Methods and Compounds

Abstract

A method for forming a photoresponsive organic device comprising an anode (107), a cathode (103), and a photoactive layer (105) disposed between the anode and the cathode, the method comprising: forming a precursor layer on one of the anode and the cathode, the precursor layer comprising a reactive nonfullerene acceptor substituted with at least two reactive groups; and forming a photoactive layer comprising reacting the reactive groups to form chains or networks comprising a plurality of reacted molecules of the nonfullerene acceptor; and forming the other of the anode and the cathode before or after reaction of the reactive groups.

Description

[Technical Field]

[0001] Embodiments of the present disclosure relate to methods of forming photoresponsive devices and electron-accepting compounds suitable for use in such methods. [Background technology]

[0002] Photoresponsive organic devices can include a photoactive layer between an anode and a cathode that is a blend of electron donating and electron accepting materials. Known electron accepting materials include fullerenes and non-fullerene acceptors (NFAs).

[0003] Examples of NFAs are disclosed in WO 2022 / 129137.

[0004] Kahle, F.-J., Saller, C., Koehler, A., Strohriegl, P., “Crosslinked Semiconductor Polymers for Photovoltaic Applications,” Adv. Energy Mater. 2017, 7, 1700306, discloses crosslinking of low bandgap polymers used as donors in bulk heterojunction cells, as well as crosslinking of fullerene acceptors.

[0005] In U.S. Patent No. 10,526,205: [ka] Disclosed is a light-absorbing composition having a structure from the group consisting of: wherein DASM is a small molecule comprising one or more electron donor moieties and one or more electron acceptor moieties; NG is a nanographene structure; and m, n, and o are integers greater than or equal to 1.

[0006] Fan Yang et al., “Boosting the Performance of Non-Fullerene Organic Solar Cells via Cross-Linked Donor Polymers Design,” Macromolecules 2019, 52, 5, 2214-2221, discloses conjugated cross-linked polymers as electron donors for applications in organic solar cells.

[0007] Chih-Ping Chen et al., “Highly Thermal Stable and Efficient Organic Photovoltaic Cells with Crosslinked Networks Appending Open-Cage Fullerenes as Additives,” vol. 25, Issue 2, pp. 207-215, 2015, discloses that organic bulk heterojunction solar cells have been demonstrated with crosslinked cage-open fullerenes as additives in the active layer. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2022 / 129137 [Patent Document 2] U.S. Patent No. 10,526,205 [Non-patent literature]

[0009] [Non-Patent Document 1] Kahle, F.-J., Saller, C., Kohler, A., Strohriegl, P., “Crosslinked Semiconductor Polymers for Photovoltaic Applications” Adv.Energy Mater.2017,7,1700306 [Non-patent document 2] Fan Yang et al, “Boosting the Performance of Non-Fullerene Organic Solar Cells via Cross-Linked Donor Polymers Design”, Macromolecules 2019,52,5,2214-2221 [Non-patent document 3] Chih-Ping Chen et al, “Highly Thermal Stable and Efficient Organic Photovoltaic Cells with Crosslinked Networks Appending Open-Cage Fullerenes as Additives” vol.25, Issue 2, p.207-215, 2015 Summary of the Invention

[0010] According to the present disclosure, there is provided a method for forming a photoresponsive organic device comprising an anode, a cathode, and a photoactive layer disposed between the anode and the cathode, the method comprising: forming a precursor layer on one of the anode and the cathode, the precursor layer comprising a reactive nonfullerene acceptor substituted with at least two reactive groups; and forming a photoactive layer, comprising reacting the reactive groups to form chains or networks comprising a plurality of reacted nonfullerene acceptor molecules; and forming the other of the anode and cathode before or after reaction of the reactive groups; The present invention provides a method comprising:

[0011] Optionally, the photoactive layer comprises a chain comprising a plurality of non-fullerene acceptor molecules linked by linking groups formed when the reactive groups react with each other or with the reactive groups of the linking agent.

[0012] Optionally, the photoactive layer is a bulk heterojunction layer that further comprises an electron donating material.

[0013] Optionally, the electron donating material is a polymer comprising a reactive group capable of reacting with a reactive group of the non-fullerene acceptor, and the photoactive layer comprises a crosslinked network comprising the electron donating polymer crosslinked by the non-fullerene acceptor.

[0014] Optionally, the photoactive layer comprises an electron donating sublayer in direct adjacent contact with the electron accepting sublayer, and the precursor layer is an electron accepting precursor sublayer that includes a reactive nonfullerene acceptor.

[0015] Optionally, the photoactive layer comprises a bulk heterojunction sublayer and at least one of an electron donating sublayer on an anode side of the bulk heterojunction sublayer and an electron accepting sublayer on a cathode side of the bulk heterojunction sublayer, and the precursor layer comprising the precursor and the reactive nonfullerene acceptor is a precursor of the electron accepting sublayer or a precursor of the bulk heterojunction sublayer.

[0016] Optionally, the reactive group at each occurrence is independently selected from the group consisting of benzocyclobutene and acyclic or cyclic groups containing non-conjugated carbon-carbon double bonds.

[0017] Optionally, the non-fullerene acceptor has Formula (I) or (II): A 1 -(B 1 )x 1 -(D 1 )y 1 -(B 1 )x 2 -A 1 (I) A 1 -(B 2 )x 5 -(D 2 )y 2 -(B 3 )x 3 -A 2 -(B 3 )x 4 -(D 3)y 3 -(B 2 )x 6 -A 1 (II) (In the formula: A for each occurrence 1 are independently monovalent electron-accepting groups; A 2 is a divalent heteroaromatic electron-accepting group; D 1 , D 2 and D 3 is independently at each occurrence an electron donating group; B 1 , B 2 and B 3 is independently at each occurrence a bridging group; x 1 ~x 6 are each independently 0, 1, 2, or 3; y 1 , y 2 and y 3 are each independently at least 1) is a compound of; The compounds of formula (I) or (II) are substituted with at least two reactive groups.

[0018] Optionally, the at least two reactive groups are D 1 , D 2 , D 3 , B 1 , B 2 and B 3 is a substituent in one of the groups.

[0019] Optionally, D 1 is represented by formula (VIIe): [ka] (In the formula, Y A is S or O, and R 51 is H or a substituent, and R 53 is a substituent) It is based on.

[0020] Optionally, A 1 is represented by formula (IXa-1): [ka] (In the formula: G is C=O, C=S SO, SO2, NR 33 or C(R 33 )2, where R 33 CN or COOR 40 and R 40 is H or a substituent; R 10 is H or a substituent; Ar 9 is an unsubstituted or substituted monocyclic or fused aromatic or heteroaromatic group; X 60 are each independently CN, CF3, or COOR 40 is is the base.)

[0021] According to the present disclosure, a compound of formula (I) or (II): A 1 -(B 1 )x 1 -(D 1 )y 1 -(B 1 )x 2 -A 1 (I) A 1 -(B 2 )x 5 -(D 2 )y 2 -(B 3 )x 3 -A 2 -(B 3 )x 4 -(D 3 )y 3 -(B 2 )x 6 -A 1 (II) (In the formula: A for each occurrence 1 are independently monovalent electron-accepting groups; A 2is a divalent heteroaromatic electron-accepting group; D 1 , D 2 and D 3 is independently at each occurrence an electron donating group; B 1 , B 2 and B 3 is independently at each occurrence a bridging group; x 1 ~x 6 are each independently 0, 1, 2, or 3; y 1 , y 2 and y 3 are each independently at least 1) A reactive compound of the formula: Compounds of formula (I) or (II) substituted with at least two first reactive groups to provide.

[0022] The present disclosure provides a composition comprising a compound of formula (I) or (II) and an electron donating material.

[0023] Optionally, the electron donor material of the composition comprises a second reactive group capable of reacting with the first reactive group.

