Organic optical detector

Abstract

To provide an organic optical detector comprising a photosensitive organic layer arranged between an anode and a cathode, and an optical sensor including the organic optical detector.SOLUTION: An organic optical detector includes a photosensitive organic layer including an electron donor and an electron acceptor, and the electron acceptor is a compound represented by EAG-EDG-EAG (I) (where each EAG is an electron acceptor group and EDG is an electron donor group expressed by specific formula (II) or specific formula (III)). An optical sensor may include an organic optical detector and a light source, for example, a near infrared light source.SELECTED DRAWING: None

Description

[Background technology]

[0001] SUMMARY OF THE DISCLOSURE Embodiments of the present disclosure relate to organic photodetectors.

[0002] Organic light-emitting devices, organic field-effect transistors, organic solar cell devices, and organic photovoltaic devices A range of organic electronic devices comprising organic semiconductor materials are known, including photodetectors (OPDs). .

[0003] WO2018 / 065352 describes a small molecule acceptor that does not contain a fullerene moiety and a donor and a photoactive layer containing a conjugated copolymer having electron donor units and acceptor units. The company has disclosed the OPD.

[0004] WO2018 / 065356 describes a small molecule receptor that does not contain a fullerene moiety and a random a conjugated copolymer electron donor having donor and acceptor units dispersed in the polymer; US Pat. No. 5,999,333 discloses an OPD having a photoactive layer comprising:

[0005] Yao et al., “Design,Synthesis,and Photovo ltaic Characterization of a Small Molecule lar Acceptor with an Ultra-Narrow Band G ap”,Angew Chem Int Ed Engl. 2017 Mar 6;5 6(11):3045-3049 is a non-fullerene with a band gap of 1.24 eV. The authors disclose a receptor for

[0006] Li et al, “Fused Tris(thienothiophene) - Based Electron Acceptor with Strong Near -Infrared Absorption for High-Performance e As-Cast Solar Cells”,Advanced Material s,Vol. 30(10),2018, describes the development of fused octacyclic electron acceptors (FOIs) for solar cells. C) is disclosed.

[0007] Gao et al., “A New Nonfullerene Acceptor with Near Infrared Absorption for High P erformance Ternary-Blend Organic Solar C ells with Efficiency over 13%” Advanced Science, Vol. 5(6), June 2018, three condensed thieno[3, 2-b]thiophene-based receptor with difluoro-substituted indanone terminal groups Solar cells containing the donor-acceptor (ADA) type non-fullerene acceptor 3TT-FIC has disclosed.

[0008] Wang et al, “Fused Hexacyclic Nonfullere ne Acceptor with Strong Near-Infrared Ab sorption for Semitransparent Organic Sol "Ar Cells with 9.77% Efficiency" is an electron donor dithiocarbamate The electron-withdrawing group 1,1-dithiophene is adjacent to enocyclopentathieno[3,2-b]thiophene. A solar cell containing an IHIC receptor based on anomethylene-3-indanone is disclosed. is. Summary of the Invention

[0009] A summary of aspects of certain embodiments disclosed herein is set forth below. These aspects include These specific embodiments are merely presented to provide the reader with a brief summary of these embodiments. It will be understood that these aspects are not intended to limit the scope of the present disclosure. Indeed, this disclosure may include various aspects and / or methods that may not be described. Combinations of aspects may be included.

[0010] The embodiments of the present disclosure include an anode, a cathode, and a cathode disposed between the anode and the cathode. and a photosensitive organic layer comprising an electron donor and and an electron acceptor. In some embodiments, the electron acceptor has formula (I): EAG-EDG-EAG (I) wherein each EAG is an electron accepting group and EDG is a group represented by formula (II) or (III): [ka] wherein each X is independently O or S; Ar 3 and Ar 4 independently, at each occurrence, a monocyclic or polycyclic aromatic group or or a heteroaromatic group, Ar 5 thiophene, which is unsubstituted or substituted by one or two substituents; selected from the group consisting of furan, and benzene; R 1 and R 2 is independently, at each occurrence, a substituent; R 4 and R 5 are each independently H or a substituent; R 3 and R 6are each independently H, a substituent, or a divalent group bonded to EAG; , Z 1 is a direct bond or Z 1 is a substituent R 4 With Ar 1 Forming Ar 1 is a monocyclic or polycyclic aromatic or heteroaromatic group, Z 2 is a direct bond or Z 2 is a substituent R 5 With Ar 2 Forming Ar 2 is a monocyclic or polycyclic aromatic or heteroaromatic group, p is 1, 2, or 3; q is 1, 2, or 3; is the electron donating group of ) which is the point of attachment to EAG.

[0011] In some embodiments, the organic photodetectors described herein and the organic photodetectors are A voltage source to apply the bias and a photodetector to measure the photocurrent generated by the photodetector. and at least one of the devices configured as above.

[0012] In some embodiments, a photosensitive light-emitting layer on one of the anode and the cathode. and forming the other of the anode and cathode on the photosensitive organic layer. As described herein, a method for forming an organic photodetector is provided.

