Ag) or gold (Au).

[0670] The requirements for photoelectric conversion layers used in image sensors are stringent and can be summarized as follows:

[0671] (i) a narrow absorption band of at least one active substance;

[0672] (ii) High extinction coefficient, ε>10 4 L mol -1 cm -1 —The corresponding high absorption coefficient of at least one active substance;

[0673] (iii) Heat resistant;

[0674] (iv) High photoelectric conversion efficiency (EQE);

[0675] (v) High-speed response / high carrier mobility;

[0676] (vi) Low dark current in the device;

[0677] (vii) Thin film, deposited by thermal vapor deposition (Tvp) <Tdec)。

[0678] The inventors have discovered that materials with specific structures that have no or very low absorption in the visible range (400 to 650 nm) for use as active materials in organic light conversion units belong to the following different families:

[0679] -Naphthalenemonimide (NMI),

[0680] -Naphthalimide (NDI), and

[0681] - Dimers of two previous types of molecules (NMI-NMI, NDI-NDI, or NMI-NDI),

[0682] -Thiophene-based materials

[0683] -Anthracene-based materials

[0684] - Zinc complex.

[0685] In the photoelectric conversion material layer, together with the material that absorbs in the visible range, the material is used for a bulk heterojunction (hybrid pn layer) or a PN heterojunction (formed between p layer and n layer) or a PiN junction (p layer-hybrid layer as pn bulk heterojunction-n layer).

[0686] The materials disclosed herein can be used as active substances in organic light conversion units.

[0687] Organic light conversion units can be used in conjunction with Si-based photoelectric conversion units, where different layers in a hybrid silicon-organic image sensor absorb different colors (BGRs), or they can be used without Si-based photoelectric conversion units. In this case, the organic light conversion unit has the ability to absorb different colors (BGRs).

[0688] The general structure of the resulting hybrid image sensor device and the detailed schematic representation of the organic photoelectric conversion unit are shown in [the diagram]. Figure 2 and Figure 3 .

[0689] The inventors have discovered transparent N or transparent P materials (transparent = thin film <60000cm). -1 Absorption coefficient from 400 nm to 700 nm or <60,000 MΩ -1 cm -1 The extinction coefficient (in toluene), and its properties in devices with P:N (generally P1:P2:N1:N2) heterojunctions:

[0690] - If N—through the LUMO dissociation process, effectively dissociates excitons generated on a colored (colored = in the VIS region with a maximum absorption coefficient of >60,000 in Vis) P (or a mixture of colored P materials) or another colored N (or a mixture of colored N materials)—then the excitons receive electrons from the excited state of the donor (the photon-absorbing P or N material).

[0691] - If P—through the HOMO dissociation process, effectively dissociates the excitons generated on a colored (colored = the VIS region with a maximum absorption coefficient of >60,000 in the VIS) N (or a mixture of colored N materials) or another colored P (or a mixture of colored P materials) to supply electrons into the excited colored material (the P material or N material that absorbs photons) HOMO, which is equivalent to receiving holes from them.

[0692] For example, in a P:N instance, the P material is the donor and the N material is the acceptor (as shown, for example). Figure 4 In one embodiment, one of the P1:P2:N1:N2:N materials can be a donor and one of the P materials can be a acceptor.

[0693] Dissociation / charge transfer efficiency (ηCT), generally described as follows:

[0694] ηCT has ηCT (HOMO) and ηCT (LUMO) components.

[0695] exist Figure 4 (As an example)

[0696] • The acceptor is an N material that receives electrons—either in its LUMO (transparent N) state and having ηCT (LUMO), or in its HOMO (transparent P) state and having ηCT (HOMO) (the last one is equivalent to transferring a hole to the donor).

[0697] • The donor is the material that gives electrons—either from its LUMO (when in the excited state, = colored P) or from its HOMO (transparent P);

[0698] • For transparent N-ηCT (LUMO), it must be high;

[0699] • For transparent P-ηCT (HOMO), it must be high.

[0700] The main advantages of the transparent N and / or P materials disclosed herein, especially for applications in photoelectric conversion layers and devices, are as follows:

[0701] 1. The possibility of tuning the absorption spectrum of an active device by adjusting the absorption spectrum of only one active component. This would be the spectrum of the mating submaterial—the p mating submaterial absorbs when using a transparent n-material, and the n mating submaterial absorbs when using a transparent p-material.

