Compounds and films, photodiodes, organic sensors, and electronic devices including the same

Abstract

Disclosed are compounds and films, photodiodes, organic sensors, and electronic devices including the same. The compounds are represented by Chemical Formula 1. In Chemical Formula 1, Ar 1 and Ar 2 , Z, L 1 , L 2 , and R 1 -R 6 are the same as defined in the detailed description. Chemical Formula 1

Description

[0001] This application claims priority and benefits, and all benefits arising therefrom, to Korean Patent Application No. 10-2019-0139719, filed on November 4, 2019, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0002] Compounds, membranes, photodiodes, organic sensors, and electronic devices have been disclosed. Background Technology

[0003] Imaging devices are used in digital cameras and camcorders to capture images and store the captured images as electrical signals. Imaging devices include image sensors that can separate incident light into individual components defined by individual wavelength spectra and convert each individual component into an electrical signal.

[0004] Recently, there has been increasing interest in photodiodes configured for detecting light in the near-infrared and infrared wavelength spectra in low-light environments or for use in biostatistical devices to improve sensor sensitivity. Summary of the Invention

[0005] Some exemplary embodiments provide compounds that exhibit good light absorption properties in the near-infrared spectrum.

[0006] Some exemplary embodiments provide membranes comprising the compound.

[0007] Some exemplary embodiments provide photodiodes comprising the compound.

[0008] Some exemplary embodiments provide organic sensors that include the compound or the photodiode.

[0009] Some exemplary embodiments provide electronic devices that include the photodiode or the organic sensor.

[0010] According to some exemplary embodiments, compounds represented by chemical formula 1 are provided.

[0011] Chemical Formula 1

[0012]

[0013] In chemical formula 1,

[0014] Ar 1 and Ar 2It may be independently a substituted or unsubstituted benzene (group); a substituted or unsubstituted heterocyclic (group) comprising at least one N, O, S, Se, Te, or a combination thereof; or two or more fused rings (groups) comprising a substituted or unsubstituted benzene (group), a substituted or unsubstituted heterocyclic (group), or a combination thereof; or a combination thereof.

[0015] Z can be N or CR a , where R a It may be a substituted or unsubstituted heterocyclic group including at least one nitrogen atom, a C1-C30 haloalkyl group, a C6-C30 haloaryl group, a halogen, or a cyano group.

[0016] L 1 and L 2 It can be independently a single bond, a substituted or unsubstituted C6-C30 arylene group, a divalent substituted or unsubstituted C3-C30 heterocyclic group, or a combination thereof.

[0017] R 1 It can be a substituted or unsubstituted C3-C30 heterocyclic group or NR b R c , where R b and R c It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof, and R b and R c It can exist independently or R b and R c They can be connected to form a ring.

[0018] R 2 It can be hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted silyl, halogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heterocyclic group, or NR. d R e , where R d and R e It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof, and R d and R e It can exist independently or R d and R eThey can be connected to form a ring.

[0019] R 3 and R 4 It can be independently a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, or a combination thereof, and

[0020] R 5 and R 6 Together they can be oxygen (=O), sulfur (=S), selenium (=Se), or tellurium (=Te), or R. 5 and R 6 It may be independently a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heterocyclic group, a halogen, a cyano, or a combination thereof.

[0021] Ar 1 and Ar 2 It may be independently a substituted or unsubstituted benzene, a substituted or unsubstituted thiophene, a substituted or unsubstituted furan, a substituted or unsubstituted selenophene, a substituted or unsubstituted tellurene, having two or more fused rings of a substituted or unsubstituted benzene, a substituted or unsubstituted thiophene, a substituted or unsubstituted furan, a substituted or unsubstituted selenophene, a substituted or unsubstituted tellurene, or any combination thereof, or a combination thereof.

[0022] Z can be N or CR a , where R a It can be substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted pyrrole, substituted or unsubstituted pyrazolyl, substituted or unsubstituted triazolyl, CH2F, CHF2, CF3, F, or CN.

[0023] L 1 and L 2 It may be a single bond independently; a substituted or unsubstituted phenylene; a substituted or unsubstituted biphenylene; a substituted or unsubstituted naphthylene; a substituted or unsubstituted terphenylene; a divalent substituted or unsubstituted C3-C30 heterocyclic group comprising at least one O, S, Se, Te, N, Si, or a combination thereof; having a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted terphenylene, a divalent substituted or unsubstituted C3-C30 heterocyclic group comprising at least one O, S, Se, Te, N, Si, or a combination thereof, or two or more fused rings of a combination thereof; or a combination thereof.

[0024] R 1 and R 2 It can be independently represented by one of the chemical formulas A-1 to A-4.

[0025]

[0026] In chemical formulas A-1 to A-4,

[0027] W 1 Can be a single bond, O, S, Se, Te, CR f R g or SiR h R i ,

[0028] W 2 Can be O, S, Se, Te, CR j R k or SiR l R m ,

[0029] R 18 -R 25 and R f -R m It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C2-C30 alkenyl, a substituted or unsubstituted C2-C30 alkynyl, a substituted or unsubstituted C1-C30 alkoxy, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted amino, a substituted or unsubstituted silyl, a halogen, or a combination thereof.

[0030] R 18 and R 19 It can exist independently or R 18 and R 19 They can be connected to form a ring.

[0031] R 20 and R 21 It can exist independently or R 20 and R 21 They can be connected to form a ring.

[0032] R 22 and R 23 It can exist independently or R 22 and R 23 They can be connected to form a ring.

[0033] R 24 and R 25 It can exist independently or R 24 and R 25 They can be connected to form a ring.

[0034] R f and R g It can exist independently or R fand R g They can be connected to form a ring.

[0035] R h and R i It can exist independently or R h and R i They can be connected to form a ring.

[0036] R j and R k It can exist independently or R j and R k They can be connected to form a ring.

[0037] R l and R m It can exist independently or R l and R m They can be connected to form a ring, and

[0038] * and * represent bonds with chemical formula 1.

[0039] R 1 and R 2 It can be independently represented by one of the chemical formulas B-1 to B-6.

[0040]

[0041] In chemical formulas B-1 to B-6,

[0042] X 1 -X 35 It can be independently N, O, S, Se, Te, C, CR n or a combination thereof,

[0043] R 26 -R 33 and R n It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C2-C30 alkenyl, a substituted or unsubstituted C2-C30 alkynyl, a substituted or unsubstituted C1-C30 alkoxy, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted amino, a substituted or unsubstituted silyl, a halogen, a bond with Formula 1, or a combination thereof, wherein R 26 -R 33 and R n One of them is the bond with L1 of chemical formula 1, and R 26 -R 33 and R n One of them is the bond with L2 of chemical formula 1.

[0044] R 3 and R4 It may be independently a substituted or unsubstituted phenyl, a substituted or unsubstituted pyrrole, a substituted or unsubstituted thiophene, a substituted or unsubstituted furanyl, a substituted or unsubstituted selenophene, a substituted or unsubstituted tellurene, or a combination of two or more fused rings of a substituted or unsubstituted phenyl, a substituted or unsubstituted pyrrole, a substituted or unsubstituted thiophene, a substituted or unsubstituted furanyl, a substituted or unsubstituted selenophene, a substituted or unsubstituted tellurene, or a combination thereof.

[0045] The compound may be represented by one of the chemical formulas 1a-1 to 1l-1.

[0046] Chemical formula 1a-1

[0047]

[0048] Chemical formula 1b-1

[0049]

[0050] Chemical formula 1c-1

[0051]

[0052] Chemical formula 1d-1

[0053]

[0054] Chemical formula 1e-1

[0055]

[0056] Chemical formula 1f-1

[0057]

[0058] Chemical formula 1g-1

[0059]

[0060] Chemical formula 1h-1

[0061]

[0062] Chemical formula 1i-1

[0063]

[0064] Chemical formula 1j-1

[0065]

[0066] Chemical formula 1k-1

[0067]

[0068] Chemical formula 1l-1

[0069]

[0070] In chemical formulas 1a-1 to 1l-1,

[0071] R b -R e It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof.

[0072] R b and R c It can exist independently or R b and R c They can be connected to form a ring.

[0073] R d and R e It can exist independently or R d and R e They can be connected to form a ring.

[0074] Y 1 -Y 22 It can be N, O, S, Se, Te, or combinations thereof, independently.