[0013] The inventors have discovered that compounds of formula (I) are capable of emitting long wavelength light, e.g., above 750 nm, optionally These compounds are capable of absorbing light above 1000 nm, and optionally below 1500 nm. The present invention relates to an organic photodetector, in particular an optical sensor containing an OPD and a near infrared light source. We have found that it is possible to

[0014] Thus, in some embodiments, a light source and a detector for detecting light emitted from the light source are provided. and an organic photodetector as described herein configured in accordance with the present invention.

[0015] In some embodiments, determining the presence and / or concentration of a target material in a sample 1. A method, comprising: illuminating a sample; and detecting light emitted from the sample upon illumination. measuring a response of an organic photodetector described herein configured to receive A method is provided that includes: [Brief description of the drawings]

[0016] The disclosed technology and the accompanying drawings illustrate several implementations of the disclosed technology. . [Figure 1] 1 illustrates an organic photodetector according to one embodiment of the present invention. [Diagram 2] 1 is a graph of external quantum efficiency versus voltage for an OPD according to some embodiments of the present disclosure, the compound having a receptor of Formula (I) and a comparative OPD having a receptor IEICO-4F.

[0017] The drawings are not drawn to scale and have various perspectives and views. Additionally, some components and / or operations may include: For purposes of discussion of some embodiments of the disclosed technology, the following may be separated into different blocks: The techniques may be combined in various modifications and variations. While alternative configurations are possible, specific embodiments have been shown by way of example in the drawings and are described in detail below. However, it is not intended to limit the technology to the particular implementations described. On the contrary, the present technology is within the scope of the technology defined by the appended claims. It is intended to cover all modifications, equivalents, and alternatives within the scope of the appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Unless the context clearly requires otherwise, the term "including" is used throughout the description and claims. Words such as "comprise" and "comprising" are used to mean exclusive or inclusive. should be interpreted in an inclusive sense, as opposed to an exclusive sense, i.e. "including, but not limited to, As used herein, the term "including but not limited to" should be construed as meaning "including but not limited to." The terms "connected" and "coupled" or any variation thereof mean two or more means any connection or coupling, either direct or indirect, between the elements of The connections or connections may be physical, logical, electromagnetic, or a combination thereof. For the purposes of this application, the words "herein," "above," "below," and words of similar meaning are used herein. When used herein, it is a reference to this application as a whole and not to any particular portions of this application. To the extent that the terms in this section use a number, the words in the Detailed Description shall The word "or" in reference to a list of two or more items may also include the plural or singular. means all of the following interpretations of the word: any of the items in the list, all of the items in the list This covers any combination of items in the list.

[0019] The teachings of the technology provided herein may be applied to other systems, not necessarily those described below. The elements and operations of the various embodiments described below may be combined to Further implementations of the technique may be provided in conjunction with the following: The embodiments may include less than or equal to the additional elements described below. It may also include elements.

[0020] These and other changes can be made to the present technology in light of the following detailed description. Although the description describes a particular example of the technology and describes the best mode contemplated, No matter how detailed the description may seem, the technology can be practiced in many ways. Although the details of the system may vary considerably in its particular implementation, As noted above, certain features or aspects of the present technology are still encompassed by the technology presented. The particular term used in describing the manner in which it is used is not intended to imply any particular characteristic of the technology to which it pertains. implying that a term has been redefined herein to be limited to a particular feature, feature, or aspect. Generally, the terms used in the following claims are intended to be understood as meaning "invention" or "disclosure." Unless the Detailed Description section expressly defines such terms, This disclosure should not be construed as limiting the technique to the specific examples disclosed herein. The actual scope of the present technology is not limited to the disclosed embodiments, but may include all or part of the claims. This includes any and all equivalent methods of practicing or implementing the method.

[0021] In order to reduce the number of claims, certain aspects of the present technology are Although presented below in the form of a set of claims, applicants contemplate various aspects of the present technology in any of the claimed forms. For example, some aspects of the present technology may be implemented in accordance with the claims of a computer readable medium. Although the scope of the invention may be recited, other aspects are likewise within the scope of the claims of the computer-readable medium. As embodied in a means-plus-function claim, It may be embodied in other forms.

[0022] In the following description, for purposes of explanation, a thorough understanding of the implementation of the disclosed technology is provided. In order to provide an understanding of the present invention, numerous specific details are set forth. It will be apparent to one skilled in the art that the present invention may be practiced without some of these specific details. Wax.

[0023] FIG. 1 shows an OPD according to some embodiments of the present disclosure. The OPD includes a cathode 103. anode 107; and a bulk heterojunction layer 10 disposed between the anode and the cathode. 5. The OPD is supported on a substrate 101, optionally a glass or plastic substrate. It can be held.

[0024] FIG. 1 shows a configuration in which a cathode is disposed between a substrate and an anode. , the anode may be disposed between the cathode and the substrate.

[0025] The bulk heterojunction layer comprises a mixture of electron acceptors and electron donors. In some embodiments, the bulk heterojunction layer consists of an electron acceptor and an electron donor. In some embodiments, the bulk heterojunction layer includes an additional electron acceptor other than the electron acceptor of formula (I). Optionally, the further electron acceptor is a fullerene.