[0024] The present disclosure provides formulations comprising a compound or composition as described herein dissolved or dispersed in one or more solvents.

[0025] The present disclosure provides a photoresponsive organic device comprising an anode, a cathode, and a photoactive layer disposed between the anode and the cathode, the photoactive layer comprising chains or networks comprising a plurality of reacted molecules of formula (I) or (II).

[0026] The present disclosure provides an optical sensor comprising a light source and an organic photodetector as described herein, the organic photodetector configured to detect light emitted from the light source. Optionally, the light source emits light having a peak wavelength greater than 900 nm.

[0027] The present disclosure provides a method for forming the photoresponsive organic device of claim 16, comprising: forming a precursor layer comprising a compound of formula (I) or (II) on one of an anode and a cathode; forming a photoactive layer comprising reacting the reactive groups to form chains or networks comprising a plurality of reacted molecules of the compound of formula (I) or (II); and forming the other of the anode or cathode before or after reaction of the reactive groups.

[0028] The accompanying figures of the disclosed technology illustrate some implementations of the disclosed technology. [Brief explanation of the drawings]

[0029] [Figure 1] FIG. 1 illustrates a photoresponsive organic device according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0030] The drawings are not drawn to scale and have various viewpoints and perspectives. The drawings are some implementations and examples. Also, some components and / or operations may be separated into different blocks or combined into a single block for convenience in discussing some of the embodiments of the technology of the present disclosure. Furthermore, while the technology is susceptible to various modifications and alternative forms, specific embodiments are shown by way of example in the drawings and are described in detail below. However, the present invention does not limit the technology to the particular implementations described. On the contrary, the technology is intended to encompass all modifications, equivalents, and alternatives included within the scope of the technology as defined by the appended claims.

[0031] Unless the context clearly requires otherwise, throughout this description and the claims, the words "comprise," "comprising," and the like, are to be construed in an inclusive sense rather than an exclusive or exhaustive sense; that is, "including, but not limited to." Also, the words "herein," "above," "below," and words of similar import, when used in this application, refer to this application as a whole and not to any particular portions of this application. Where permitted by context, words in the detailed description using the singular or plural number may also include the plural or singular number, respectively. The word "or," in reference to a list of two or more objects, includes all of the following interpretations of that word: any object in the list, all objects in the list, and any combination of objects in the list. As used herein, a reference to a layer "over" another layer means that the layers may be in direct contact or that there may be one or more intervening layers. As used herein, a reference to a layer "on" another layer means that the layers are in direct contact. A reference to a particular atom includes any isotope of that atom unless specifically stated otherwise.

[0032] The teachings of the technology provided herein may be applied to other systems, not necessarily the systems described below. The components and functions of the various embodiments described below may be combined to obtain further implementations of the technology. Some alternative implementations of the technology may include additional components as well as fewer components than the implementations described below.

[0033] These and other modifications to the present technology can be made in light of the following detailed description. Although this description has described some specific embodiments of the present technology and set forth the contemplated best mode, no matter how detailed this description may appear, the present technology can be implemented in many ways. As described above, specific terminology used when describing certain features or aspects of the present technology should not be interpreted as suggesting that the terminology has been redefined herein to be limited to any specific feature, characteristic, or aspect of the present technology to which the terminology pertains. In general, the terms used in the following claims should not be interpreted as limiting the present technology to the specific embodiments disclosed herein, unless such terms are explicitly defined in the detailed description section. Therefore, the actual scope of the present technology encompasses not only the disclosed embodiments, but also any equivalent implementations or realizations based on the claims of the present technology.

[0034] To minimize the number of claims, certain aspects of the present technology are presented below in certain claim forms, but applicants contemplate various aspects of the present technology in any number of claim forms.

[0035] In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of implementations of the disclosed technology. However, it will be apparent to one skilled in the art that embodiments of the disclosed technology may be practiced without some of these specific details.

[0036] Organic Electronics Devices 1 shows a photoresponsive organic device according to some embodiments of the present disclosure, comprising a cathode 103, an anode 107, and a bulk heterojunction layer 105 disposed between the anode and the cathode. The photoresponsive organic device may be supported on a substrate 101, optionally a glass or plastic substrate.

[0037] The photoactive layer, as described herein, comprises an electron-accepting material and an electron-donating material. Figure 1 shows a photoresponsive organic device in which the photoactive layer is a single bulk heterojunction layer that includes both an electron-accepting material and an electron-donating material. In other embodiments, the photoactive layer comprises two or more sublayers.

[0038] In some embodiments, the photoactive layer comprises a crosslinked electron-accepting sublayer comprising an electron-accepting material and an electron-donating sublayer comprising an electron-donating material, the sublayers being in direct adjacent contact with each other.

[0039] In still further embodiments, the photoactive layer comprises a bulk heterojunction layer comprising both an electron-accepting material and an electron-donating material, and one or both of an electron-accepting layer comprising an electron-accepting material on the cathode side of the device and an electron-donating layer comprising an electron-donating material on the anode side of the device.

[0040] Each of the anode and cathode may independently be a single conductive layer or may comprise multiple layers.

[0041] At least one of the anode and cathode is transparent so that light entering the device can reach the photoactive layer. In some embodiments, both the anode and the cathode are transparent. The transmittance of the transparent electrode can be selected depending on the emission wavelength of the light source for use with the organic photodetector.

[0042] 1 shows a configuration in which the cathode is disposed between the substrate and the anode. In other embodiments, the anode may be disposed between the cathode and the substrate.

[0043] Photoresponsive organic devices may include layers other than an anode, a cathode, and a photoactive layer. In some embodiments, a hole transport layer and / or an electron blocking layer is disposed between the anode and the photoactive layer. In some embodiments, an electron transport layer and / or a hole blocking layer is disposed between the cathode and the photoactive layer. In some embodiments, a work function adjusting layer is disposed between the photoactive layer and the anode and / or between the photoactive layer and the cathode.

[0044] The substrate may be, but is not limited to, a glass or plastic substrate. The substrate may be an inorganic semiconductor. In some embodiments, the substrate may be silicon. For example, the substrate may be a silicon wafer. A substrate is transparent if, in use, incident light passes through the substrate and the electrodes supported by the substrate.

[0045] The bulk heterojunction layer comprises, or consists of, at least one electron donating material and at least one electron accepting material that includes a chain or network comprising a plurality of nonfullerene acceptor (NFA) molecules.

[0046] In some embodiments, the weight ratio of electron donor material(s) to electron acceptor material(s) is from about 1:0.5 to about 1:2, preferably from about 1:1.1 to about 1:2.

[0047] Forming a bulk heterojunction layer involves forming a precursor layer containing NFA molecules substituted with reactive groups, where the chains or networks are formed by reacting the reactive groups on the NFA molecules, which can react with each other to form linking groups between NFA molecules and / or can react with the reactive groups of another material in the precursor layer substituted with reactive groups, such as an electron donor material or another linking agent, such as a crosslinker, substituted with reactive groups.

[0048] The reactive groups of the NFA can react to form chains or networks.

[0049] Chains can be formed by reacting NFAs with only two reactive groups either with each other or with a linking agent that has only two reactive groups.

[0050] The cross-linked network is: - NFAs with more than two reactive groups, for example, three or four reactive groups, with each other; or - NFA having at least two reactive groups with a linking agent having more than two reactive groups It can be formed by reacting

[0051] The linking agent can be a non-polymeric linking agent having more than two reactive groups, for example, three or four reactive groups.

[0052] The linking agent can be a polymer containing repeating units substituted with reactive groups that can react with the reactive groups of the NFA to form a crosslinked network, hi a preferred embodiment, the linking agent is an electron donating polymer of the bulk heterojunction layer.