[0075] X 1a and X 1b It can be independently N, O, S, Se, Te, or combinations thereof, and

[0076] R 34 -R 67 and R n It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C2-C30 alkenyl, a substituted or unsubstituted C2-C30 alkynyl, a substituted or unsubstituted C1-C30 alkoxy, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted amino, a substituted or unsubstituted silyl, a halogen, or a combination thereof.

[0077] The compound may be represented by one of the chemical formulas 1a-2 to 1l-2.

[0078] Chemical formula 1a-2

[0079]

[0080] Chemical formula 1b-2

[0081]

[0082] Chemical formula 1c-2

[0083]

[0084] Chemical formula 1d-2

[0085]

[0086] Chemical formula 1e-2

[0087]

[0088] Chemical formula 1f-2

[0089]

[0090] Chemical formula 1g-2

[0091]

[0092] Chemical formula 1h-2

[0093]

[0094] Chemical formula 1i-2

[0095]

[0096] Chemical formula 1j-2

[0097]

[0098] Chemical formula 1k-2

[0099]

[0100] Chemical formula 1l-2

[0101]

[0102] In chemical formulas 1a-2 to 1l-2,

[0103] R a It can be a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted triazine, a substituted or unsubstituted pyrrole, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted triazolyl, a C1-C30 haloalkyl, a C6-C30 haloaryl, a halogen, or a cyano, R b -R eIt may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof.

[0104] R b and R c It can exist independently or R b and R c They can be connected to form a ring.

[0105] R d and R e It can exist independently or R d and R e They can be connected to form a ring.

[0106] Y 1 -Y 22 It can be N, O, S, Se, Te, or combinations thereof, independently.

[0107] X 1a and X 1b It can be independently N, O, S, Se, Te, or combinations thereof, and

[0108] R 34 -R 67 and R n It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C2-C30 alkenyl, a substituted or unsubstituted C2-C30 alkynyl, a substituted or unsubstituted C1-C30 alkoxy, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted amino, a substituted or unsubstituted silyl, a halogen, or a combination thereof.

[0109] The peak absorption wavelength of the compound can be in the wavelength spectrum from about 780 nm to about 3000 nm.

[0110] According to some exemplary embodiments, a membrane comprising the compound is provided.

[0111] According to some exemplary embodiments, a photodiode includes: a first electrode and a second electrode facing each other, and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by chemical formula 1.

[0112] The peak absorption wavelength of the organic layer can be in the wavelength spectrum from about 780 nm to about 3000 nm.

[0113] According to some exemplary embodiments, an organic sensor including the photodiode is provided.

[0114] According to some exemplary embodiments, an electronic device including the photodiode or the organic sensor is provided.

[0115] The compounds, which have good light absorption properties in the near-infrared region, can be effectively used in photodiodes and / or organic sensors. Attached Figure Description

[0116] Figure 1 This is a schematic diagram illustrating an example of a pixel array of an organic sensor according to an exemplary embodiment.

[0117] Figure 2 To show a cross-sectional view of an example of a photodiode according to an exemplary embodiment,

[0118] Figure 3 To show a cross-sectional view of an organic sensor according to an exemplary embodiment,

[0119] Figure 4 To show a cross-sectional view of an organic sensor according to an exemplary embodiment,

[0120] Figure 5 To show a cross-sectional view of an organic sensor according to an exemplary embodiment,

[0121] Figure 6 This is a schematic cross-sectional view of an organic sensor according to an exemplary embodiment.

[0122] Figure 7 This is a schematic cross-sectional view of an organic sensor according to an exemplary embodiment.

[0123] Figure 8 To illustrate a schematic cross-sectional view of an organic sensor according to an exemplary embodiment,

[0124] Figure 9 This is a schematic top view of an example of an organic sensor according to some exemplary embodiments.

[0125] Figure 10 for Figure 9 A schematic cross-sectional view of an organic sensor.

[0126] Figure 11 This is a schematic cross-sectional view of an example of an organic sensor according to some exemplary embodiments.

[0127] Figure 12 This is a schematic perspective view of an example of an organic sensor according to some exemplary embodiments.

[0128] Figure 13 According to Figure 12A schematic cross-sectional view of an example of an organic sensor, and

[0129] Figure 14 This is a schematic diagram of an electronic device according to some exemplary embodiments. Detailed Implementation

[0130] Exemplary embodiments will be described in detail below, and they can be readily implemented by those skilled in the art. However, this disclosure may be embodied in many different forms and is not to be construed as limited to the exemplary embodiments set forth herein.

[0131] In the accompanying drawings, the thickness of the magnified layers, films, panels, areas, etc., is shown for clarity.

[0132] It will be understood that when an element, such as a layer, film, region, or substrate, is referred to as being "on" another element, it may be directly on said other element or there may be intermediate elements present. Conversely, when an element is referred to as being "directly on" another element, there are no intermediate elements present.

[0133] It will be understood that although the terms “first,” “second,” “third,” etc., may be used herein to describe various elements, components, regions, layers, and / or parts, these elements, components, regions, layers, and / or parts should not be limited by these terms. These terms are used only to distinguish one element, component, region, layer, or part from another. Therefore, without departing from the teachings herein, the first element, component, region, layer, or part discussed below may be referred to as the second element, component, region, layer, or part.

[0134] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, “a,” “the,” and “at least one” do not indicate a limitation of quantity and are intended to include both the singular and the plural unless the context clearly indicates otherwise. For example, “(a) element” has the same meaning as “at least one element” unless the context clearly indicates otherwise.

[0135] "Or" means "and / or". As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms "comprising" or "including", when used in this specification, indicate the presence of the stated features, areas, integrals, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more additional features, areas, integrals, steps, operations, elements, components, and / or collections thereof.

[0136] Furthermore, relative terms such as “lower” or “bottom” and “upper” or “top” may be used herein to describe the relationship between one element and another element as shown in the figures. It will be understood that, in addition to the orientations shown in the figures, relative terms are also intended to include different orientations of the device. For example, if the device in one of the figures is flipped, an element described as being on the “lower” side of another element will be oriented on the “upper” side of said other element. Therefore, depending on the specific orientation of the figure, the exemplary term “lower” can include both “lower” and “upper” orientations. Similarly, if the device in one of the figures is flipped, an element described as being “below” or “under” other elements will be oriented “above” said other elements. Therefore, the exemplary terms “below” or “under” can include both “above” and “below” orientations.

[0137] As used herein, “about” or “approximately” includes the stated value and means within an acceptable range of deviation from the specific value, as determined by one of ordinary skill in the art taking into account the measurement in question and the errors associated with the measurement of the specific quantity (i.e., limitations of the measurement system). For example, “about” may mean a deviation from the stated value within one or more standard deviations, or within ±10% or 5%.

[0138] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. It will be further understood that terms, such as those defined in common dictionaries, should be interpreted as having the same meaning as they have in the context of this disclosure and the relevant field, and will not be interpreted in an idealized or overly formal sense unless clearly defined herein.

[0139] Exemplary embodiments are described herein with reference to cross-sectional views that serve as schematic representations of idealized embodiments. Thus, deviations from the shapes shown in the figures will be anticipated as a result of, for example, manufacturing techniques and / or tolerances. Therefore, the embodiments described herein should not be construed as limited to the specific shapes of the regions illustrated herein, but rather include deviations in shape caused, for example, by manufacturing processes. For example, regions illustrated or described as flat may typically have rough and / or non-linear characteristics. Furthermore, sharp corners in the figures may be rounded. Therefore, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shapes of the regions nor to limit the scope of the claims.

[0140] In the following text, as used herein, unless otherwise defined, “substituted” means that the hydrogen atoms of a compound or group are replaced by substituents such as: halogen atom, hydroxyl, nitro, cyano, amino, azide, amido, hydrazine, hydrazone, carbonyl, carbamoyl, thiol, ester, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphate or a salt thereof, silyl, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C30 aryl, C7-C30 aralkyl, C1-C30 alkoxy, C1-C20 heteroalkyl, C3-C20 heterocyclic group, C3-C20 heteroaralkyl, C3-C30 cycloalkyl, C3-C15 cycloalkenyl, C6-C15 cycloalkynyl, C3-C30 heterocyclic alkyl, or combinations thereof.

[0141] As used in this article, unless otherwise specifically defined, “mixed” refers to 1-4 of N, O, S, Se, Te, Si, and P.

[0142] As used herein, unless otherwise defined, the term "aromatic ring" refers to a cyclic functional group in which all cyclic atoms have p-orbitals, wherein these p-orbitals are conjugated.