[0026] Each of the anode and cathode may independently be a single conductive layer, or may include multiple layers.

[0027] An OPD may include layers other than the anode, cathode, and bulk shown in FIG. In some embodiments, the hole transport layer is disposed between the anode and the bulk heterojunction layer. In some embodiments, the electron transport layer is disposed between the cathode and the bulk heterojunction layer. In some embodiments, the work function modifying layer is disposed between the bulk heterojunction layer and the anodic The bulk heterojunction layer may be disposed between the cathode and the bulk heterojunction layer, and / or between the bulk heterojunction layer and the cathode.

[0028] In use, the photodetectors described in this disclosure may be used to measure the device and / or photocurrent. The device may be connected to a voltage source for applying a reverse bias to the device configured to The voltage applied to the photodetector can be variable. In some embodiments, the photodetector is The bias may be applied continuously during use.

[0029] In some embodiments, the photodetector system comprises a plurality of photodetectors as described herein. , for example including an image sensor of a camera.

[0030] In some embodiments, the sensor comprises an OPD as described herein and a detector for detecting a light source from the OPD. and a light source configured to receive light emitted from the

[0031] In some embodiments, the light from the light source may be modified before reaching the OPD. For example, the light may be filtered, or may be unaltered before it reaches the OPD. It may be down-converted or up-converted.

[0032] In some embodiments, the light source has a peak greater than 750 nm, optionally less than 1500 nm. It has a wavelength.

[0033] The bulk heterojunction layer may have the formula (I): EAG-EDG-EAG (I) wherein each EAG is an electron accepting group and EDG is a group represented by formula (II) or (III): [ka] (In the formula, wherein each X is independently O or S; Ar 3 and Ar 4 independently, at each occurrence, a monocyclic or polycyclic aromatic group or or a heteroaromatic group, Ar 5 thiophene, which is unsubstituted or substituted by one or two substituents; selected from the group consisting of furan, and benzene; R 1 and R 2 is independently, at each occurrence, a substituent; R 4 and R 5 are each independently H or a substituent; R 3 and R 6 are each independently H, a substituent, or a divalent group bonded to EAG; , Z 1 is a direct bond or Z 1 is a substituent R 4 With Ar 1 Forming Ar 1 is a monocyclic or polycyclic aromatic or heteroaromatic group, Z 2 is a direct bond or Z 2 is a substituent R 5 With Ar 2 Forming Ar 2 is a monocyclic or polycyclic aromatic or heteroaromatic group, p is 1, 2, or 3; q is 1, 2, or 3; ---- is the electron donor group of ) which is the point of attachment to EAG. It may contain substances.

[0034] Optionally, R of formula (Ia) or (Ib) 1 and R 2 independently at each occurrence And, Linear, branched, or cyclic C 1-20 Alkyl (one or more non-adjacent, non-terminal C atoms are O, S, and NR 12 R may be replaced by CO, CO, or COO. 12 But, C 1-12 Hydrocarbyl, C 1-20 One or more H atoms of the alkyl are replaced by F. may be replaced), and Formula (Ak)u-(Ar 6 )v group (Ak is a group in which one or more C atoms are O, S, CO or COO may be replaced by C 1-12 an alkylene chain, u being 0 or 1; Yes, Ar 6 is, at each occurrence, independently unsubstituted or substituted with one or more is an aromatic or heteroaromatic group substituted with a group, v is at least 1, and (optionally 1, 2, or 3).

[0035] C 1-12 Hydrocarbyl is C 1-12 alkyl, unsubstituted phenyl, and one or more C 1-6 It may be a phenyl substituted with an alkyl group.

[0036] Ar 6 is preferably phenyl.

[0037] If present, Ar 6 The substituent of is a substituent R 16 R may be 16 is the time of each occurrence Independently, C 1-20 Alkyl (one or more non-adjacent, non-terminal C atoms are O, S, and NR 12 , CO, or COO, and C 1-20 a one or more H atoms of the alkyl may be replaced by F).

[0038] When v is 3 or more, −(Ar 6 )v is Ar 6 The group may be linear or branched. The linear chain of Ar groups described herein is defined as having a monovalent terminal Ar 6 on the group only, whereas Ar 6 The branched chain of the group has at least two monovalent terminal Ar 6 It has a group.

[0039] Optionally, R 1 and R 2 At least one of the following must be unsubstituted in each occurrence: or R as described above 16 Phenyl substituted with one or more substituents selected from It's Nil. Optionally, each R 3 ~R 6 is, independently, H, C 1-12 Alkyl (one or more non-adjacent, non-terminal C atoms are O, S, COO, or CO), and Aromatic or heteroaromatic group Ar 6 (unsubstituted or substituted with one or more substituents) The selected item is the one that is currently selected. Ar 6 is preferably an aromatic group, more preferably phenyl.

[0040] Ar 6 If present, one or more of the substituents in 1-12 Alkyl (one or more adjacent Non-terminal C atoms may be replaced by O, S, COO, or CO. ) may be selected from.