[0702] 2. The electron mobility in transparent n-materials only and the hole mobility in transparent p-materials only can be adjusted.

[0703] 3. Adjust the HOMO or LUMO level (and ensure a large band gap to achieve high transparency in the visible range).

[0704] 4. Only one type of exciton dissociation / charge generation efficiency can be optimized: via LUMO (for transparent n) or via HOMO (for transparent p) materials (see...). Figure 4 ).

[0705] The main advantages of new n and p materials, which have no absorption or very low absorption in the visible wavelength range (400-700 nm), as active materials for use in photoelectric conversion layers are as follows:

[0706] Excellent photostability—especially due to UV absorption only;

[0707] • The absorption spectrum of the device can be tuned by the absorption of the other active component, namely, the absorption spectrum of the p material in the case of transparent n and the absorption of the n material in the case of transparent p;

[0708] • It is easy to change the HOMO and LUMO energy levels;

[0709] • High thermal stability (300 to 500 °C, depending on the substituents, but at least 300 °C);

[0710] • High electron (for n) and / or hole (for p) mobility—especially independent tuning of mobility—for example, for transparent n materials, only high electron mobility is required;

[0711] • High exciton dissociation capability—to allow optical conversion devices to have high EQE;

[0712] • High charge generation efficiency of the device—high charge transfer efficiency and charge separation efficiency;

[0713] • Especially the independent adjustment of charge generation efficiency—through LUMO (for transparent N) and through HOMO (for transparent P);

[0714] • It can be used accordingly as an n-buffer or p-buffer layer—allowing for further device optimization, with possible tuning of the morphology through the active layer and / or energy level alignment (through the device).

[0715] The main advantages of naphthalene monoimide (NMI) and naphthalene diimide (NDI) for photoelectric conversion layers, as well as naphthalene-based molecule dimer combinations, are as follows:

[0716] -Exhibits excellent photostability and thermal stability (300 to 500°);

[0717] - HOMO and LUMO functions can be easily replaced;

[0718] - Very low extinction coefficient in the visible range;

[0719] -High electron mobility;

[0720] -In the case of dimers:

[0721] - 3D structure and LUMO degradation, which increase dissociation efficiency (LUMO dissociation);

[0722] -High electron mobility;

[0723] - Enables efficient LUMO-based dissociation of excitons formed in the absorbed p-partons.

[0724] The energy levels and morphology in the thin film can be tuned by the type of substituents R, R1, and bridging groups. This makes naphthalene monoimide (NMI) and naphthalene diimide (ND), as well as dimer combinations of these naphthalene-based molecules, highly versatile molecules for use in organic photoelectric conversion layers, along with materials that absorb in the visible range.

[0725] The main advantages of using transparent thiophene-based molecules for photoelectric conversion layers are as follows:

[0726] - Exhibits good photostability and thermal stability (up to 300℃);

[0727] - HOMO and LUMO functions can be easily replaced;

[0728] - Very low extinction coefficient in the visible range;

[0729] -High hole mobility;

[0730] - Enables efficient HOMO-based dissociation of excitons formed in the absorption of n-terminals;

[0731] -In the case of dimers:

[0732] - 3D structure and HOMO degradation, which increase dissociation efficiency (HOMO dissociation);

[0733] - Higher hole mobility.

[0734] The energy levels and morphology in thin films can be tuned by the types of substituents R, R1, and R2, as well as the heteroatoms in the core structure. This makes thiophene-based molecules highly versatile, suitable for use in organic photoelectric conversion layers along with materials that absorb in the visible range.

[0735] The main advantages of anthracene-based molecules for use in photoelectric conversion layers are as follows:

[0736] -Exhibits good photostability

[0737] - And thermal stability (up to 300°C)

[0738] - HOMO and LUMO functions can be easily replaced;

[0739] - Very low extinction coefficient in the visible range;

[0740] -High hole mobility;

[0741] - This enables efficient HOMO-based dissociation of excitons formed in the absorption of n-terminals;

[0742] -They are dimers:

[0743] - 3D structure and HOMO degradation, which increase dissociation efficiency (HOMO dissociation);

[0744] - Higher hole mobility.

[0745] The main advantages of zinc complex molecules used in photoelectric conversion layers are as follows:

[0746] -Exhibits good photostability and thermal stability (up to 350℃);

[0747] The substitution of HOMO and LUMO energy is possible;

[0748] - Extremely low extinction coefficient in the visible range;

[0749] -Potentially high electron and hole mobility -requires regulation;

[0750] - 3D structure — expected to support high exciton dissociation efficiency.