[0143] In the following text, as used herein, unless otherwise defined, “aryl” refers to a group comprising at least one aromatic hydrocarbon moiety. All elements of the aromatic hydrocarbon moiety have conjugated p-orbitals, such as phenyl, naphthyl, etc.; two or more aromatic hydrocarbon moieties may be linked by σ bonds, such as biphenyl, terphenyl, tetraphenyl, etc.; and two or more aromatic hydrocarbon moieties may be directly or indirectly fused to provide a non-aromatic fused ring, such as fluorene. The aryl group may include monocyclic, polycyclic, or fused-ring polycyclic (i.e., rings sharing adjacent carbon pairs) functional groups.

[0144] As used herein, unless otherwise defined, "heterocyclic group" means a group obtained by replacing a carbon atom in an aryl, alicyclic hydrocarbon, or a fused ring thereof with at least one of N, O, S, Se, Te, P, and Si. As used herein, unless otherwise defined, "ring" means an aromatic ring, a non-aromatic ring, a heteroaromatic ring, a heterononaromatic ring, its fused ring, and / or combinations thereof.

[0145] In the following text, as used herein, unless otherwise defined, the term “C1-C30 alkyl” refers to a straight-chain or branched monovalent group of a saturated aliphatic hydrocarbon having 1-30 carbon atoms.

[0146] In the following text, as used herein, unless otherwise defined, the term "C1-C30 alkoxy" refers to the compound formed by -OA 101 (where A) 101Monovalent groups (represented by C1-C30 alkyl groups) are methoxy, ethoxy, propoxy, butoxy, and pentoxy groups.

[0147] In the following text, as used herein, unless otherwise defined, the term “C2-C30 alkenyl” refers to a hydrocarbon group formed by substituting at least one carbon-carbon double bond at the middle or end of a C2-C30 alkyl group, and examples of such groups include vinyl, propenyl, and butenyl.

[0148] In the following text, as used herein, unless otherwise defined, the term “C2-C30 ynyl” refers to a hydrocarbon group formed by substituting at least one carbon-carbon triple bond at the middle or end of a C2-C30 alkyl group, and examples of such groups include ethynyl and propynyl.

[0149] In the following text, as used herein, unless otherwise defined, the term "haloalkyl" refers to an alkyl group in which at least one hydrogen atom is replaced by F, Cl, Br, I, or a combination thereof. Specific examples of haloalkyl groups may be fluoroalkyl groups, such as perfluoroalkyl groups.

[0150] In the following text, as used herein, unless otherwise defined, the term "haloaryl" refers to an aryl group in which at least one hydrogen atom is replaced by F, Cl, Br, I, or a combination thereof. Specific examples of haloaryl groups may be fluoroaryl groups, such as perfluoroaryl groups.

[0151] The compounds according to embodiments are described below.

[0152] The compound according to the embodiments can be represented by chemical formula 1.

[0153] Chemical Formula 1

[0154]

[0155] In chemical formula 1,

[0156] Ar 1 and Ar 2 It may be independently substituted or unsubstituted benzene; substituted or unsubstituted heterocycles comprising at least one N, O, S, Se, Te, or any combination thereof; fused rings having two or more of substituted or unsubstituted benzene, substituted or unsubstituted heterocycles, or combinations thereof; or combinations thereof.

[0157] Z can be N or CR a , where R a It can be an electron-withdrawing group.

[0158] L 1 and L 2It can be independently a single bond, a substituted or unsubstituted C6-C30 arylene group, a divalent substituted or unsubstituted C3-C30 heterocyclic group, or a combination thereof.

[0159] R 1 It can be a substituted or unsubstituted C3-C30 heterocyclic group or NR b R c , where R b and R c It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof, and R b and R c It can exist independently or R b and R c They can be connected to form a ring.

[0160] R 2 It can be hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted silyl, halogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heterocyclic group, or NR. d R e , where R d and R e It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof, and R d and R e It can exist independently or R d and R e They can be connected to form a ring.

[0161] R 3 and R 4 It can be independently a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, or a combination thereof, and

[0162] R 5 and R 6 Together they can be oxygen (=O), sulfur (=S), selenium (=Se), or tellurium (=Te), or R. 5 and R 6It may be independently a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heterocyclic group, a halogen, a cyano, or a combination thereof.

[0163] The compound has a structure in which two pyrrole atoms form a complex with disubstituted boron atoms. By combining the core and / or substituents with the electron-donating moieties, the compound can be configured to absorb light in the near-infrared wavelength spectrum and can exhibit good electrical properties.

[0164] The peak absorption wavelength (λ) of the compound 最大 It can be, for example, greater than or equal to about 700 nm, such as greater than or equal to about 720 nm, greater than or equal to about 730 nm, greater than or equal to about 750 nm, greater than or equal to about 780 nm, greater than or equal to about 790 nm, greater than or equal to about 800 nm, greater than or equal to about 810 nm, greater than or equal to about 820 nm, greater than or equal to about 830 nm, greater than or equal to about 840 nm, greater than or equal to about 850 nm, greater than or equal to about 870 nm, greater than or equal to about 890 nm, greater than or equal to about 900 nm, or greater than or equal to about 910 nm. The peak absorption wavelength of the compound may be, for example, in the wavelength spectrum of about 700 nm to about 3000 nm, or, within the range of about 750 nm to about 2500 nm, about 780 nm to about 2200 nm, about 790 nm to about 2100 nm, about 800 nm to about 2000 nm, about 810 nm to about 2000 nm, about 820 nm to about 2000 nm, about 830 nm to about 2000 nm, about 850 nm to about 1900 nm, about 870 nm to about 1800 nm, about 900 nm to about 1600 nm, or about 910 nm to about 1500 nm.

[0165] For example, Ar 1 and Ar 2 It may be independently a substituted or unsubstituted benzene, a substituted or unsubstituted thiophene, a substituted or unsubstituted furan, a substituted or unsubstituted selenophene, a substituted or unsubstituted tellurene, having two or more fused rings of a substituted or unsubstituted benzene, a substituted or unsubstituted thiophene, a substituted or unsubstituted furan, a substituted or unsubstituted selenophene, a substituted or unsubstituted tellurene, or a combination thereof, or a combination thereof.

[0166] For example, Ar 1 and Ar 2It may independently be substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted thiophene, substituted or unsubstituted benzothiophene, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted furan, substituted or unsubstituted benzofuran, substituted or unsubstituted dibenzofuran, substituted or unsubstituted selenophene, substituted or unsubstituted benzoselenophene, substituted or unsubstituted dibenzoselenophene, substituted or unsubstituted tellurophene, substituted or unsubstituted benzotellurophene, substituted or unsubstituted dibenzotellurophene, or combinations thereof.

[0167] For example, Ar 1 and Ar 2 They can be the same.

[0168] For example, Ar 1 and Ar 2 They can be different.

[0169] For example, Z can be nitrogen (N) or an electron-withdrawing group (R). a The electron-withdrawing group is a substituted carbon, wherein the electron-withdrawing group may be, for example, a substituted or unsubstituted heterocyclic group comprising at least one nitrogen atom; a C1-C30 haloalkyl group; a C6-C30 haloaryl group; a halogen; a cyano group; or a combination thereof. For example, the electron-withdrawing group (R) a It can be substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted pyrrole, substituted or unsubstituted pyrazolyl, substituted or unsubstituted triazolyl, CH2F, CHF2, CF3, F, or CN.

[0170] For example, L 1 and L 2 It can be a single bond independently; a substituted or unsubstituted phenylene; a substituted or unsubstituted biphenylene; a substituted or unsubstituted naphthylene; a substituted or unsubstituted terphenylene; a divalent substituted or unsubstituted C3-C30 heterocyclic group comprising at least one O, S, Se, Te, N, Si, or a combination thereof; having a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted terphenylene, a divalent substituted or unsubstituted C3-C30 heterocyclic group comprising at least one O, S, Se, Te, N, Si, or a combination thereof, or two or more fused rings of a combination thereof; or combinations thereof. For example, L 1 and L 2It can independently be a single bond, substituted or unsubstituted p-phenylene, substituted or unsubstituted m-phenylene, substituted or unsubstituted o-phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted terphenylene, substituted or unsubstituted thiopheneylene, substituted or unsubstituted benzothiopheneylene, substituted or unsubstituted dibenzothiopheneylene, substituted or unsubstituted furanylene, substituted or unsubstituted benzofuran. The group consisting of substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted selenidephenyl, substituted or unsubstituted benzoselenophenyl, substituted or unsubstituted dibenzoselenophenyl, substituted or unsubstituted telluridephenyl, substituted or unsubstituted benzotelluridephenyl, substituted or unsubstituted dibenzotelluridephenyl, substituted or unsubstituted pyrroleyl, substituted or unsubstituted benzopyrroleyl, substituted or unsubstituted dibenzopyrroleyl, or combinations thereof.