[0041] As used herein, a "non-terminal" C atom of an alkyl group refers to a straight-chain (n-alkyl) C atom of an alkyl group other than the methyl C atom of a branched alkyl chain or the methyl C atom of a branched alkyl chain. Taste.

[0042] Optionally, Ar 3 and Ar 4 each independently represents thiophene, furan, bifuran, and bithiophene.

[0043] Ar 3 , Ar 4 , and Ar 5 are each independently unsubstituted or one or more Substituted by a substituent. 3 , Ar 4 , and Ar 5 Preferred substituents of are In the case of 3 ~R 6 , preferably C 1-20 Alkyl (one or more adjacent Non-contact, non-terminal C atoms are replaced by O, S, CO, or COO) is selected from.

[0044] Optionally, the EDG is represented by formula (IIa) and (IIIa): [ka] is selected from. Optionally, the EDG has formula (IIb) and (IIIb): [ka] (In the formula, R 7 is independently at each occurrence H or a substituent group; .

[0045] Optionally, R 7 may, at each occurrence, independently: H, C 1-12 Alkyl (one or more non-adjacent, non-terminal C atoms are O, S, CO O, or CO), and Aromatic or heteroaromatic group Ar 6 (unsubstituted or substituted with one or more substituents) The selected item is the one that is currently selected.

[0046] In some embodiments, each R 3 ~R 6 , and, if present, R 7 , H, C 1-2 0 alkyl, or C 1-20 It is an alkoxy.

[0047] In some embodiments, R 4 and R 5 At least one of, and optionally both of , H, but each R 3 , R 6 , and, if present, R 7 is H.

[0048] Optionally, at least one of p and q is 2.

[0049] Optionally, Z 1 is R 4 to form a monocyclic aromatic or heteroaromatic group. , and / or Z 2 is R 5 to form a monocyclic aromatic or heteroaromatic group. do.

[0050] Optionally, Z 1 is R 4 to form a thiophene or furan ring, and / or or Z 2 is R 5 to form a thiophene ring or a furan ring.

[0051] Each EAG has a LUMO level that is deeper (i.e., deeper from vacuum) than that of the EDG. The LUMO levels of the EAG and EDG are preferably at least 1 eV deep. By modeling the LUMO level of EAG-H with that of H-EDG-H, i.e., by replacing the bond between EAG and EDG with a bond to a hydrogen atom. The modeling is performed using B3LYP (functionals) and LACVP* (basis functions). Gaussian09 with the Gaussian number system was used to This may be implemented using ussian09 software.

[0052] Optionally, each EAG has formula (IV) or (V): [ka] wherein A is a 5- or 6-membered ring which is unsubstituted or substituted with one or more substituents. and R 10 and R 11 is independently, at each occurrence, a substituent; Ar 7 but , an aromatic or heteroaromatic group which is unsubstituted or substituted with one or more substituents (which is the base).

[0053] Optionally, each EAG has formula (VI): [ka] (In the formula, R 10 is H or a substituent, ---- represents the linkage position to EDG, each X 1 ~X 4 But independently, CR 13 or N and R 13 However, at each occurrence, H or a substituent).

[0054] Optionally, each R 13 are independently H, C 1-12 Alkyl and electron-withdrawing groups Optionally, the electron withdrawing group is F or CN.

[0055] R 10 is preferably H.

[0056] Substituent R 10 is preferably C 1-12 Alkyl (one or more non-adjacent, non-terminal The terminal C atom may be replaced by O, S, COO, or CO, and one of the alkyl one or more H atoms may be replaced by F), and an aromatic group Ar 9 , optional phenyl (unsubstituted or substituted with F and C 1-12 Alkyl (one or more adjacent Non-terminal C atoms may be replaced by O, S, COO, or CO. ) may be substituted with one or more substituents selected from

[0057] Optionally, R 3 and / or R 6 is B(R 14 )2(wherein, R 14 is the time of each occurrence is a substituent in 1-20is a hydrocarbyl group, while Both EAG groups have the formula (VII): [ka] (In the formula, Ar 8 is a monocyclic or or a fused heteroaromatic group, where → is R 3 or R 6 to the boron atom, - is the bond to EDG).

[0058] Ar 8 or Ar 8 Each of the substituents (if present) in 7 Explained regarding The substituents may be selected from those listed above.

[0059] Optionally, R 14 is C 1-20 R is a hydrocarbyl group 14 is C 1-12 Al phenyl, unsubstituted phenyl, and one or more C 1-12 Phenyl substituted with alkyl groups are selected.

[0060] Optionally, the group of formula (VII) is selected from the group represented by formula (VIIa), (VIIb), and (VIIc ): [ka] (In the formula, R 15 is, at each occurrence, independently H or a substituent, optionally H or Or R 7 The substituents are selected from EDG, EAG, and and EDG's B(R 14 ) The two substituents may be linked together to form a 5- or 6-membered ring. .

[0061] Optionally, the EAG is represented by formula (XIV)-(XXV): [ka] TIFF2024037774000010.tif41162J is O or S.

[0062] A is unsubstituted or substituted with one or more substituents and may further include one or more It is a 5- or 6-membered ring which may be fused to a ring.