[0053] Exemplary compounds of formula (I) are: [ka] wherein Sp is a spacer group or is absent; and Alk is C1-12 alkyl. is.

[0054] The bulk heterojunction layer may consist of the NFA, the electron donor compound, and (if present) the linking agent, and may also include one or more additional materials, such as one or more additional electron donor materials and / or one or more additional electron acceptor compounds.

[0055] FIG. 1 schematically illustrates an OPD having a photoactive bulk heterojunction layer including an electron-donating material, a chain or network including multiple nonfullerene acceptor molecules. In other embodiments, the photoactive layer may include an electron-accepting sublayer including NFA chains or networks, or an electron-accepting sublayer including an electron-donating material in direct contact with the electron-accepting sublayer, or an electron-donating sublayer including an electron-donating material. In such embodiments, the sublayers may be formed in any order. Preferably, the electron-accepting sublayer including NFA chains or networks is formed first, and the electron-donating sublayer is formed on the electron-donating sublayer. The electron-accepting sublayer including NFA chains or networks may be less susceptible to dissolution than a layer including unreacted NFA when a solution or suspension is deposited thereon.

[0056] Preferably, the electron donor material has a Type II interface with the electron acceptor material, i.e., the electron donor material has a HOMO and LUMO that are shallower than the corresponding HOMO and LUMO levels of the electron acceptor material. Preferably, the compound of formula (I) or (II) has a HOMO level that is at least 0.05 eV deeper, optionally at least 0.10 eV deeper, than the HOMO of the electron donor material.

[0057] Optionally, the gap between the HOMO level of the electron donating material of formula (I) or (II) and the LUMO level of the electron accepting compound is less than 1.4 eV.

[0058] The NFA substituted with at least two reactive groups has formula (I) or (II): A 1 -(B 1 )x 1 -(D 1 )y 1 -(B 1 )x 2 -A 1 (I) A 1-(B 2 )x 5 -(D 2 )y 2 -(B 3 )x 3 -A 2 -(B 3 )x 4 -(D 3 )y 3 -(B 2 )x 6 -A 1 (II) (In the formula: A for each occurrence 1 are independently monovalent electron-accepting groups; A 2 is a divalent heteroaromatic electron-accepting group; D 1 , D 2 and D 3 is independently at each occurrence an electron donating group; B 1 , B 2 and B 3 is independently at each occurrence a bridging group; x 1 ~x 6 are each independently 0, 1, 2, or 3; y 1 , y 2 and y 3 are each independently at least 1) wherein the compound of formula (I) or (II) is substituted with at least two reactive groups, optionally two, three or four reactive groups, that can react with each other or with the reactive groups of the linking agent to form a chain or network of NFAs.

[0059] Electron-accepting group A 1 and A 2 Each of the groups is an electron donating group D 1 , D 2 or D 3The lowest unoccupied molecular orbital (LUMO) levels of the electron-accepting and electron-donating groups are deeper (i.e., farther from vacuum) than the LUMO levels of any of the groups, preferably at least 1 eV deeper. The LUMO levels of the electron-accepting and electron-donating groups can be determined by modeling the LUMO levels of these groups, replacing each bond to an adjacent group with a bond to a hydrogen atom. The modeling was performed using Gaussian09 software available from Gaussian, Inc., using B3LYP (functional) and LACVP. * This can be done using Gaussian09 with (basis set).

[0060] In the case of compounds of formula (I), A 1 , B 1 and D 1 At least one of x is substituted with a reactive group. 1 and x 2 At least one of B is at least 1, and at least one 1 is substituted with at least one reactive group.

[0061] In the case of compounds of formula (II), A 1 , A 2 , B 2 , B 3 , D 2 and D 3 At least one of x is substituted with a reactive group. 3 ~x 6 At least one of B is at least 1, 2 and B 3 At least one of x is substituted with at least one reactive group. 5 and x 6 At least one of B is at least 1, and at least one 2 is substituted with at least one reactive group.

[0062] reactive groups NFA has the formula (III): [ka] (wherein Sp represents a spacer group; x is 0 or 1; RG represents a reactive group; * represents the attachment point of the reactive group with NFA) Preferably, x is 1.

[0063] RG can be selected from any reactive group known to one of skill in the art that can react with itself to form a covalent bond or with a reactive group on a linking agent.

[0064] Optionally, the reactive group is: (i) R in the formula 1 is H or a substituent of the formula -CR 1 acyclic units of =CH2, preferably C 1~6 alkyl groups, such as vinyl, acrylate or methacrylate-containing groups; (ii) a group containing a cyclic alkene, preferably an optionally substituted norbornene, cyclopropene, or cyclobutene; (iii) optionally substituted benzocyclobutene; (iv) a halogen, preferably Cl, Br, or I; (v) boronic acids or esters thereof; (vi) cyclic ethers, preferably optionally substituted, e.g., C 1~6 Alkyl-substituted epoxides or oxetanes; and (vii) azide is selected from.

[0065] The reactive groups of the non-fullerene acceptor as described herein can be selected for reaction with the reactive groups of the linker or electron donating material. Exemplary combinations of groups that can react with each other include: boronic acids or esters and halogens; 1 Examples include a =CH2 group and an optionally substituted benzocyclobutene; a fullerene and an optionally substituted benzocyclobutene; and an azide and an optionally substituted benzocyclobutene.

[0066] The optionally substituted benzocyclobutene has the formula (IV): [ka] (wherein, R 2 is H or a substituent; q is 0, 1, 2 or 3, preferably 0; and each occurrence of R 3 is H or a substituent) It may have the following structure:

[0067] Preferably, two R are bonded to the same carbon atom. 2 At least one of the groups R 2 is H. Optionally, each R in formula (IV) 2 is H or R of formula (IV) 2 Only one of these is not H. An example of a non-H R 2 The base is C 1~6 Alkyl and C 1~6 It is an alkoxy.

[0068] R 3 If present, is preferably F, Cl, NO2, CN, C 1~6 Alkyl and C 1~6 Alkoxy is selected from:

[0069] Sp is preferably optionally substituted phenylene; and C 1~20 alkylene, wherein the C 1~20 One or more H atoms of the alkylene may be replaced by F, and one or more non-adjacent C atoms may be replaced by O, S, NR 6 , Si(R 4 )2, CO, COO or CONR 6 may be replaced by R 6 is H or a substituent, and each R 4 are independently substituents.

[0070] Optional substituents of the phenylene group Sp are F; CN; NO; and one or more H atoms may be replaced by F and one or more non-adjacent C atoms may be replaced by O, S, NR 6 , Si(R 4 )2, CO, COO or CONR 6 may be replaced by C 1~20 It is alkylene.

[0071] Crosslinking Unit Crosslinking unit B 1 , B 2 and B 3 are preferably each selected from vinylene, arylene, heteroarylene, arylenevinylene, and heteroarylenevinylene, where the arylene and heteroarylene groups are monocyclic or bicyclic groups, each of which may be unsubstituted or substituted with one or more substituents.

[0072] Optionally, B 1 , B 2 and B 3 independently at each occurrence, represent formulas (VIa) to (VIo): [ka] TIFF2025538632000009.tif132152 (in the formula, R 55 is H or a substituent, optionally H or C 1~20 is a hydrocarbyl group; each occurrence of R 8 are independently H or a substituent, preferably H or a reactive group as described herein; F; CN; NO; one or more non-adjacent C atoms are O, S, NR 6 , C may be replaced by COO or CO 1~20 alkyl, in which one or more H atoms may be replaced by F; phenyl, which is unsubstituted or substituted by one or more substituents; and each occurrence of R 14 is a substituent, optionally C 1~20 The hydrocarbyl group -B(R 14) is a substituent selected from 2) R in formulas (VIa), (VIb) and (VIc) is selected from the following units: 8 The groups may be linked to form a bicyclic ring, for example a thienopyrazine.