[0171] For example, L 1 and L 2 They can be the same.

[0172] For example, L 1 and L 2 They can be different.

[0173] For example, R 1 and R 2 It can be the same or different substituted or unsubstituted amino groups and can be represented, for example, independently by one of the chemical formulas A-1 to A-4.

[0174]

[0175]

[0176] In chemical formulas A-1 to A-4,

[0177] W 1 For single bonds, O, S, Se, Te, CR f R g or SiR h R i ,

[0178] W 2 For O, S, Se, Te, CR j R k or SiR l R m ,

[0179] R 18 -R 25 and R f -R mIndependently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof.

[0180] R 18 and R 19 It can exist independently or R 18 and R 19 They can be connected to form a ring.

[0181] R 20 and R 21 It can exist independently or R 20 and R 21 They can be connected to form a ring.

[0182] R 22 and R 23 It can exist independently or R 22 and R 23 They can be connected to form a ring.

[0183] R 24 and R 25 It can exist independently or R 24 and R 25 They can be connected to form a ring.

[0184] R f and R g It can exist independently or R f and R g They can be connected to form a ring.

[0185] R h and R i It can exist independently or R h and R i They can be connected to form a ring.

[0186] R j and R k It can exist independently or R j and R k They can be connected to form a ring.

[0187] R l and R m It can exist independently or R l and R m They can be connected to form a ring, and

[0188] * and * represent bonds with chemical formula 1.

[0189] For example, in Equation 1, R 1 and R 2 It can be the same or different substituted or unsubstituted heterocyclic groups and can be represented, for example, independently by one of the chemical formulas B-1 to B-6.

[0190]

[0191] In chemical formulas B-1 to B-6,

[0192] X 1 -X 35 It can be independently N, O, S, Se, Te, C, or CR n or combinations thereof, and

[0193] R 26 -R 33 and R n It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C2-C30 alkenyl, a substituted or unsubstituted C2-C30 alkynyl, a substituted or unsubstituted C1-C30 alkoxy, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted amino, a substituted or unsubstituted silyl, a halogen, a bond with Formula 1, or a combination thereof, wherein R 26 -R 33 and R n One of them is the bond with L1 of chemical formula 1, and R 26 -R 33 and R n One of them is the bond with L2 of chemical formula 1.

[0194] For example, X 1 and X 2 It can be O, S, Se, or Te independently.

[0195] For example, X 1 and X 2 It can be either O or S independently.

[0196] For example, X 3 X 6 X 11 X 18 X 23 X 26 and X 33 It can be independently O, S, Se, Te, C, or CR n .

[0197] For example, X 3 X 6 X 11 X18 X 23 X 26 and X 33 It can be independently O, S, or CR n .

[0198] For example, X 4 X 5 X 7 -X 10 X 12 -X 17 X 19 -X 22 X 24 X 25 X 27 -X 32 X 34 and X 35 It can be N or CR independently. n .

[0199] For example, R in Equation 1 1 and R 2 It can be a group derived from one of the compounds in Group 1, but is not limited to this:

[0200] Group 1

[0201]

[0202] In Group 1, R1 is connected to Formula 1 via a single bond between a carbon atom of the compound in Group 1 and L1, and R2 of Group 1 is connected to Formula 1 via a single bond between a carbon atom of the compound in Group 1 and L2.

[0203] For example, in Equation 1, R 3 and R 4 It can be independently a substituted or unsubstituted C6-C30 aryl group; a substituted or unsubstituted heterocyclic group comprising at least one N, O, S, Se, Te, or a combination thereof; or a combination thereof. For example, R 3 and R 4 It may independently be a substituted or unsubstituted phenyl, a substituted or unsubstituted pyrrole, a substituted or unsubstituted thiophene, a substituted or unsubstituted furanyl, a substituted or unsubstituted selenophene, a substituted or unsubstituted tellurene, a fused ring having two or more of the following: a substituted or unsubstituted phenyl, a substituted or unsubstituted pyrrole, a substituted or unsubstituted thiophene, a substituted or unsubstituted furanyl, a substituted or unsubstituted selenophene, a substituted or unsubstituted tellurene, or a combination thereof, and combinations thereof, and for example R 3 and R 4It may independently be a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted thiophene, a substituted or unsubstituted benzothiophene, a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted furanyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted selenophene, a substituted or unsubstituted benzoselenophene, a substituted or unsubstituted dibenzoselenophene, a substituted or unsubstituted tellurophene, a substituted or unsubstituted benzotellurophene, a substituted or unsubstituted dibenzotellurophene, a substituted or unsubstituted pyrrole, a substituted or unsubstituted benzopyrrole, a substituted or unsubstituted dibenzopyrrole, or a combination thereof. Here, “substitution” can mean that at least one hydrogen atom is replaced, for example, by a C1-C20 alkyl group, a C1-C20 haloalkyl group, a C1-C20 alkoxy group, a C6-C30 aryl group, or a C3-C30 heterocyclic group, or a combination thereof, but is not limited thereto.

[0204] For example, R 3 and R 4 They can be the same.

[0205] For example, R 3 and R 4 They can be different.

[0206] For example, R 5 and R 6 It can be independently halogenated or C1-C20 haloalkyl, and R 5 and R 6 It can be, for example, fluorine.

[0207] For example, R 5 and R 6 They can be the same.

[0208] For example, R 5 and R 6 They can be different.

[0209] For example, Z can be N.

[0210] Compounds of Formula 1 may be represented by one of the chemical formulas 1a-1 to 1l-1.

[0211] Chemical formula 1a-1

[0212]

[0213] Chemical formula 1b-1

[0214]

[0215] Chemical formula 1c-1

[0216]

[0217] Chemical formula 1d-1

[0218]

[0219] Chemical formula 1e-1

[0220]

[0221] Chemical formula 1f-1

[0222]

[0223] Chemical formula 1g-1

[0224]

[0225] Chemical formula 1h-1

[0226]

[0227] Chemical formula 1i-1

[0228]

[0229] Chemical formula 1j-1

[0230]

[0231] Chemical formula 1k-1

[0232]

[0233] Chemical formula 1l-1

[0234]

[0235] In chemical formulas 1a-1 to 1l-1,

[0236] R b -R e It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof.

[0237] R b and R c It can exist independently or R b and R c They can be connected to form a ring.

[0238] R d and R e It can exist independently or R d and Re They can be connected to form a ring.

[0239] Y 1 -Y 22 It can be N, O, S, Se, Te, or combinations thereof, independently.

[0240] X 1a and X 1b It can be independently N, O, S, Se, or Te, and

[0241] R 34 -R 67 and R n It may independently be hydrogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C2-C30 alkenyl, a substituted or unsubstituted C2-C30 alkynyl, a substituted or unsubstituted C1-C30 alkoxy, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heterocyclic group, a substituted or unsubstituted amino, a substituted or unsubstituted silyl, a halogen, or a combination thereof.

[0242] For example, Z can be CR a .

[0243] Compounds of Formula 1 can be represented by one of the chemical formulas 1a-2 to 1l-2.

[0244]

[0245]

[0246] Chemical formula 1b-2

[0247]

[0248] Chemical formula 1c-2

[0249]

[0250] Chemical formula 1d-2

[0251]

[0252] Chemical formula 1e-2

[0253]

[0254] Chemical formula 1f-2

[0255]

[0256] Chemical formula 1g-2

[0257]

[0258] Chemical formula 1h-2

[0259]

[0260] Chemical formula 1i-2

[0261]

[0262] Chemical formula 1j-2

[0263]

[0264] Chemical formula 1k-2

[0265]

[0266] Chemical formula 1l-2

[0267]

[0268] In chemical formulas 1a-2 to 1l-2,

[0269] R a It can be a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted triazine, a substituted or unsubstituted pyrrole, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted triazolyl, a C1-C30 haloalkyl, a C6-C30 haloaryl, a halogen, or a cyano, R b -R e Y 1 -Y 22 X 1a and X 1b R 34 -R 67 and R n It can be the same as described above.