[0063] R 23 represents, in each occurrence, a substituent, optionally C 1-12 Alkyl (one or more adjacent Non-terminal C atoms that are not adjacent may be replaced by O, S, COO, or CO. Preferably, one or more H atoms of the alkyl may be replaced by F.

[0064] R 25 are, independently at each occurrence, H;F;C 1-12 Alkyl (one or more adjacent Non-terminal C atoms that are not adjacent may be replaced by O, S, COO, or CO. Preferably, one or more H atoms of the alkyl may be replaced by F), or aromatic Ar group 2 , optionally phenyl (unsubstituted or selected from F and C 1-12 Alki (one or more non-adjacent, non-terminal C atoms are replaced by O, S, COO, or CO) (which may be substituted with one or more substituents selected from the group consisting of The compound is selected from the group consisting of:

[0065] R 26 is a substituent, preferably -(Ar 13 )w (In the formula, Ar 13 is, at each occurrence, independently unsubstituted or substituted. is a substituted aryl or heteroaryl group, preferably thiophene; w is 1, 2 or 3), [ka] C 1-12 Alkyl (one or more non-adjacent, non-terminal C atoms are O, S, COO, or CO, and one or more H atoms of the alkyl are replaced by F. is a substituent selected from the group consisting of aryl, aryloxy ...

[0066] Ar 14 is a 5-membered heteroaromatic group, preferably unsubstituted or one or more substituted The aryl group is substituted with a thiophene or a furan.

[0067] Ar 13 and Ar 14 The substituents, when present, are optionally 1-12 Alkyl (One or more non-adjacent, non-terminal C atoms are replaced by O, S, CO, or COO. and one or more H atoms may be replaced by F. can be.

[0068] Z 1 is N or P T 1 , T 2 , and T 3 each independently represents an aryl group which may be fused to one or more additional rings; represents an aryl or heteroaryl ring. 1 , T 2 , and T 3 The substituents, if present, , optionally, R 15 is selected from the non-H groups:

[0069] Exemplary compounds of formula (XIVa) or (XIVb) include: [ka] (Wherein, Ak is C 1-12 Alkylene chain (where one or more C atoms are O, S, CO or COO), where An is an anion, and optionally - SO3 - and each benzene ring is independently unsubstituted or R 10 Explanation regarding substituted with one or more substituents selected from the substituents set forth above.

[0070] Exemplary EAGs of formula (XXI) are [Chemical formula 12] [ka] Exemplary EAG groups of formula (XXII) are: [Chemical formula 13] [ka] Exemplary compounds of formula (I) are [ka] TIFF2024037774000016.tif206166 (wherein EH is ethylhexyl).

[0071] The compounds of formula (I) may be used in combination with a fullerene acceptor.

[0072] The weight ratio of the compound of formula (I) to the fullerene acceptor ranged from about 1:0.1 to 1:1. The ratio may be in the range of about 1:0.1 to 1:0.5, preferably.

[0073] Fullerene is C 60 , C70 , C 76 , C 78 , or C 84 Fullerene, or It may be a derivative thereof, which may include, but is not limited to, a PCBM-type fullerene derivative. (phenyl-C61-butyric acid methyl ester (C 60 PCBM) and phenyl-C 71-Butyric acid methyl ester (C 70 PCBM) and TCBM-type fullerene derivatives Tolyl-C61-butyric acid methyl ester (C 60 TCBM), and T hCBM-type fullerene derivatives (e.g., thienyl-C61-butyric acid methyl ester (C 60 ThCBM).

[0074] When present, the fullerene acceptor has formula (VIII): [ka] (wherein A, together with the C-C groups of the fullerene, may be unsubstituted or may be one or more The substituents may be substituted with the above groups to form a monocyclic or fused ring group.

[0075] Exemplary fullerene derivatives include those represented by formulae (IIIa), (IIIb), and (III c): [ka] (In the formula, R 30 ~R 42 are each independently H or a substituent.

[0076] Substituent R 30 ~R 42 is optionally independently, at each occurrence, aryl or Heteroaryl, optionally phenyl (which may be unsubstituted or substituted with one or more substituents); may be substituted with a substituent), and C 1-20 Alkyl (without one or more adjacent Non-terminal C atoms may be replaced by O, S, CO, or COO, and one or more H atoms may be replaced by F).

[0077] an aryl or heteroaryl group R 30 ~R 42 The substituents of are optionally 1-12 Alkyl (one or more non-adjacent, non-terminal C atoms are O, S, CO, or COO) and one or more H atoms may be replaced by F) are selected.

[0078] The donor (p-type) compound is not particularly limited and may be an organic polymer or a non-polymer organic molecule. The p-type compound can be appropriately selected from electron donating materials known to those skilled in the art, including those having the formula ( I) has a HOMO deeper (deeper than vacuum) than the LUMO of compound I. The HOMO level of the p-type donor and the LUMO level of the n-type acceptor compound of formula (I) The gap between them is less than 1.4 eV.