[0073] R 8 is preferably H, C 1~20 Alkyl or C 1~19 It is an alkoxy.

[0074] R in formulas (VIa), (VIb) and (VIc) 8 The groups may be linked to form an optionally substituted bicyclic ring.

[0075] In the compound of formula (I), each x 1 is preferably 0 or 1.

[0076] In the compound of formula (II), x 3 and x 4 are each preferably 0, and x 5 and x 6 are each preferably 0 or 1.

[0077] Electron-accepting group A 1 Monovalent acceptor group A 1 may each independently be selected from any such unit known to one of skill in the art. 1 may be the same or different, and preferably the same.

[0078] Exemplary monovalent acceptor groups include, but are not limited to, those represented by formulae (IXa) to (IXq): [ka] Examples include TIFF2025538632000011.tif211159 and TIFF2025538632000012.tif22142.

[0079] U is a 5- or 6-membered ring that is unsubstituted or substituted with one or more substituents and that is optionally fused to one or more additional rings.

[0080] G is C=O, C=S SO, SO2, NR 33 or C(R 33 )2, where R 33 CN or COOR 40 G is preferably C=O or SO2, more preferably C=O.

[0081] The N atom of formula (IXe) may be unsubstituted or substituted.

[0082] R 10 is H or a substituent, preferably one or more non-adjacent C atoms are O, S, NR 6 may be replaced by COO or COC 1~12 alkyl, in which one or more H atoms may be replaced by F; and unsubstituted or in which F and one or more non-adjacent C atoms are O, S, NR 6 may be replaced by COO or COC 1~12 is an aromatic group substituted with one or more substituents selected from alkyl, optionally with a substituent selected from the group consisting of phenyl.

[0083] Preferably, R 10 is H.

[0084] J is O or S, preferably O.

[0085] R for each occurrence 13 is a substituent, optionally one or more non-adjacent C atoms are O, S, NR 6 may be replaced by COO or COC 1~12 alkyl in which one or more H atoms may be replaced by F;

[0086] R for each occurrence15 are independently H; F; one or more non-adjacent C atoms are O, S, or NR 6 , C may be replaced by COO or CO 1~12 alkyl, in which one or more H atoms may be replaced by F; unsubstituted or in which F and one or more non-adjacent C atoms are replaced by O, S, NR 6 , C may be replaced by COO or CO 1~12 an aromatic group Ar substituted with one or more substituents selected from alkyl; 2 , optionally phenyl; or: [ka] is a group selected from

[0087] R 16 is H or a substituent, preferably: -(Ar 3 ) w , where each occurrence of Ar 3 is independently an unsubstituted or substituted aryl or heteroaryl group, preferably thiophene, and w is 1, 2, or 3; [ka] and One or more non-adjacent C atoms are O, S, or NR 6 may be replaced by COO or COC 1~12 Alkyl in which one or more H atoms may be replaced by F is a substituent selected from:

[0088] Ar 6 is a 5-membered heteroaromatic group, preferably thiophene or furan, which is unsubstituted or substituted with one or more substituents.

[0089] Ar 3 and Ar 6 The substituents, if present, may be substituted by one or more non-adjacent C atoms, such as O, S, NR6 may be replaced by COO or COC 1~12 Optionally, the alkyl is selected from alkyl, in which one or more H atoms may be replaced by F.

[0090] T 1 , T 2 and T 3 Each independently represents an aryl or heteroaryl ring optionally fused to one or more additional rings, optionally benzene. 1 , T 2 and T 3 If present, the substituents of R are not H. 25 In one preferred embodiment, T 3 is benzothiadiazole.

[0091] Z 1 is N or P.

[0092] Ar 8 is unsubstituted or contains one or more substituents, optionally one or more non-H substituents R 10 a fused heteroaromatic group substituted with B 1 or B 2 Aromatic C atoms and B 1 or B 2 is a fused heteroaromatic group bonded to a boron substituent of

[0093] Preferred A 1 The group D of formula (I) 1 or D of formula (II) 2 Or D 3 or B of formula (I), if present 1 or B of formula (II) 2 is a group having a non-aromatic carbon-carbon bond directly bonded to

[0094] Preferably, at least one A 1 , preferably both A 1 The group has the formula (IXa-1): [ka] (In the formula: G is as defined above, preferably C=O or SO2, more preferably C=O; R 10 is as above; Ar 9 is an unsubstituted or substituted monocyclic or fused aromatic or heteroaromatic group, preferably a benzene or monocyclic or bicyclic heteroaromatic group having only C or N ring atoms; X 60 are each independently CN, CF3, or COOR 40 where R for each occurrence 40 is H or a substituent, preferably H or C 1~20 is a hydrocarbyl group) Preferably, each X 60 is CN.

[0095] Ar 9 Ar may be unsubstituted or substituted with one or more substituents. 9 The substituents in are preferably R as described below. 12 is selected from the group

[0096] Optionally, the group of formula (IXa-1) can be a group of formula (IXa-2): [ka] and each X 7 ~X 10 is an independent CR 12 or N, where each occurrence of R 12 is H or C 1~20 The substituent is selected from hydrocarbyl and electron-withdrawing groups. Preferably, the electron-withdrawing group is F, Cl, Br or CN, more preferably F, Cl or CN; for example, F or CN.

[0097] C 1~20 R is a hydrocarbyl group 12 is C 1~20alkyl; unsubstituted phenyl; and one or more C 1~12 It may be selected from phenyl substituted with an alkyl group.

[0098] In one particularly preferred embodiment, X 7 ~X 10 Each of these is CR 12 and each R 12 are independently selected from H or electron-withdrawing groups, preferably H, F or CN. 8 and X 9 R 12 is an electron withdrawing group, preferably F or CN.

[0099] Exemplary groups of formula (IXd) include: [ka] The following are mentioned: Exemplary groups of formula (IXe) include: [ka] The following are mentioned: An example of an exemplary group of formula (IXq) is: [ka] and An example of an exemplary group of formula (IXg) is: [ka] and An example of an exemplary group of formula (IXj) is: [ka] and In the formula, Ak is a group in which one or more C atoms are O, S, NR 6 C may be replaced by CO or COO 1~12 An is an anion, optionally -SO3 - and each benzene ring is independently unsubstituted or R 10and is substituted with one or more substituents selected from the substituents described for:

[0100] Exemplary groups of formula (IXm) are: [ka] is.

[0101] An example of an exemplary group of formula (IXn) is: [ka] is.

[0102] The group of formula (IXo) is a group of formula -B(R 14 )2 groups, 1 or B 2 where each occurrence of R 14 is a substituent, optionally C 1~20 is a hydrocarbyl group; → is a boron atom -B(R 14 )2; --- is a CC bond between formula (IXo) and the bridging group.

[0103] Optionally, R 14 is C 1~12 alkyl; unsubstituted phenyl; and one or more C 1~12 phenyl substituted with alkyl groups.

[0104] Group of formula (IXo), B 1 or B 2 Groups and B 1 or B 2 B(R 14 ) Two substituents may be linked together to form a 5- or 6-membered ring.

[0105] Optionally, the group of formula (IXo) is: [ka] is selected from.

[0106] Acceptor unit A 2 A 2 is preferably a fused heteroaromatic group containing at least two fused rings, preferably at least three fused rings.

[0107] In some embodiments, A of formula (II) 2 is represented by formula (VIII): [ka] (In the formula: Ar 1 is an aromatic or heteroaromatic group; Y is O, S, NR 6 or R 7 -C=CR 7 where R for each occurrence 7 are independently H or a substituent, and two substituents R 7 may be linked to form a monocyclic or polycyclic ring; R 6 is H or a substituent) It is based on.