[0751] According to this disclosure, when one of the active materials is transparent, this provides the following possibilities for corresponding devices, etc.:

[0752] The total absorption spectrum can be adjusted by regulating the absorption of only one active substance;

[0753] Only the exciton diffusion efficiency of the splice (absorbing) material is adjusted;

[0754] The charge generation efficiency can be adjusted independently using HOMO or LUMO.

[0755] Adjust the mobility of electrons only (for transparent n) or holes only (for transparent p);

[0756] Typically: absorption characteristics are decoupled from electron / hole transfer and migration characteristics within the visible range.

[0757] Example

[0758] Example 1: Materials based on naphthalene monoimide (NMI)

[0759] exist Figure 5A The scheme shown reports a general synthetic route for naphthalene monoimide.

[0760] Using this synthetic route, several compounds have been synthesized, such as compound NMI1.

[0761]

[0762] NMI1 exhibits good thermal stability, as can be seen from TG (T starts at approximately 280°C), non-crystallization (DSC curve does not show melting and crystallization transitions), and the absence of absorption in the visible range. See Figure 5B .

[0763] In the following configuration, an NMI1 derivative is used as the n-material, and quinacridone (QD) is used as the p-material (absorbent pair): ITO / QD:NMI1 = 70:30 (120nm) / LiF (0.5nm) / AlSiCu 100nm. The above device produces an EQE at 550nm: 28% at 0V and 40% at -1V. With device optimization, an EQE up to 45% is achieved.

[0764] The electron mobility of this material is 1 x 10⁻⁶. -9 cm 2 / V.

[0765] Example 2: Materials based on NMI dimers

[0766] exist Figure 6A The schemes shown report synthetic routes for preparing two different naphthalene monoimide dimers, NMI-B11 and NMI-B15.

[0767] Both compounds exhibit excellent thermal stability, as shown by TG(T) 开始 (Approximately 400℃) and visible without absorption in the visible range. See Figure 6B .

[0768] In the following configuration, NMI-B11 derivatives are used as the transparent n-material and quinacridone (QD) as the absorbing p-material: ITO / 8nm HG01 / 120nm QD&NMI-B11(7:3) / 5nm NBPhen / 0.5nm LiF / 100nm AlSiCu / 100nm LiF. The above devices produce an EQE at 550nm of 15% at 0V and 23% at -1V. Figure 6C The charge transfer efficiency ηCT (-1V, 10ns) is 95%. The electron mobility of this material is 3 x 10⁻⁶. -5 cm 2 / V.

[0769] Compared to NMI, the improvement in electron mobility of NMI dimers is 2–4 orders of magnitude for all synthesized and characterized molecules. Therefore, all NMI dimers are suitable for use as electron buffers or electron transport layers.

[0770] Example 3: DTP-based materials

[0771] exist Figure 7A The scheme shown reports a synthetic route for DTP6, a material based on dithiophenepyrrole (DTP).

[0772] DTP6, such as based on TG(T) 开始 Approximately 310°C), no crystallinity (DSC curve does not show melting and crystallization transition), and no absorption observed in the visible range. See Figure 7B .

[0773] In the following configuration, a DTP6 derivative is used as the donor and sub-PcCl chloride as the acceptor: ITO / 8nm α-NPD / 120nm DTP5 & SubPcCl / 5nm NBPhen / 100nm AlSiCu / 100nm LiF. The above devices produce an EQE of 0.7% at 0V and 2% at -1V. Figure 7C ).

[0774] Example 4: Materials based on naphthalimide (NDI)

[0775] Naphthalimide (NDI) NDI1 has the following chemical structure:

[0776]

[0777] The absorption spectrum shows very low optical density in the visible range. Figure 8B The electron mobility is 10. -7 Up to 10 - 5 cm 2 / V( Figure 8C ).