[0079] In a preferred embodiment, the p-type donor compound is an organic conjugated polymer. The monomers may be homopolymers or copolymers, including alternating, random, or block copolymers. Preferred are amorphous or semi-crystalline conjugated organic polymers. Preferably, the p-type organic semiconductor has a low band gap, typically 2.5 eV to 1.5 e V, preferably 2.3 eV to 1.8 eV. As polymers, mention may be made of polymers selected from conjugated hydrocarbons or heterocyclic polymers. These may be polyacenes, polyanilines, polyazulenes, polybenzofurans, etc. , polyfluorene, polyfuran, polyindenofluorene, polyindole, polyphenylene Polypyrazoline, polypyrene, polypyridazine, polypyridine, polytriaryl amine, poly(phenylenevinylene), poly(3-substituted thiophene), poly(3,4-disubstituted substituted thiophenes), polyselenophenes, poly(3-substituted selenophenes), poly(3,4-disubstituted selenophenes), substituted selenophene), poly(bisthiophene), poly(terthiophene), poly(bisselenophene) Poly(tert-butyl selenophene), polythieno[2,3-b]thiophene, poly Thieno[3,2-b]thiophene, polybenzothiophene, polybenzo[1,2-b:4 ,5-b'j dithiophene, polyisothianaphthene, poly(monosubstituted pyrrole), poly(3 ,4-substituted pyrrole), poly-1,3,4-oxadiazole, polyisothianaphthene, and co-derivatives thereof. Preferred examples of p-type donors include poly(phenylene ether), each of which may be substituted. Copolymers of trifluorene and polythiophene, and optionally substituted phenyl groups It is a polymer containing benzothiadiazole and thiophene repeat units. It will be appreciated that the donor may also be comprised of a mixture of multiple electron donating materials.

[0080] Optionally, the donor polymer has the formula (XXX): [ka] (In the formula, R 50 and R 51 is independently, at each occurrence, H or a substituent. Contains repeating units of the formula:

[0081] Substituent R 50 and R 51 is R 7 is selected from the groups other than H described for Good too.

[0082] Preferably, each R 50 is a substituent. In a preferred embodiment, R 50 The group has the formula -Y 1 -C(R 52 )2-, wherein Y 1 , O, NR 5 3 , or C(R 52 )2, and R 52 In each occurrence, represents H or a substituent, preferably Or R 1 The substituents described for 1-30 Hydrocarbyl groups R 53 is a substituent, preferably C 1-30 It is a hydrocarbyl group.

[0083] Preferably, each R 51 is H.

[0084] Optionally, the donor polymer has the formula: [ka] (In the formula, R 25 , Z 1 , R 23 , and R 25 (as described above) The repeating unit may be selected from the group consisting of aryl, ...

[0085] Exemplary donor materials are disclosed, for example, in WO2013 / 051676, The contents are incorporated herein by reference.

[0086] Optionally, the p-type donor has a HOMO level 5.5 eV or less from the vacuum level. Optionally, the p-type donor has a HOMO level at least 4.1 eV above the vacuum level. Yes.

[0087] Unless otherwise specified, the HOMO and LUMO levels of the compounds described herein are , measured from a film of the compound using square wave voltammetry.

[0088] In some embodiments, the ratio of donor compound to acceptor compound is about 1:0.5 by weight. ~Approximately 1:2.

[0089] Preferably, the weight ratio of the donor compound to the acceptor compound is about 1:1 or about 1:1.5. It is.

[0090] At least one of the first and second electrodes is configured to direct light incident on the device through a bulk In some embodiments, the first and second electrodes are transparent to allow access to the bonding layer. Both poles are transparent.

[0091] Each transparent electrode preferably has a reflectance of at least 70% for wavelengths in the range of 300 to 900 nm. %, optionally having a transmittance of at least 80%.

[0092] In some embodiments, one electrode is transparent and the other electrode is reflective.

[0093] Optionally, the transparent electrode is made of a transparent conductive oxide, preferably indium tin oxide or In a preferred embodiment, the electrode comprises or consists of a layer of indium zinc oxide. The polymer may include poly(3,4-ethylenedioxythiophene) (PEDOT). In a preferred embodiment, the electrode is a mixture of PEDOT and polystyrene sulfonate (PSS). The electrode may comprise a layer of PEDOT:PSS.

[0094] Optionally, the reflective electrode may include a layer of reflective metal. The layer of reflective material may be aluminum. In some embodiments, a bilayer electrode may be used. For example, the electrodes can be indium tin oxide (ITO) / silver bilayer, ITO / aluminum The substrate may be a gold bilayer or an ITO / gold bilayer.

[0095] The device comprises a balloon on one of the anode and cathode supported by a substrate. A bulk heterojunction layer is formed, and the other of the anode or the cathode is connected to the bulk heterojunction layer. The insulating layer may be formed by depositing the insulating layer on the insulating layer.

[0096] The area of ​​the OPD is approximately 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 The substrate may be less than The substrate is not limited to, but may be a glass or plastic substrate. In some embodiments, the substrate may be silicon. For example, the substrate may be a silicon wafer. In use, incident light penetrates the substrate and the The substrate is transparent when transmitted through the electrodes supported by the

[0097] The substrate supporting one of the anode and the cathode is adapted to, in use, direct incident light to the anode. and the cathode, if any, may or may not be transparent.