[0108] A 2 is a group of formula (VIII), Ar 1 is unsubstituted or substituted with one or more R 9 and R is a monocyclic or polycyclic heteroaromatic group substituted with a group, wherein each occurrence of R 9 are independently substituents.

[0109] Preferred R 9 The base is F; CN; NO2; One or more non-adjacent C atoms are O, S, or NR 17 may be replaced by R 17 is C 1~12 C is hydrocarbyl, COO or CO 1~20 alkyl, in which one or more H atoms may be replaced by F; an aromatic or heteroaromatic group, preferably phenyl, which is unsubstituted or substituted with one or more substituents; and [ka] (In the formula, Z 40 , Z 41 , Z 42 and Z 43 are each independently CR 13 or N, where each occurrence of R 13 is H or a substituent, preferably C 1~20 is a hydrocarbyl group; Y 40 and Y 41 are each independently O, S, NX 71 where X 71 CN or COOR 40 ;or CX 60 X 61 and X 60 and X 61 are independently CN, CF3 or COOR 40 and;W 40 and W 41 are each independently O, S, NX 71 or CX 60 X 61 where X 60 and X 61 are independently CN, CF3 or COOR 40 and for each occurrence R 40 is H or a substituent, preferably H or C 1~20 is a hydrocarbyl group) A group selected from R is an aromatic or heteroaromatic group. 9 Exemplary substituents for are F, CN, NO, and those in which one or more non-adjacent C atoms are O, S, NR 6 may be replaced by COO or COC 1~12 alkyl in which one or more H atoms may be replaced by F;

[0110] R 17Wherever described herein, for example, C 1~12 alkyl, unsubstituted phenyl; or one or more C 1~6 It may be a phenyl substituted with an alkyl group.

[0111] When a C atom of an alkyl group is replaced by another atom or group, as described anywhere in this specification, the replaced C atom may be a terminal C atom or a non-terminal C atom of the alkyl group.

[0112] By "non-terminal C atom" of an alkyl group, as used anywhere in this specification, is meant a C atom other than the C atom of the methyl group at the end of an n-alkyl chain or the C atom of the methyl group at the end of a branched alkyl chain.

[0113] If the terminal C atom of a group, as described anywhere herein, is replaced, the resulting group may be an anionic group comprising a countercation, such as an ammonium or metal countercation, preferably an ammonium or alkali metal cation.

[0114] The C atom of the alkyl substituent group that is replaced by another atom or group, wherever mentioned herein, is preferably a non-terminal C atom, and the resulting substituent group is preferably non-ionic.

[0115] Exemplary monocyclic heteroaromatic groups Ar 1 are oxadiazoles, thiadiazoles, triazoles, and 1,4-diazines which are unsubstituted or substituted by one or more substituents. Thiadiazoles are particularly preferred.

[0116] Exemplary Polycyclic Heteroaromatic Groups Ar 1 is expressed by formula (V): [ka] It is based on.

[0117] X 1 and X 2 are each independently N and CR 10 where R 10 is H or a substituent, optionally H or a substituent R as defined above 9 is.

[0118] X 3 , X 4 , X 5 and X 6 are N and CR, respectively. 10 are independently selected from X 3 , X 4 , X 5 and X 6 At least one of the 10 It is assumed that:

[0119] Z is O, S, SO2, NR 6 , PR 6 , C(R 10 )2, Si(R 10 )2C=O, C=S and C=C(R 5 )2, where R 10 is as above; R 6 is H or a substituent; each occurrence of R 5 is an electron-withdrawing group.

[0120] Preferably, each R 5 CN, COOR 40 ;or CX 60 X 61 where X 60 and X 61 are independently CN, CF3 or COOR 40 and R for each occurrence 40 is H or a substituent, preferably H or C 1~20 It is a hydrocarbyl group.

[0121] A in formula (VIII) 2 The groups preferably have the formulae (VIIIa) and (VIIIb): [ka] is selected from the group

[0122] For compounds of formula (VIIIb), two R 7 The groups may or may not be linked.

[0123] Preferably, the two R 7 When no groups are linked, each R 7 are independently H; F; CN; NO2; one or more non-adjacent C atoms are O, S, or NR 6 , CO, COO, NR 6 , PR 6 or Si(R 10 ) 2, and one or more H atoms may be replaced by F. 1~20 alkyl, where R 10 and R 6 is as defined above; and aryl or heteroaryl, preferably phenyl, which may be unsubstituted or substituted with one or more substituents. The substituents of the aryl or heteroaryl group are F; CN; NO; and one or more non-adjacent C atoms may be O, S, NR 6 , CO, COO, and one or more H atoms may be replaced by F. 1~20 The alkyl may be selected from one or more of:

[0124] Preferably, the two R 7 When groups are linked, the group of formula (VIIIb) can be represented by formula (VIIIb-1) or (VIIIb-2): [ka] It has.

[0125] Ar 2 is an aromatic or heteroaromatic group, preferably benzene, which is unsubstituted or substituted with one or more substituents. 2 Even if unsubstituted, H, F, Cl, CN, NO2, C 1~16 Alkyl or C1~16 alkoxy, wherein the C 1~16 Alkyl or C 1~16 One or more H atoms of the alkoxy may be replaced by F.

[0126] X is O, S, SO2, NR 6 , PR 6 , C(R 10 )2, Si(R 10 )2C=O, C=S and C=C(R 5 )2, where R 10 , R 6 and R 5 is as above.

[0127] Exemplary electron accepting groups of formula (VIII) include, but are not limited to: [ka] (In the formula, Ak 1 is C 1~20 alkyl group) Examples include:

[0128] Divalent electron-accepting group A other than formula (VIII) 2 are represented by the formulas (IVa) to (IVj) [ka] Optionally selected from TIFF2025538632000032.tif102149.

[0129] Y A1 is O or S, preferably S.

[0130] R for each occurrence 23 is a substituent, optionally Z 3 One or more non-adjacent C atoms other than the C atom bonded to 6 may be replaced by COO or COC 1~12alkyl in which one or more H atoms may be replaced by F;

[0131] R for each occurrence 25 are independently H; F; CN; NO2; one or more non-adjacent C atoms are O, S, or NR 6 , C may be replaced by COO or CO 1~12 alkyl, in which one or more H atoms may be replaced by F; unsubstituted or in which F and one or more non-adjacent C atoms are replaced by O, S, NR 6 , C may be replaced by COO or CO 1~12 an aromatic group substituted with one or more substituents selected from alkyl, optionally phenyl; or [ka] (In the formula, Z 40 , Z 41 , Z 42 and Z 43 are each independently CR 13 or N, where each occurrence of R 13 is H or a substituent, preferably C 1~20 is a hydrocarbyl group; Y 40 and Y 41 are each independently O, S, NX 71 where X 71 is CN or COOR 40 ;or CX 60 X 61 and X 60 and X 61 are independently CN, CF3 or COOR 40 and; W 40 and W 41 are each independently O, S, NX 71 where X 71 is CN or COOR 40 ;or CX 60 X 61 and X 60 and X 61are independently CN, CF3 or COOR 40 and; R for each occurrence 40 is H or a substituent, preferably H or C 1~20 is a hydrocarbyl group) is.

[0132] Z 3 is N or P.

[0133] T 1 , T 2 and T 3 Each independently represents an aryl or heteroaryl ring optionally fused to one or more additional rings, optionally benzene. 1 , T 2 and T 3 If present, the substituents of R are not H. 25 In one preferred embodiment, T 3 is benzothiadiazole.

[0134] R for each occurrence 12 is a substituent, preferably C 1~20 It is a hydrocarbyl group.

[0135] Ar 5 may be unsubstituted or may contain one or more substituents, optionally R 25 an arylene or heteroarylene group optionally substituted with one or more non-H groups selected from: thiophene, fluorene, or phenylene.