[0778] In the following configuration, NDI1 is used as the acceptor material, and quinacridone (QD) and tert-butylquinacridone (BQD) are used as donors:

[0779] ITO / 8nm HG01 / 120nm QD&NDI1(1:1) / 3,5nmNBPhen / 100nm AlSiCu / 100nm LiF

[0780] ITO / 5nm MoO3 / 8nm HG01 / 120nm QD&NDI1(1:1) / 3,5nmNBPhen / 100nm AlSiCu / 100nm LiF

[0781] ITO / 8nm HG01 / 120nm BQD&NDI1(7:3) / 3,5nmNBPhen / 100nm AlSiCu / 100nm LiF

[0782] ITO / 5nm MoO3 / 8nm HG01 / 120nm BQD&NDI1(7:3) / 3,5nmNBPhen / 100nm AlSiCu / 100nm LiF

[0783] The above-mentioned device was characterized by IV darkness, IV light (1.62 μW / cm², 550 nm) and interaction spectra measured at 0 V and -1 V. The results are shown in... Figure 8D and Figure 8E .

[0784] In the following configurations, NDI1 or NMI-NDI1 is used as the acceptor material and sub-phthalocyanine chloride (SubPcCl) is used as the donor:

[0785] ITO / 8nm HG01 / 80nm SubPcCl&NDI1(1:1) / 5nmNBPhen / 0.5nm LiF / 100nm AlSiCu / 100nm LiF

[0786] ITO / 6nm MoO3 / 8nm HTM065 / 148nm SubPcCl&NMI-NDI1(1:1) / 5nm NBPhen / 0.5nmLiF / 100nm AlSiCu / 100nm LiF

[0787] The above-mentioned device was characterized by measuring its operating spectra at 0V and -1V. The results are shown in... Figure 8F .

[0788] Example 5: Another Naphthalimide (NDI)-based material

[0789] Naphthalimide (NDI) NDI20-26, NDI 28-29 and NDI35-38 have the following chemical structures:

[0790]

[0791]

[0792] exist Figure 13 The scheme shown reports a general synthetic route for the synthesis of materials.

[0793] NDI materials show maximum absorption in the range of 379 to 385 nm. Figure 14 ).

[0794] Energy levels are shown Figures 15 to 17A and Figure 17B .

[0795] Example 6: p-type material

[0796] The following p-type materials were synthesized and characterized (see also...) Figure 18A and Figure 18B ):

[0797]

[0798]

[0799] In the following configurations, in devices with F6SubPcOC6F5 respectively, DTT2, DTT9, DTT10, or DTT11, NDI35 is used as the n-buffer material:

[0800] LiF 150nm / AlSiCu 100nm / NDI35 10nm / DTT9:F6SubPcOC6F5(1:1) 200nm / ST1163 10nm / ITO / Glass

[0801] For example, the device can be characterized by measuring its operating spectra at 0V and -1V. The results are shown in Figure 19A- Figure 19C and Figures 20A-20C .

Claims

1. An organic image sensor, comprising: substrate; First electrode; The second electrode; and An organic photoelectric conversion unit between the first electrode and the second electrode; The organic photoelectric conversion unit comprises a naphthalimide-based material of the following general formula IIIa: IIIa, R is independently selected from the following groups each time it appears: -C x H 2x+1 , , , and x is an integer from 1 to 10, and R2 is independently selected from the group consisting of straight-chain or branched alkyl and haloalkyl groups each time it appears.

2. The organic image sensor according to claim 1, In the P:N heterojunction or P:N bilayer or multilayer junction, the naphthalimide-based material dissociates via a HOMO dissociation process to generate excitons on colored N or a mixture of colored N materials (N1:N2) or another colored P or a mixture of colored P and N materials (P2:N or P2:N1:N2). And color refers to a wavelength greater than 60,000 cm⁻¹ in the visible light wavelength range from 400 nm to 700 nm. -1 The absorption coefficient.

3. The organic image sensor of claim 1, wherein the naphthalimide-based material has a wavelength range of less than 60,000 cm⁻¹ in the visible light wavelength range from 400 to 700 nm. -1 The absorption coefficient, or less than 60,000 M in toluene. -1 cm -1 The extinction coefficient is obtained, and a homogeneous film is formed by deposition.

4. The organic image sensor according to claim 1, wherein R is selected from the group consisting of: 、 、 、 、 、 、 、 、 and .

5. A hybrid silicon-organic image sensor, comprising: One or more organic photoelectric conversion units as defined in any one of claims 1 to 4 Metal wire CMOS substrate, and At least one insulating layer.

6. A hybrid silicon-organic image sensor, comprising: One or more organic photoelectric conversion units as defined in any one of claims 1 to 4 Si-based photoelectric conversion unit Metal wire CMOS substrate, and At least one insulating layer.

Images