[0098] Bulk heterojunction layers can be fabricated using any method, including, but not limited to, thermal evaporation and solvent deposition techniques. The nanoparticles may be formed by any process.

[0099] Preferably, the bulk heterojunction layer is a mixture of a receptor material and a solvent or a mixture of two or more solvents. and an electron donor material dissolved or dispersed in the The formulation is formed by spin coating, dip coating, roll coating, etc. Coating, spray coating, doctor blade coating, wire bar coating printing, slit coating, inkjet printing, screen printing, gravure printing, Any coating or printing method, including but not limited to flexography and flexography Thus, it may be deposited.

[0100] The one or more solvents of the formulation are optionally selected from chlorine, C 1-10 Alkyl, and C 1-1 0 alkoxy (two or more substituents may be linked together, either unsubstituted or with one or more C 1-6 forming a ring which may be substituted with an alkyl group; optionally toluene, xyloxy benzene, trimethylbenzene, tetramethylbenzene, anisole, indane, and and tetralin and its alkyl-substituted derivatives. It may comprise or consist of a benzene substituted with one or more substituents.

[0101] The formulation may comprise two or more solvents, preferably substituted with one or more substituents as described above. and mixtures comprising at least one benzene and one or more additional solvents. The one or more further solvents may be esters of alkyl or aryl carboxylic acids, optionally and alkyl or aryl esters, optionally C 1-10 Alkyl benzoates, benzoates In a preferred embodiment, the aryl benzoate or dimethoxybenzene may be selected from In the present invention, a mixture of trimethylbenzene and benzyl benzoate is used as the solvent. In an embodiment, a mixture of trimethylbenzene and dimethoxybenzene is used as the solvent. Use.

[0102] The formulation may contain, in addition to the electron acceptor, the electron donor, and one or more solvents, further components. Examples of such ingredients include adhesives, defoamers, degassing agents, viscosity enhancers, diluents, etc. agents, adjuvants, flow improvers, colorants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface active agents Mention may be made of antibacterial compounds, lubricants, wetting agents, dispersants, and inhibitors.

[0103] The organic photodetectors described herein include those that detect the presence and / or brightness of ambient light. In a wide range of applications including, but not limited to, organic photodetectors and light sources. The photodetector may be used in a photodetector in which light emitted from a light source is incident on the photodetector and a wave of light is detected. The change in length and / or brightness may be achieved, for example, by placing the light path between the light source and the organic photodetector. due to the absorption of light by and / or emission of light from the target material in the sample. The sensor may be configured to detect a gas, a biosensor, an X-ray imaging sensor, or the like. Devices, imaging sensors such as camera imaging sensors, motion sensors (e.g., security a proximity sensor, or a fingerprint sensor, for use in security applications. However, the 1D or 2D photosensor array may be included in the image sensor as described herein, but is not limited to the 1D or 2D photosensor array. The light detector may include a plurality of light detectors as described in claim 1, wherein the light detector emits light upon illumination by the light source. or released from a target analyte that is attached to a luminescent tag that emits light upon illumination by a light source. The light detector may be configured to detect light emitted from the target analyte or a binding thereto. The device may be configured to detect the wavelength of light emitted by the selected light emitting tag. EXAMPLES

[0104] synthesis The compounds may be prepared according to the following reaction scheme: [ka]

[0105] Compound Example 1 was prepared according to the following reaction scheme. [ka] Stage 1 The aldehyde (3 g, 9.4 mmol) was dissolved in chloroform (30 mL) and pyridine (5 The solvent was degassed for 0.5 h and then cooled to 0° C. Difluoro unit (3.2 g, 15.5 mmol) was added and the reaction mixture was degassed for an additional 0.25 h, then The mixture was then allowed to warm to room temperature for 3 hours. Methanol was added and the solvent was removed to give a red solid. The crude material was purified by column chromatography on silica eluting with petrol ether:DCM 9:1. The product-containing fractions were concentrated to give Stage 1 elution with a purity of 98%. Material (3.5 g) was obtained.

[0106] Stage 2 Condensed thiophene materials (Macromolecular Rapid Communic ations,2011,32,1664 or Chem. Mater.,2017,2 9,8369) (1 g, 1.0 mmol) was added to T Dissolve in HF and cool to -78 °C under nitrogen. N-Butyllithium (1.65 mL, 4.1 mmol) was added dropwise and the solution was stirred at -78 °C for 1 h, after which it was dissolved in THF (5 mL) Tributyltin chloride (0.99 mg, 3.0 mmol) was added dropwise. The reaction mixture was stirred for 16 The reaction was quenched by the addition of methanol and the solvent was removed. The crude material was triturated several times with methanol to give Stage 2 material, which was further purified. It was used in the next step.