[0136] Electron-donating group D 1 、D 2 and D 3 The electron-donating group is preferably a fused aromatic or heteroaromatic group containing three or more rings, more preferably a fused heteroaromatic group. Particularly preferred electron-donating groups are those containing a fused thiophene or furan ring, optionally containing a fused ring containing a thiophene or furan ring and one or more rings selected from a benzene ring, a cyclopentadiene ring, a tetrahydropyran ring, a tetrahydrothiopyran ring, and a piperidine ring, each of which is unsubstituted or substituted with one or more substituents.

[0137] Electron donating groups as described herein may be substituted with one or more reactive groups.

[0138] Exemplary Electron-Donating Groups D 1 , D 2 and D 3 Examples include compounds of the formulas (VIIa) to (VIIm): [ka] TIFF2025538632000035.tif85145 (where Y A are independently 0, S or NR 55 and X A is C or Si; each occurrence of Y A1 is independently O or S; each occurrence of Z A O, CO, S, NR 55 or C(R 54 )2;R 51 , R 52 R 54 and R 55 is independently at each occurrence H or a substituent; R 53 is independently a substituent at each occurrence; Ar 4 is an optionally substituted monocyclic or fused heteroaromatic group Examples of the group include the following.

[0139] Optionally, R 51 and R 52independently in each occurrence: H; F; one or more non-adjacent C atoms are O, S, NR 6 may be replaced by COO or COC 1~20 alkyl, in which one or more H atoms may be replaced by F; and aromatic or heteroaromatic groups Ar which are unsubstituted or substituted by one or more substituents. 3 is selected from.

[0140] In some embodiments, Ar 3 can be an aromatic group, for example phenyl.

[0141] Ar 4 is preferably selected from optionally substituted oxadiazoles, thiadiazoles, triazoles and 1,4-diazines. 4 is a 1,4-diazine, the 1,4-diazine may be fused with a further heterocyclic group, optionally a group selected from optionally substituted oxadiazole, thiadiazole, triazole, 1,4-diazine and succinimide.

[0142] Ar 3 If present, one or more non-adjacent C atoms may be O, S, NR 6 may be replaced by COO or COC 1~12 It may be selected from alkyl in which one or more H atoms may be replaced by F.

[0143] Preferably, each R 54 teeth: H; a reactive group as described herein; F; One or more non-adjacent C atoms are O, S, or NR 17 , linear, branched or cyclic C may be replaced by CO or COO 1~20 C alkyl in which one or more H atoms may be replaced by F 1~20 alkyl, where R 17 is C1~12 is a hydrocarbyl; and Formula (Ak)u-(Ar 7 )v groups (where Ak is a group in which one or more non-adjacent C atoms are O, S, NR 6 C may be replaced by CO or COO 1~20 is an alkylene chain; u is 0 or 1; and each occurrence of Ar 7 is independently an aromatic or heteroaromatic group that is unsubstituted or substituted with one or more substituents; and v is at least 1, optionally 1, 2, or 3. is selected from the group consisting of:

[0144] Ar 7 The substituents, if present, are preferably F; Cl; NO; CN; and one or more non-adjacent C atoms are O, S, NR 6 , C, C, or CO; and one or more H atoms may be replaced by F. 1~20 alkyl. Preferably, Ar 7 is phenyl.

[0145] Preferably, each R 51 is H.

[0146] Optionally, R 53 independently at each occurrence, a reactive group as described herein; one or more non-adjacent C atoms are O, S, NR 6 may be replaced by COO or COC 1~20 alkyl, in which one or more H atoms may be replaced by F; and unsubstituted or with one or more substituents, optionally with one or more non-adjacent C atoms being O, S, NR 6 , one or more C atoms which may be replaced by COO or CO and one or more H atoms which may be replaced by F 1~12 phenyl substituted with alkyl groups.

[0147] Preferably, R 55is H or C wherever described herein. 1~30 It is a hydrocarbyl group.

[0148] In one preferred embodiment, D of the compound of formula (I) 1 is a group of formula (VIIe).

[0149] In some embodiments, y in formula (I) 1 is 1.

[0150] In some embodiments, y in formula (II) 2 and y 3 are each 1.

[0151] In some embodiments, y in formula (I) 1 or y in formula (II) 2 and y 3 In such an embodiment, at least one of D 1 , D 2 or D 3 The chains of groups may each be linked in any orientation.

[0152] Exemplary compounds of formula (I) or (II) having a reactive group include, but are not limited to: [ka] TIFF2025538632000037.tif239148 is an example.

[0153] Electron-donating materials A bulk heterojunction layer as described herein comprises an electron donating material and a compound of formula (I) or (II) as described herein.

[0154] Exemplary donor materials are disclosed, for example, in WO 2013 / 051676, the contents of which are incorporated herein by reference.

[0155] The electron donating material can be a non-polymeric or polymeric material.

[0156] In a preferred embodiment, the electron-donating material is an organic conjugated polymer, which can be a homopolymer or a copolymer, such as an alternating, random, or block copolymer. The conjugated polymer is preferably a donor-acceptor polymer, which contains alternating electron-donating and electron-accepting repeating units.

[0157] Preferred are amorphous or semi-crystalline conjugated organic polymers.

[0158] More preferably, the electron donating polymer is a conjugated organic polymer having a small band gap, typically 2.5 eV to 1.5 eV, and preferably 2.3 eV to 1.8 eV.

[0159] Optionally, the electron donating polymer has a HOMO level 5.5 eV or less from the vacuum level. Optionally, the electron donating polymer has a HOMO level at least 4.1 eV from the vacuum level. Exemplary electron donating polymers include conjugated hydrocarbon or heterocyclic polymers, such as polyacenes, polyanilines, polyazulenes, polybenzofurans, polyfluorenes, polyfurans, polyindenofluorenes, polyindoles, polyphenylenes, polypyrazolines, polypyrenes, polypyridazines, polypyridines, polytriarylamines, poly(phenylene vinylenes), poly(3-substituted thiophenes), poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3-substituted selenophenes), poly(3,4-di ... Examples of suitable polymers include polymers selected from polythieno[2,3-b]thiophenes, poly(bisthiophenes), poly(terthiophenes), poly(bisselenophenes), poly(terselenophenes), polythieno[2,3-b]thiophenes, polythieno[3,2-b]thiophenes, polybenzothiophenes, polybenzo[1,2-b:4,5-b']dithiophenes, polyisothianaphthenes, poly(monosubstituted pyrroles), poly(3,4-disubstituted pyrroles), poly-1,3,4-oxadiazoles, polyisothianaphthenes, derivatives and copolymers thereof.

[0160] Preferred examples of donor polymers are copolymers of polyfluorene and polythiophene, each of which may be substituted, and polymers comprising benzothiadiazole-based repeating units and thiophene-based repeating units, each of which may be substituted.

[0161] One particularly preferred example of a donor polymer has the formula (X): [ka] (In the formula, Y A , Z A , R 51 and R 54 is as above) It contains repeating units of

[0162] Another particularly preferred donor polymer has formula (XI): [ka] (In the formula, R 18 and R 19 are each H; F; C in which one or more non-adjacent, non-terminal C atoms may be replaced by O, S, COO, or CO. 1~12 alkyl, in which one or more H atoms may be replaced by F; or C, which is unsubstituted or in which F and one or more non-adjacent, non-terminal C atoms may be replaced by O, S, COO or CO; 1~12 an aromatic or heteroaromatic group Ar substituted with one or more substituents selected from alkyl; 6 (independently selected from It contains repeating units of

[0163] The donor polymer preferably comprises donor repeating units, such as repeating units of formula (X) or (XI), and acceptor repeating units, such as divalent electron-accepting units A as described herein, provided as polymeric repeating units. 2 is a donor-acceptor (DA) copolymer comprising:

[0164] The donor polymer may be substituted with one or more reactive groups as described herein.