[0270] For example, a compound of Formula 1 may be one of the compounds of Group 2, but is not limited thereto.

[0271] Group 2

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280] The compound may be a light-absorbing material, for example, a light-absorbing material configured to absorb light in the near-infrared wavelength spectrum. For example, the peak absorption wavelength of the compound may be greater than or equal to about 700 nm, greater than or equal to about 720 nm, greater than or equal to about 730 nm, greater than or equal to about 750 nm, greater than or equal to about 780 nm, greater than or equal to about 790 nm, greater than or equal to about 800 nm, greater than or equal to about 810 nm, greater than or equal to about 820 nm, greater than or equal to about 830 nm, greater than or equal to about 840 nm, greater than or equal to about 850 nm, greater than or equal to about 870 nm, greater than or equal to about 890 nm, greater than or equal to about 900 nm, or greater than or equal to about 910 nm. The peak absorption wavelength of the compound may be in, for example, a wavelength spectrum of about 700 nm to about 3000 nm, or within the range of about 750 nm to about 2500 nm, about 780 nm to about 2200 nm, about 790 nm to about 2100 nm, about 800 nm to about 2000 nm, about 810 nm to about 2000 nm, about 820 nm to about 2000 nm, about 830 nm to about 2000 nm, about 850 nm to about 1900 nm, about 870 nm to about 1800 nm, about 900 nm to about 1600 nm, or about 910 nm to about 1500 nm.

[0281] The compound exhibits good charge transport (transfer) properties and therefore has good photoelectric conversion properties for absorbing light and converting light into electrical signals, making the compound effective as a photoelectric conversion material for photodiodes.

[0282] The compound exhibits good heat resistance, which prevents or reduces thermal decomposition during deposition, and therefore allows for repeated deposition. The compound can be deposited thermally or under vacuum and can be deposited, for example, by sublimation. For example, deposition by sublimation can be confirmed by thermogravimetric analysis (TGA), and at a pressure less than or equal to about 10 Pa, the temperature at which a 10% weight loss relative to the initial weight occurs is less than or equal to about 450°C, and the temperature at which a 50% weight loss relative to the initial weight occurs is less than or equal to about 500°C. For example, at a pressure less than or equal to about 10 Pa, the temperature at which a 10% weight loss relative to the initial weight occurs is, for example, about 230°C to about 450°C, and the temperature at which a 50% weight loss relative to the initial weight occurs is about 300°C to about 500°C.

[0283] The compound can be manufactured in the form of a membrane.

[0284] The membrane can be applied to a variety of fields where absorption characteristics in the near-infrared wavelength range are required, and can be used as, for example, a near-infrared absorbing / blocking membrane.

[0285] Since the compound possesses both light absorption and photoelectric conversion properties in the near-infrared wavelength spectrum, it can be effectively used as a photoelectric conversion material.

[0286] In the following description, examples of the application of the compound of Formula 1 in photodiodes and organic sensors are illustrated with reference to the accompanying drawings.

[0287] Figure 1 This is a schematic diagram illustrating an example of a pixel array of an organic sensor according to some exemplary embodiments.

[0288] Reference Figure 1 The organic sensor 200 may include a plurality of pixels PX, and the plurality of pixels PX may have a matrix arrangement that is repeatedly arranged along rows and / or columns. The plurality of pixels PX may include, for example, a unit pixel group A, such as a 2×2 pixel array. However, the arrangement of the pixels is not limited to this and can be varied, and the unit pixel group A may be, for example, various pixel arrays such as a 3×3 pixel array and a 4×4 pixel array.

[0289] Figure 2 A cross-sectional view showing an example of a photodiode according to some exemplary embodiments.

[0290] Reference Figure 2 According to some exemplary embodiments, a photodiode 100 includes a first electrode 10 and a second electrode 20 facing each other, and an organic layer 30 between the first electrode 10 and the second electrode 20.

[0291] A substrate (not shown) may be disposed on the side of the first electrode 10 or the second electrode 20. The substrate may be made, for example, of: inorganic materials such as glass; organic materials such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone, or combinations thereof; or a silicon wafer. The substrate may be omitted.

[0292] One of the first electrode 10 and the second electrode 20 is an anode and the other is a cathode. For example, the first electrode 10 may be an anode and the second electrode 20 may be a cathode.

[0293] At least one of the first electrode 10 and the second electrode 20 may be a light-transmitting electrode, and the light-transmitting electrode may be made, for example, of a conductive oxide such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), and fluorine-doped tin oxide (FTO), or a single or multiple metal thin layer. When one of the first electrode 10 and the second electrode 20 is a non-light-transmitting electrode, the non-light-transmitting electrode may be made of, for example, an opaque conductor such as aluminum (Al), silver (Ag), or gold (Au). For example, both the first electrode 10 and the second electrode 20 may be light-transmitting electrodes. For example, the second electrode 20 may be a light-receiving electrode disposed on the light-receiving side.

[0294] The organic layer 30 may include an active layer.

[0295] The active layer is a layer comprising p-type semiconductors and n-type semiconductors to provide a pn junction, which generates excitons by receiving light from the outside and then separates holes and electrons from the generated excitons.

[0296] The p-type semiconductor and the n-type semiconductor can be independently configured as light-absorbing materials for absorbing light in at least a portion of the wavelength spectrum, and the compound of Formula 1 can be either a p-type semiconductor or an n-type semiconductor. For example, the compound of Formula 1 can be used as a p-type semiconductor and fullerenes or fullerene derivatives can be included as n-type semiconductors, but are not limited thereto.

[0297] The active layer may include an intrinsic layer (I layer) in which the aforementioned p-type semiconductor and an n-type semiconductor, including a fullerene derivative, are co-deposited. Here, the volume ratio of the p-type semiconductor and the n-type semiconductor may be about 1:9 to about 9:1, for example, about 2:8 to about 8:2, about 3:7 to about 7:3, about 4:6 to about 6:4, or about 5:5.

[0298] In addition to the intrinsic layer, the active layer may further include a p-type layer and / or an n-type layer. The p-type layer may include the aforementioned p-type semiconductor, and the n-type layer may include the aforementioned n-type semiconductor. For example, it may include various combinations of p-type layer / I-layer, I-layer / n-type layer, p-type layer / I-layer / n-type layer, etc.

[0299] The organic layer 30 comprises a compound of formula 1 and is therefore effectively configured to absorb light in the near-infrared wavelength spectrum and perform photoelectric conversion. For example, the peak absorption wavelength of the organic layer 30 may be greater than or equal to about 700 nm, greater than or equal to about 720 nm, greater than or equal to about 730 nm, greater than or equal to about 750 nm, greater than or equal to about 780 nm, greater than or equal to about 790 nm, greater than or equal to about 800 nm, greater than or equal to about 810 nm, greater than or equal to about 820 nm, greater than or equal to about 830 nm, greater than or equal to about 840 nm, greater than or equal to about 850 nm, greater than or equal to about 870 nm, greater than or equal to about 890 nm, greater than or equal to about 900 nm, or greater than or equal to about 910 nm. The peak absorption wavelength of the organic layer 30 may be, for example, in the wavelength spectrum of about 700 nm to about 3000 nm, or in the range of about 750 nm to about 2500 nm, about 780 nm to about 2200 nm, about 790 nm to about 2100 nm, about 800 nm to about 2000 nm, about 810 nm to about 2000 nm, about 820 nm to about 2000 nm, about 830 nm to about 2000 nm, about 850 nm to about 1900 nm, about 870 nm to about 1800 nm, about 900 nm to about 1600 nm, or about 910 nm to about 1500 nm.

[0300] The organic layer 30 may further include a charge-assisted layer (not shown) between the first electrode 10 and the active layer and / or between the second electrode 20 and the active layer. The charge-assisted layer allows holes and electrons separated in the active layer 30 to be easily transported to improve efficiency.

[0301] The charge-assisted layer may include at least one selected from: a hole injection layer (HIL) for promoting hole injection, a hole transport layer (HTL) for promoting hole transport, an electron blocking layer (EBL) for preventing electron transport, an electron injection layer (EIL) for promoting electron injection, an electron transport layer (ETL) for promoting electron transport, and a hole blocking layer (HBL) for preventing hole transport.

[0302] The charge-assisted layer may include, for example, organic materials, inorganic materials, or organic-inorganic materials. The organic material may be an organic material with hole or electron correlation properties, and the inorganic material may be, for example, a metal oxide such as molybdenum oxide, tungsten oxide, or nickel oxide.