[0107] Compound Example 1 Stage 1 material (1.3 g, 2.4 mmol) and Stage 2 material (1.5 g, 0. 97mmol) was dissolved in toluene and degassed. mg, 0.3 mmol) and tris(dibenzylideneacetone)dipalladium (71 m g, 0.08 mmol) was added and the reaction mixture was stirred at 80° C. for 5 hours. It was cooled and passed through a plug of Celite eluted with toluene. The filtrate was concentrated to give a black semi-solid. This was triturated with methanol to give the crude product as a solid. The product was purified by column chromatography on silica using 100 ml of DCM. The fractions were concentrated to give the product as a black solid (530 mg) of 97.8% purity.

[0108] Modeling Data We modeled the LUMO levels and HOMO-LUMO band gaps of the following compounds: Ta. [ka] TIFF2024037774000024.tif59163

[0109] Gaussian0 with B3LYP (functional) and LACVP* (basis set) 9 using the Gaussian09 software available from Gaussian. Quantum chemical modeling was performed using the [Table 1]

[0110] Referring to Table 1, model compounds Examples 1 and 2 were more potent than model comparative compounds 1 or 2. It has a shallower HOMO (i.e., closer to the vacuum level) and a smaller band gap. do.

[0111] Device Example 1 A device was prepared having the following structure: Cathode / donor:acceptor layer / anode A glass-like substrate coated with an indium-tin oxide (ITO) layer was placed on a polyethylene The working function of ITO was modified by treating it with polyphenylene imine (PEIE).

[0112] A bulk heterojunction of about 500 nm thick was prepared by mixing the donor polymer 1 and compound Example 1. The combined layer was washed with a solvent mixture of 1,2,4 trimethylbenzene and dimethoxybenzene 95:5 v / v. The mass ratio of donor to acceptor was 1:1.5. Therefore, it was deposited on the modified ITO layer.

[0113] The anode available from Heraeus (Clevios HIL-E100) was It was formed on the donor / receiver mixture layer by pin coating. [ka]

[0114] Donor Polymer 1 Device Example 1 For Device Example 1, except that Compound Example 1 was replaced with IEICO-4F. The devices were prepared as described above. [ka] Referring to FIG. 2, the external quantum efficiency of Device Example 1 is approximately 1000 nm above wavelength. Higher than comparison device 1.

[0115] Although the present invention has been described with respect to certain exemplary embodiments, the features disclosed herein Various modifications, variations and / or combinations of the present invention are contemplated by the following claims. It should be understood that such modifications would be apparent to one skilled in the art without departing from the spirit and scope of the invention.

Claims

1. A circuit comprising: an organic photodetector; and at least one of a voltage source for applying a reverse bias to the organic photodetector and a device configured to measure a photocurrent generated by the organic photodetector, the organic photodetector comprises an anode, a cathode, and a photosensitive organic layer disposed between the anode and the cathode, the photosensitive organic layer comprising an electron donor and an electron acceptor; The electron acceptor is represented by formula (I): EAG-EDG-EAG (I) wherein each EAG is an electron accepting group and EDG is a group of formula (IIa): 【Chemistry 1】 (In the formula, Each X is S; Ar ３ and Ar ４ However, all of them are thiophenes. R １ and R ２ are independently linear, branched or cyclic C 1-20 alkyl (one or more non-adjacent, non-terminal C atoms may be replaced by O, S, NR 12 , CO or COO, R 12 is C 1-12 hydrocarbyl, and one or more H atoms of said C 1-20 alkyl may be replaced by F); each R 3 to R 6 is H, C 1-20 alkyl, or C 1-20 alkoxy; Z １ is a direct bond, Z ２ is a direct bond, p is 1, q is 1, is an electron donating group of) which is the point of attachment to EAG; Each EAG has the formula (V): 【Chemistry 2】 (In the formula, R 10 in each occurrence is H or a substituent; --- represents the linkage position to EDG, each X 1 -X 4 is independently CR 13 , where R 13 at each occurrence is H or a substituent, and at least one R 13 is F or CN; The electron donor has the formula (XXX): 【Transformation 3】 wherein R 51 in each occurrence is independently H or a substituent; R 50 are linked to form a group of formula -Y 1 -C(R 52 ) 2 -, where Y 1 is O, NR 53 , or C(R 52 ) 2 , R 52 in each occurrence is H or a substituent, and R 53 is a substituent. circuit.

2. Each R １３ However, independently, H, C １－１２ 10. The circuit of claim 1, wherein the aryl group is selected from alkyl, and electron-withdrawing groups.

3. 3. The circuit of claim 2, wherein the electron-withdrawing group is F or CN.

4. A light sensor comprising a light source and a circuit according to any one of claims 1 to 3 configured to detect light emitted from the light source.

5. The optical sensor of claim 4 , wherein the light source emits light having a peak wavelength greater than 750 nm.

6. 6. The optical sensor of claim 4 or 5, configured to receive a sample in an optical path between the organic photodetector and the light source.

7. 4. A method for determining the presence and / or concentration of a target material in a sample, the method comprising illuminating the sample and measuring the response of a circuit according to any one of claims 1 to 3 configured to receive light emitted from the sample upon illumination.

8. The method according to claim 7, wherein the circuit is a circuit of an optical sensor according to any one of claims 4 to 6.

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