[0165] fullerene In some embodiments, the compound of Formula (I) or (II) is the only electron-accepting material of a bulk heterojunction layer as described herein.

[0166] In some embodiments, the bulk heterojunction layer comprises a compound of Formula (I) or (II) and one or more additional electron-accepting materials. A preferred additional electron-accepting material is a fullerene. The weight ratio of the compound of Formula (I) or (II) to the fullerene acceptor can be in the range of about 1:0.1 to 1:1, preferably about 1:0.1 to 1:0.5.

[0167] Fullerenes include, but are not limited to, C 60 , C 70 , C 76 , C 78 and C 84 fullerene or its derivatives, including but not limited to PCBM-type fullerene derivatives, such as phenyl-C 61 -Butyric acid methyl ester (C 60 PCBM), TCBM-type fullerene derivatives (e.g., tolyl-C 61 -Butyric acid methyl ester (C 60 TCBM), and ThCBM-type fullerene derivatives (e.g., thienyl-C 61 -Butyric acid methyl ester (C 60 ThCBM).

[0168] The fullerene derivative has the formula (V): [ka] (wherein A, together with the CC group of the fullerene, forms a monocyclic or fused ring group which may be unsubstituted or substituted with one or more substituents). It may have the following structure:

[0169] Exemplary fullerene derivatives include those represented by formulae (Va), (Vb), and (Vc): [ka] (In the formula, R 20 ~R 32 are each independently H or a substituent. Examples include:

[0170] Substituent R 20 ~R 32 represents independently at each occurrence aryl or heteroaryl, which may be unsubstituted or substituted by one or more substituents, optionally phenyl; and one or more non-adjacent C atoms are O, S, NR 6 , C, C, or CO; and one or more H atoms may be replaced by F. 1~20 is optionally selected from the group consisting of alkyl.

[0171] The substituents of an aryl or heteroaryl, if present, may be such that one or more non-adjacent C atoms are O, S, NR 6 , C, C, or CO; and one or more H atoms may be replaced by F. 1~12 alkyl.

[0172] NFA chain or network formation A layer comprising NFA chains or networks can be formed by depositing the reactive NFA and any other components of the layer by any process, including but not limited to thermal evaporation and solution deposition, followed by reaction of the reactive groups.

[0173] Preferably, the precursor layer is formed by depositing a formulation comprising an electron-accepting material(s), such as a reactive NFA, and any other components of the precursor layer, such as one or more electron-donating materials in the case of a bulk heterojunction layer, dissolved or dispersed in a solvent or a mixture of two or more solvents, followed by evaporation of the solvent(s). The formulation can be deposited by any coating or printing method, including, but not limited to, spin coating, dip coating, roll coating, spray coating, doctor blade coating, wire bar coating, slit coating, inkjet printing, screen printing, gravure printing, and flexographic printing.

[0174] The formulation may comprise a mixture of two or more solvents, preferably a mixture comprising at least one benzene substituted with one or more substituents as described above and one or more additional solvents, the one or more additional solvents being esters, optionally alkyl or aryl esters of alkyl or aryl carboxylic acids, optionally C 1~10 The solvent may be selected from alkyl benzoates, benzyl benzoate, or dimethoxybenzene. In a preferred embodiment, a mixture of trimethylbenzene and benzyl benzoate is used as the solvent. In another preferred embodiment, a mixture of trimethylbenzene and dimethoxybenzene is used as the solvent.

[0175] The formulation may contain additional ingredients, examples of which may include crosslinkers, adhesives, defoamers, deaerators, viscosity improvers, diluents, adjuvants, flow improvers, colorants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface active compounds, lubricants, wetting agents, dispersants and inhibitors.

[0176] After deposition of the precursor layer material, reaction can be carried out by any method known to those skilled in the art, such as by heat treatment and / or UV irradiation.

[0177] A photoactive layer is formed on one of the anode and cathode of the photoresponsive organic device, and the other of the anode and cathode is formed on the bulk heterojunction layer either before or after reaction of the reactive NFA.

[0178] In some embodiments, a reactive NFA is deposited and crosslinked to form an additional active organic layer on the crosslinked bulk heterojunction layer. The additional active organic layer can be an electron donor layer, a charge transport organic layer, or a charge blocking organic layer. The material or materials of the additional active organic layer can be deposited from a solution or suspension thereof.

[0179] Purpose The circuit may include an OPD connected to one or more voltage sources such that a reverse bias is applied to the OPD; a device configured to measure a photocurrent; and an amplifier configured to amplify the OPD's output signal. The voltage applied to the photodetector may vary. In some embodiments, the photodetector may be continuously biased during use.

[0180] In some embodiments, the photodetector system comprises a plurality of photodetectors as described herein, for example, camera image sensors.

[0181] In some embodiments, a sensor can include an OPD and a light source as described herein, where the OPD is configured to receive light emitted from the light source. In some embodiments, the light source has a peak wavelength of at least 900 nm or at least 1000 nm, optionally in the range of 900-1500 nm.

[0182] In some embodiments, the light from the light source may or may not be modified before reaching the OPD, for example, the light may be reflected, filtered, downconverted, or upconverted before reaching the OPD.

[0183] The photoresponsive organic device as described herein can be an organic photovoltaic device or an organic photodetector. The organic photodetectors as described herein can be used in a wide range of applications, including, but not limited to, detecting the presence and / or brightness of ambient light, and in sensors comprising an organic photodetector and a light source. The photodetector can be configured so that light emitted from the light source is incident on the photodetector, and changes in the wavelength and / or brightness of the light due to absorption, reflection, and / or light emission by an object, e.g., a substance of interest in a sample, placed in the optical path between the light source and the organic photodetector can be detected. The sample can be a non-biological sample, e.g., a water sample, or a biological sample collected from a human or animal subject. The sensor can be, but is not limited to, a gas sensor, a biosensor, an X-ray imaging device, an image sensor, e.g., a camera image sensor, a motion sensor (e.g., for use in security applications), a proximity sensor, or a fingerprint sensor. A 1D or 2D photodetector array can include a plurality of photodetectors as described herein within an image sensor. The light detector may be configured to detect light emitted from an analyte of interest that emits light when illuminated by a light source or that is coupled to a light-emitting tag that emits light when illuminated by a light source. The light detector may be configured to detect the wavelength of light emitted by the analyte of interest or its coupled light-emitting tag.

[0184] The detection surface area of ​​an OPD as described herein can be selected depending on the desired application. Optionally, an OPD as described herein has a surface area of ​​about 3 cm 2 Less than 2cm 2 Less than 1cm 2 Less than 0.75cm 2 Less than 0.5cm 2 Less than or about 0.25 cm 2 Optionally, each OPD may be part of an OPD array, where each OPD has an area as described herein, optionally less than 1 mm 2 Less than, optionally 0.5 microns 2 ~900 microns 2The pixels of the array have an area in the range of .times. ...

[0185] [Example] measurement Unless otherwise specified, the HOMO and LUMO levels of the materials as described herein are as measured by square wave voltammetry (SWV).

[0186] In SWV, the current at the working electrode is measured while linearly sweeping the potential between the working and reference electrodes without delay. The difference current between the forward and reverse pulses is plotted as a function of potential to obtain a voltammogram. Measurements can be made with a CHI 660D Potentiostat.

[0187] An apparatus for measuring HOMO or LUMO energy levels by SWV can include a cell containing 0.1 M tertiary butylammonium hexafluorophosphate in acetonitrile; a 3 mm diameter glassy carbon working electrode; a platinum counter electrode; and a leak-free Ag / AgCl reference electrode.

[0188] At the end of the experiment, for calculation purposes, ferrocene is added directly to the existing cell, and the oxidation and reduction potentials of ferrocene versus Ag / AgCl are measured using cyclic voltammetry (CV).