[0303] The charge-assisted layer may include, for example, a compound of Formula 1.

[0304] The photodiode 100 may further include an anti-reflective layer (not shown) on the first electrode 10 or the second electrode 20. The anti-reflective layer may be disposed on the light incident side and reduce light reflection of the incident light, thereby further improving light absorption. For example, when light enters through the first electrode 10, the anti-reflective layer may be disposed on the first electrode 10, while when light enters through the second electrode 20, the anti-reflective layer may be disposed below the second electrode 20.

[0305] The antireflective layer may include, for example, a material having a refractive index of about 1.6 to about 2.5 and may include at least one of, for example, metal oxides, metal sulfides, and organic materials having a refractive index within the said range. The antireflective layer may include, for example, metal oxides such as oxides containing aluminum, oxides containing molybdenum, oxides containing tungsten, oxides containing vanadium, oxides containing rhenium, oxides containing niobium, oxides containing tantalum, oxides containing titanium, oxides containing nickel, oxides containing copper, oxides containing cobalt, oxides containing manganese, oxides containing chromium, oxides containing tellurium, or combinations thereof; metal sulfides such as zinc sulfide; or organic materials such as amine derivatives, but are not limited thereto.

[0306] In the photodiode 100, when light enters through the first electrode 10 or the second electrode 20 and the organic layer 30 is configured to absorb light in a predetermined wavelength spectrum, excitons can be generated within it. In the organic layer 30, the excitons can be separated into holes and electrons, and the separated holes can be transported to the anode, which is one of the first electrode 10 and the second electrode 20, while the separated electrons can be transported to the cathode, which is the other of the first electrode 10 and the second electrode 20, to allow current to flow.

[0307] The photodiode 100 can be used in solar cells, image sensors, photodetectors, or photoelectric sensors, but is not limited thereto.

[0308] The photodiode can be used, for example, in an organic sensor. The organic sensor can be an organic CMOS sensor, such as an organic CMOS infrared sensor or an organic CMOS image sensor.

[0309] Figure 3 This is a cross-sectional view of an organic sensor according to an exemplary embodiment.

[0310] The organic sensor 300 according to this embodiment includes a semiconductor substrate 110, an insulating layer 80, and a photodiode 100.

[0311] The semiconductor substrate 110 may be a silicon substrate and integrates a transfer transistor (not shown) and a charge memory 55. The charge memory 55 may be integrated in each pixel. The charge memory 55 is electrically connected to the photodiode 100, which will be described later, and the information in the charge memory 55 can be transmitted through the transfer transistor.

[0312] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110. To reduce signal delay, the metal lines and pads may be made of metals with low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto. Furthermore, the structure is not limited to the above, and the metal lines and pads may be disposed beneath the semiconductor substrate 110.

[0313] An insulating layer 80 is formed on the metal lines and pads. The insulating layer 80 may be made of inorganic insulating materials such as silicon oxide and / or silicon nitride, or low dielectric constant (low K) materials such as SiC, SiCOH, SiCO, and SiOF. The insulating layer 80 has trenches 85 that expose the charge storage device 55.

[0314] Groove 85 can be filled with packing material.

[0315] The aforementioned photodiode 100 is formed on the insulating layer 80. As described above, the photodiode 100 includes a first electrode 10, an organic layer 30, and a second electrode 20. Although the figure shows a structure in which the first electrode 10, the organic layer 30, and the second electrode 20 are stacked sequentially as an example, this disclosure is not limited to this structure, and the second electrode 20, the organic layer 30, and the first electrode 10 can be arranged in this order.

[0316] The first electrode 10 and the second electrode 20 may both be transparent electrodes, and the organic layer 30 is the same as described above. The organic layer 30 can selectively absorb light in the near-infrared wavelength spectrum. In the organic layer 30, incident light from the second electrode 20 side can be photoelectrically converted by mainly absorbing light in the near-infrared wavelength spectrum.

[0317] A focusing lens (not shown) may be further formed on the photodiode 100. The focusing lens can control the direction of the incident light and converge the light into a region. The focusing lens may have, for example, a cylindrical or hemispherical shape, but is not limited thereto.

[0318] The organic sensor according to this embodiment can be an organic infrared light sensor, such as an iris sensor or a depth sensor.

[0319] The iris sensor identifies a person by: taking an image of the user's eyes at an appropriate distance, specifically using each person's unique iris characteristics, processing the image, and comparing it with his / her stored images.

[0320] The depth sensor identifies the shape and position of an object from its three-dimensional information by capturing an image of the object at an appropriate distance from the user and processing the image. This depth sensor can be used, for example, as a facial recognition sensor.

[0321] Figure 4 A cross-sectional view showing another example of an organic sensor according to an exemplary embodiment.

[0322] The organic sensor according to this embodiment may include multiple sensors with different functions. For example, at least one of the multiple sensors with different functions may be a biostatistical sensor, and the biostatistical sensor may be, for example, an iris sensor, a depth sensor, a fingerprint sensor, a vascular distribution sensor, etc., but is not limited thereto. For example, one of the multiple sensors with different functions may be an iris sensor and another may be a depth sensor.

[0323] For example, multiple sensors may include, for example, a first infrared light sensor configured to sense light in a near-infrared region having a first wavelength (λ1) in the infrared wavelength spectrum and a second infrared light sensor configured to sense light in a near-infrared region having a second wavelength (λ2) in the infrared wavelength spectrum.

[0324] In a wavelength spectrum from about 750 nm to about 3000 nm, the first wavelength (λ1) and the second wavelength (λ2) may be, for example, different, and the difference between the first wavelength (λ1) and the second wavelength (λ2) may be greater than or equal to about 30 nm, greater than or equal to about 50 nm, greater than or equal to about 70 nm, greater than or equal to about 80 nm, or greater than or equal to about 90 nm.

[0325] For example, one of the first wavelength (λ1) and the second wavelength (λ2) may belong to the wavelength spectrum from about 780 nm to about 900 nm, and the other of the first wavelength (λ1) and the second wavelength (λ2) may belong to the wavelength spectrum from about 830 nm to about 1000 nm.

[0326] For example, one of the first wavelength (λ1) and the second wavelength (λ2) may belong to the wavelength spectrum from about 780 nm to about 840 nm, and the other of the first wavelength (λ1) and the second wavelength (λ2) may belong to the wavelength spectrum from about 910 nm to about 970 nm.

[0327] For example, one of the first wavelength (λ1) and the second wavelength (λ2) may belong to the wavelength spectrum of about 800 nm to about 830 nm, and the other of the first wavelength (λ1) and the second wavelength (λ2) may belong to the wavelength spectrum of about 930 nm to about 950 nm.

[0328] For example, one of the first wavelength (λ1) and the second wavelength (λ2) may belong to the wavelength spectrum from about 805 nm to about 815 nm, and the other of the first wavelength (λ1) and the second wavelength (λ2) may belong to the wavelength spectrum from about 935 nm to about 945 nm.

[0329] For example, one of the first wavelength (λ1) and the second wavelength (λ2) may be about 810 nm and the other of the first wavelength (λ1) and the second wavelength (λ2) may be about 940 nm.

[0330] The organic sensor 400 according to this embodiment includes a dual-bandpass filter 40, a first infrared light sensor 100A, an insulating layer 80, and a semiconductor substrate 110 on which a second infrared light sensor 120 is integrated. The first infrared light sensor 100A and the second infrared light sensor 120 can be stacked.

[0331] A dual-bandpass filter 40 may be disposed on the front side of the organic sensor 400 and may selectively transmit infrared light including the first wavelength (λ1) and infrared light including the second wavelength (λ2) while blocking and / or absorbing other light. Here, other light may include light in the ultraviolet (UV) and visible regions.

[0332] The first infrared light sensor 100A may be a photodiode 100 according to the foregoing embodiment, and its details are omitted.

[0333] The second infrared light sensor 120 may be integrated in the semiconductor substrate 110 and may be a light sensing device. The semiconductor substrate 110 may be, for example, a silicon substrate and may integrate the second infrared light sensor 120, a charge memory 55, and a transfer transistor (not shown).