[0189] The sample is dissolved in toluene (3 mg / ml) and spun at 3000 rpm directly onto the glassy carbon working electrode.

[0190] LUMO = 4.8 - E of ferrocene (peak-to-peak average) - E of reduced sample (maximum peak). HOMO = 4.8 - E of ferrocene (peak-to-peak average) + E of oxidation of sample (maximum peak). A typical SWV experiment is performed at a frequency of 15 Hz; amplitude of 25 mV and increment steps of 0.004 V. Results are calculated from three freshly spun film samples, both HOMO and LUMO data.

[0191] Unless otherwise stated, absorption spectra were measured using a Cary 5000 UV-VIS-NIR Spectrometer. Measurements were taken from 175 nm to 3300 nm using a PbSmart NIR detector for an extended photometric range, with variable slit widths (down to 0.01 nm) for optimal control of data resolution.

[0192] Unless otherwise stated, absorption values ​​are for solutions. Absorption data is obtained by measuring the intensity of light radiation transmitted through a solution sample. The absorption intensity is plotted against the wavelength of incident light to obtain an absorption spectrum. A method for measuring absorption may involve measuring a 15 mg / ml solution in a quartz cuvette and comparing it to a cuvette containing only solvent.

[0193] Unless otherwise stated, solution absorption data presented herein was measured in toluene solution. Compound example 1 Compound Example 1 can be prepared according to the following scheme: [ka]

[0194] modeling Modeling of model compounds 1 and 2 was performed using Gaussian09 software available from Gaussian Corporation, using B3LYP (functional) and LACVP. * The results are shown in Table 1.

[0195] Table 1 [Table 1]

[0196] As shown in Table 1, the acceptor group A 1Functionalization of NFA with a group suitable for attachment of a reactive group, e.g., an alkoxy group as in model compound 2, can shallow the HOMO and result in an increase in the band gap. Therefore, it is preferred to functionalize another group of the NFA with a reactive group, preferably a bridging or donor unit.

Claims

1. 1. A method for forming a photoresponsive organic device comprising an anode, a cathode, and a photoactive layer disposed between the anode and the cathode, comprising: forming a precursor layer on one of the anode and the cathode, the precursor layer comprising a reactive nonfullerene acceptor substituted with at least two reactive groups; and forming a photoactive layer, comprising reacting the reactive groups to form chains or networks comprising a plurality of reacted non-fullerene acceptor molecules; and forming the other of the anode and cathode before or after reaction of the reactive groups; A method comprising:

2. 10. The method of claim 1, wherein the photoactive layer comprises a chain comprising a plurality of nonfullerene acceptor molecules linked by linking groups formed when the reactive groups react with each other or with the reactive groups of the linking agent.

3. The method of claim 1 or 2, wherein the photoactive layer is a bulk heterojunction layer further comprising an electron donating material.

4. 4. The method of claim 3, wherein the electron donating material is a polymer comprising a reactive group capable of reacting with a reactive group of the nonfullerene acceptor, and the photoactive layer comprises a crosslinked network comprising the electron donating polymer crosslinked by the nonfullerene acceptor.

5. 3. The method of claim 1 or 2, wherein the photoactive layer comprises an electron donating sublayer in direct adjacent contact with an electron accepting sublayer, and the precursor layer is an electron accepting precursor sublayer comprising a reactive nonfullerene acceptor.

6. 3. The method of claim 1, wherein the photoactive layer comprises a bulk heterojunction sublayer and at least one of an electron donating sublayer on the anode side of the bulk heterojunction sublayer and an electron accepting sublayer on the cathode side of the bulk heterojunction sublayer, and the precursor layer comprising a precursor and a reactive nonfullerene acceptor is a precursor of the electron accepting sublayer or a precursor of the bulk heterojunction sublayer.

7. 10. The method of any one of the preceding claims, wherein each occurrence of the reactive group is independently selected from the group consisting of benzocyclobutene and acyclic or cyclic groups containing non-conjugated carbon-carbon double bonds.

8. The non-fullerene acceptor is represented by formula (I) or (II): A １ -(B １ )x １ -(D １ )y １ -(B １ )x ２ -A １ (I) A １ -(B ２ )x ５ -(D ２ )y ２ -(B ３ )x ３ -A ２ -(B ３ )x ４ -(D ３ )y ３ -(B ２ )x ６ -A １ (II) (In the formula: A for each occurrence １ are independently monovalent electron-accepting groups; A ２ is a divalent heteroaromatic electron-accepting group; D １ , D ２ and D ３ is independently at each occurrence an electron donating group; B １ , B ２ and B ３ is independently at each occurrence a bridging group; x １ ~x ６ are each independently 0, 1, 2, or 3; y １ , y ２ and y ３ are each independently at least 1. is a compound of the formula: The compound of formula (I) or (II) is substituted with at least two reactive groups.

10. A method according to any one of the preceding claims.

9. The at least two reactive groups are D １ , D ２ , D ３ , B １ , B ２ and B ３ The method of claim 8, wherein the substituent is one of:

10. D １ is represented by formula (VIIe): 【Chemistry 1】 (In the formula, Y Ａ is S or O, and R ５１ is H or a substituent, and R ５３ is a substituent) The method according to claim 8 or 9, wherein the group is

11. A １ is represented by formula (IXa-1): 【Chemistry 2】 (In the formula: G is C=O, C=S SO, SO ２ , N.R. ３３ or C(R ３３ ) ２ where R ３３ is CN or COOR ４０ and R ４０ is H or a substituent; R １０ is H or a substituent; Ar ９ is an unsubstituted or substituted monocyclic or fused aromatic or heteroaromatic group; X ６０ are each independently CN, CF ３ or COOR ４０ is) The method according to any one of claims 8 to 10, wherein the group is

12. Formula (I) or (II): A １ -(B １ )x １ -(D １ )y １ -(B １ )x ２ -A １ (I) A １ -(B ２ )x ５ -(D ２ )y ２ -(B ３ )x ３ -A ２ -(B ３ )x ４ -(D ３ )y ３ -(B ２ )x ６ -A １ (II) (In the formula: A for each occurrence １ are independently monovalent electron-accepting groups; A ２ is a divalent heteroaromatic electron-accepting group; D １ , D ２ and D ３ is independently at each occurrence an electron donating group; B １ , B ２ and B ３ is independently at each occurrence a bridging group; x １ ~x ６ are each independently 0, 1, 2, or 3; y １ , y ２ and y ３ are each independently at least 1. A reactive compound of the formula: A compound of formula (I) or (II) substituted with at least two first reactive groups.

13. A composition comprising the compound of claim 12 and an electron donating material.

14. 14. The composition of claim 13, wherein the electron donating material comprises a second reactive group capable of reacting with the first reactive group.

15. A formulation comprising a compound or composition according to any one of claims 12 to 14 dissolved or dispersed in one or more solvents.

16. 13. A photoresponsive organic device comprising an anode, a cathode, and a photoactive layer disposed between the anode and the cathode, wherein the photoactive layer comprises chains or networks comprising a plurality of reacted molecules of formula (I) or (II) according to claim 12.

17. 17. A light sensor comprising a light source and the organic photodetector of claim 16, wherein the organic photodetector is configured to detect light emitted from the light source.

18. 18. The optical sensor of claim 17, wherein the light source emits light having a peak wavelength greater than 900 nm.

19. 17. A method of forming a photoresponsive organic device according to claim 16, comprising: forming a precursor layer comprising a compound of formula (I) or (II) on one of an anode and a cathode; forming a photoactive layer comprising reacting the reactive groups to form chains or networks comprising a plurality of reacted molecules of the compound of formula (I) or (II); and forming the other of the anode or cathode before or after reaction of the reactive groups.

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