[0334] The second infrared light sensor 120 may be a photodiode and can sense incoming light, and the sensed information is transmitted through the transmission transistor. Here, the light entering the second infrared light sensor 120 is light that has passed through the dual-bandpass filter 40 and the first infrared light sensor 100A, and may be infrared light in a predetermined region including the second wavelength (λ2). All infrared light in the predetermined region including the first wavelength (λ1) may be absorbed by the organic layer 30 and may not reach the second infrared light sensor 120. In this case, a separate filter for wavelength selectivity of the light entering the second infrared light sensor 120 is not required. However, when not all infrared light in the predetermined region including the first wavelength (λ1) is absorbed by the organic layer 30, a filter may be further provided between the first infrared light sensor 100A and the second infrared light sensor 120.

[0335] The organic sensor according to this embodiment may include two infrared light sensors that perform functions independently and thus can operate as a combined sensor. Furthermore, the two independently functioning sensors are stacked within each pixel, thus doubling the number of pixels performing the functions of each sensor while maintaining the size, resulting in a significant improvement in sensitivity.

[0336] Figure 5 A cross-sectional view showing another example of an organic sensor according to some exemplary embodiments.

[0337] The organic sensor according to this embodiment can be an organic CMOS image sensor.

[0338] Reference Figure 5 The organic sensor 500 according to the embodiment includes a semiconductor substrate 110 integrating photosensitive devices 50a, 50b and 50c, a transfer transistor (not shown) and a charge memory 55, a lower insulating layer 60, color filter layers 70a, 70b and 70c, an upper insulating layer 80, and a photodiode 100.

[0339] The semiconductor substrate 110 may integrate photosensing devices 50a, 50b, and 50c, a transfer transistor (not shown), and a charge storage device 55. The photosensing devices 50a, 50b, and 50c may be photodiodes.

[0340] Light sensing devices 50a, 50b, and 50c, the transmission transistor, and / or charge memory 55 may be integrated into each pixel. For example, light sensing device 50a may be included in the red pixel, light sensing device 50b may be included in the green pixel, and light sensing device 50c may be included in the blue pixel.

[0341] Light sensing devices 50a, 50b and 50c sense light, and the information sensed by the light sensing devices can be transmitted through the transmission transistor. Charge memory 55 is electrically connected to photodiode 100, which will be described later, and the information in charge memory 55 can be transmitted through the transmission transistor.

[0342] Metal lines (not shown) and pads (not shown) are formed on the semiconductor substrate 110. To reduce signal delay, the metal lines and pads may be made of metals with low resistivity, such as aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto. However, the structure is not limited to this, and the metal lines and pads may be disposed below the photosensitive devices 50a, 50b, and 50c.

[0343] A lower insulating layer 60 is formed on the metal wire and the pad.

[0344] Color filters 70a, 70b, and 70c are formed on the lower insulating layer 60. Color filters 70a, 70b, and 70c include a red filter 70a formed in a red pixel, a green filter 70b formed in a green pixel, and a blue filter 70c formed in a blue pixel.

[0345] An upper insulating layer 80 is formed on color filters 70a, 70b and 70c. The upper insulating layer 80 eliminates the steps caused by color filters 70a, 70b and 70c and flattens the surface.

[0346] A photodiode 100 is formed on the upper insulating layer 80. As described above, the photodiode 100 includes a first electrode 10, an organic layer 30, and a second electrode 20. Although the figure shows a structure in which the first electrode 10, the organic layer 30, and the second electrode 20 are stacked sequentially as an example, this disclosure is not limited to this structure, and the second electrode 20, the organic layer 30, and the first electrode 10 can be arranged in this order.

[0347] The first electrode 10 and the second electrode 20 may both be transparent electrodes, and the organic layer 30 is the same as described above. The organic layer 30 may be configured to selectively absorb light in the near-infrared wavelength spectrum.

[0348] Incident light from the second electrode 20 side can be photoelectrically converted as follows: light in the near-infrared wavelength spectrum is mainly absorbed in the organic layer 30. Light in the remaining wavelength spectrum can pass through the first electrode 10 and color filters 70a, 70b and 70c. Light in the red wavelength spectrum passing through color filter 70a can be sensed by photosensitive device 50a, light in the green wavelength spectrum passing through color filter 70b can be sensed by photosensitive device 50b, and light in the blue wavelength spectrum passing through color filter 70c can be sensed by photosensitive device 50c.

[0349] Figure 6 This is a schematic cross-sectional view of another example of an organic sensor according to some exemplary embodiments.

[0350] Reference Figure 6 The organic sensor 600 according to an embodiment includes a semiconductor substrate 110 comprising photosensing devices 50a, 50b, and 50c, a transfer transistor (not shown), and a charge storage device 55; a lower insulating layer 60; a color filter layer 70 including color filters 70a, 70b, and 70c; and a photodiode 100. (See also...) Figure 6 The photodiode 100 can be disposed between the semiconductor substrate 110 and the color filter layer 70, such that the color filter layer 70 is located away from the photosensitive devices 50a, 50b, and 50c relative to the photodiode 100. Other constituent elements and Figure 5 It is the same as the organic sensor.

[0351] For example, color filter layer 70 may further include a color mixing filter configured to transmit the wavelength spectrum of light for mixing colors. For example, in Figure 6 In this configuration, color filter 70a can be configured to selectively filter light in the magenta wavelength spectrum, color filter 70b can be configured to selectively filter light in the cyan wavelength spectrum, and color filter 70c can be configured to selectively filter light in the yellow wavelength spectrum.

[0352] Figure 7 This is a schematic cross-sectional view of another example of an organic sensor according to some exemplary embodiments.

[0353] Reference Figure 7 The organic image sensor 700 according to the embodiment includes a semiconductor substrate 110 comprising light sensing devices 50a, 50b and 50c, a transfer transistor (not shown) and a charge memory 55; a lower insulating layer 60; a color filter layer 70 including color filters 70a, 70b and 70c; an upper insulating layer 80; and a photodiode 100 beneath the semiconductor substrate 110.

[0354] like Figure 7 As shown, the photodiode 100 is disposed beneath the semiconductor substrate 110, and the color filter layer 70 is thus located away from the photosensitive devices 50a, 50b, and 50c relative to the photodiode 100. Other constituent elements and Figure 5 It is the same as the organic sensor.

[0355] Figure 8 A schematic cross-sectional view is shown to illustrate an organic sensor according to some exemplary embodiments.

[0356] Reference Figure 8An organic sensor 800 according to an embodiment includes a semiconductor substrate 110 comprising photosensing devices 50a, 50b, and 50c, a transfer transistor (not shown), and a charge memory 55; an insulating layer 60 having trenches 85; and a photodiode 100. In the organic sensor 800, the photosensing devices 50a, 50b, and 50c are stacked vertically, and the color filter layer 70 is omitted. The photosensing devices 50a, 50b, and 50c are electrically connected to the charge memory (not shown), and their information can be transmitted via the transfer transistor. The photosensing devices 50a, 50b, and 50c can selectively absorb light in various wavelengths of the light spectrum depending on the stacking depth. Other constituent elements are... Figure 5 It is the same as the organic sensor.

[0357] Figure 9 A schematic top view of an example of an organic sensor according to some exemplary embodiments and Figure 10 for Figure 9 A schematic cross-sectional view of an organic sensor.

[0358] Reference Figure 9 and 10 The organic sensor 900 according to an embodiment includes a near-infrared photodiode configured to selectively absorb light in the near-infrared wavelength spectrum, a red photodiode configured to selectively absorb light in the red wavelength spectrum and convert it into an electrical signal, a green photodiode configured to selectively absorb light in the green wavelength spectrum and convert it into an electrical signal, and a blue photodiode configured to selectively absorb light in the blue wavelength spectrum and convert it into an electrical signal. The near-infrared photodiode, red photodiode, green photodiode, and blue photodiode are arranged in parallel (side-by-side) in a horizontal direction.

[0359] Reference Figure 10 The organic sensor 900 according to an embodiment includes a photodiode 100 comprising a plurality of photodiodes 100a, 100b, 100c, and 100d on a semiconductor substrate 110. The plurality of photodiodes 100a, 100b, 100c, and 100d are configured to absorb light in one wavelength spectrum of the red, blue, green, and near-infrared wavelength spectra, respectively, and convert it into an electrical signal.

[0360] Reference Figure 10The organic sensor 900 according to an embodiment includes a semiconductor substrate 110 integrating photosensing devices 55a to 55d and a transmission transistor (not shown); a lower insulating layer 60; and photodiodes 100a to 100d. The photodiodes 100a to 100d are disposed in parallel on the semiconductor substrate 110 and partially overlap each other. Each of the photodiodes 100a to 100d overlaps each other in a parallel direction on a surface 110a of the semiconductor substrate 110. Each of the photodiodes 100a to 100d can be electrically connected via a trench 85 to a charge storage device 55 integrated into the semiconductor substrate 110. One of the photodiodes 100a to 100d can be the aforementioned photodiode 100. For example, the photodiodes 100a to 100d can share the same common electrode as the second electrode 20. Other constituent elements and... Figure 5 It is the same as the organic sensor.

[0361] Figure 11 This is a schematic cross-sectional view of an example of an organic sensor according to some exemplary embodiments.

[0362] Reference Figure 11 The organic sensor 1100 according to an embodiment includes a semiconductor substrate 110 integrating a charge memory and a transfer transistor (not shown); a lower insulating layer 60; a first photodiode 1190; a second photodiode 1190a; a third photodiode 1190b; and a fourth photodiode 1190c. The first photodiode 1190 may be a photodiode that absorbs light in the near-infrared wavelength spectrum and may be formed on the second to fourth photodiodes 1190a to 1190c. The first photodiode 1190 may be the aforementioned photodiode 100. The second to fourth photodiodes 1190a to 1190c may be configured to selectively absorb light in different wavelength spectra of the blue, red, and green wavelength spectra. For example, the second to fourth photodiodes 1190a to 1190c may share a common electrode 1120 and may each include a separate pixel electrode 1110 and separate photoelectric conversion layers 1130a, 1130b, and 1130c. Other constituent elements are... Figure 5 It is the same as the organic sensor.

[0363] Reference Figure 11 The first photodiode 1190 is stacked on the second to fourth photoelectric elements 1190a to 1190c, and the second to fourth photoelectric elements 1190a to 1190c overlap each other in a direction perpendicular to the surface of the semiconductor substrate 110. The second to fourth photodiodes 1190a to 1190c may partially overlap in a direction parallel to the surface of the semiconductor substrate 110.

[0364] Figure 12This is a schematic perspective view of an example of an organic sensor according to some exemplary embodiments, and Figure 13 According to Figure 12 A schematic cross-sectional view of an example of an organic sensor.

[0365] Reference Figure 12 The organic sensor 1200 according to the embodiment includes a photodiode configured to selectively absorb light in the near-infrared wavelength spectrum, a photodiode configured to selectively absorb and electro-convert light in the red wavelength spectrum, a photodiode configured to selectively absorb and electro-convert light in the green wavelength spectrum, and a photodiode configured to selectively absorb and electro-convert light in the blue wavelength spectrum.

[0366] Reference Figure 13 The organic sensor 1200 according to an embodiment includes a semiconductor substrate 110 integrating charge memories 55a to 55d and a transmission transistor; a lower insulating layer 80a; intermediate insulating layers 80b and 80c; an upper insulating layer 80d; a first photodiode 1200a; a second photodiode 1200b; a third photodiode 1200c; and a fourth photodiode 1200d. The first to fourth photodiodes 1200a to 1200d are vertically stacked on the semiconductor substrate 110.

[0367] A first photodiode 1200a includes a first electrode 10a and a second electrode 20a facing each other, and a photoelectric conversion layer 30a disposed between the first electrode 10a and the second electrode 20a. A second photodiode 1200b includes a first electrode 10b and a second electrode 20b facing each other, and a photoelectric conversion layer 30b disposed between the first electrode 10b and the second electrode 20b. A third photodiode 1200c includes a first electrode 10c and a second electrode 20c facing each other, and a photoelectric conversion layer 30c disposed between the first electrode 10c and the second electrode 20c. A fourth photodiode 1200d includes a first electrode 10d and a second electrode 20d facing each other, and a photoelectric conversion layer 30d disposed between the first electrode 10d and the second electrode 20d. The photoelectric conversion layers 30a, 30b, 30c, and 30d can selectively absorb light in one wavelength spectrum of the red, green, blue, and near-infrared wavelength spectra, respectively, and can perform photoelectric conversion on the light. One of the photoelectric conversion layers 30a, 30b, 30c, and 30d may be the aforementioned organic layer 30. The first electrodes 10a, 10b, 10c, and 10d, and the second electrodes 20a, 20b, 20c, and 20d are the same as the first electrode 10 and the second electrode 20 described above.

[0368] A focusing lens 1300 may be further formed on the fourth photodiode 1200d. The focusing lens 1300 can control the direction of the incident light and converge the light into a region. The focusing lens 1300 may have, for example, a cylindrical or hemispherical shape, but is not limited thereto.

[0369] In the figure, the first to fourth photodiodes 1200a to 1200d are stacked sequentially, but this disclosure is not limited thereto, and they can be stacked in various orders.

[0370] Figure 14 This is a schematic diagram of an electronic device according to some exemplary embodiments.

[0371] Reference Figure 14 The electronic device 1400 may include a processor 1420, a memory 1430, and an organic sensor 1440 electrically coupled (combined) together via a bus 1410. The organic sensor 1440 may be any of the organic sensors described in the foregoing embodiments.

[0372] The memory 1430, which may be a non-transitory computer-readable medium, may store a program of instructions. The processor 1420 may execute the program of stored instructions to perform one or more functions. For example, the processor 1420 may be configured to process electrical signals generated by the organic sensor 1440. The processor 1420 may be configured to generate output (e.g., an image to be displayed on a display interface) based on, for example, processing.

[0373] The organic sensor can be applied to, for example, a variety of electronic devices, which may include, for example, cameras, video cameras, mobile phones having them internally, display devices, security devices, or medical devices, but are not limited thereto.

[0374] The embodiments are described in more detail below with reference to examples. However, these embodiments are exemplary and the scope is not limited thereto.

[0375] Simulation evaluation of light absorption properties

[0376] The light absorption properties of the compound were evaluated using the Gaussian09 program. The optimized structure was obtained by using the DGDZVP basis set to represent the wavefunction and by B3LYP hybrid density functional calculation. The structure was then used for B3LYP hybrid density functional or ωB97X-D range separated density functional time-correlated DFT (density functional theory) calculations, and the absorption wavelength was obtained (by calculating the energy difference between the singlet excited state and the ground state).

[0377] The results are shown in Table 1.

[0378] Table 1

[0379]

[0380]

[0381] Synthesis Examples

[0382] Synthesis Example 1: Synthesis of Compound 35

[0383] Reaction Scheme 1

[0384]

[0385] Synthesis of intermediate I-11

[0386] 1 g of 4H-thieno[3,2-b]pyrrole-5-carboxylic acid was dissolved in 50 mL of ethanol. 10 mL of 0.1 N HCl was added, and the mixture was refluxed and stirred at 100 °C for 24 hours and then cooled to room temperature. When the reaction was complete, the ethanol was evaporated under reduced pressure, and 200 mL of ethyl acetate was added for dilution. The organic layer was washed with saturated NaHCO3 aqueous solution (50 mL × 2) and saturated NaCl aqueous solution (50 mL × 2), dried over MgSO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / hexane = 1:5 v / v) to obtain 0.8 g of intermediate I-11. The yield was 69%.

[0387] The prepared compound was confirmed by LC-MS.

[0388] LC-MS m / z = 196.24(M+H)+

[0389] Synthesis of intermediate I-12

[0390] 1 g of ethyl 4H-thieno[3,2-b]pyrrole-5-carboxylate (intermediate I-11) was dissolved in 50 mL of dichloromethane. 0.2 g of bromine was slowly added dropwise, followed by stirring at room temperature for 24 hours. When the reaction was complete, the organic layer was diluted with 100 mL of dichloromethane, washed with two 50 mL solutions of NaHCO3 and two 50 mL solutions of saturated NaCl, dried over MgSO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / hexane = 1:5 v / v) to obtain 1.7 g of intermediate I-12. The yield was 94%.

[0391] The compound was identified using LC-MS.

[0392] LC-MS m / z = 354.03(M+H)+

[0393] Synthesis of intermediate I-13

[0394] 2.3 g (6.94 mmol) of ethyl 2,6-dibromo-4H-thieno[3,2-b]pyrrole-5-carboxylate (intermediate I-12) and 1.5 g (7.64 mmol) of (4-(dimethylamino)phenyl)boronic acid were placed in a flask, and 150 mL of a tetrahydrofuran / distilled water (4:1 volume ratio) mixture was added under a nitrogen stream. Then, 0.4 g (0.35 mmol) of tetrakis(triphenylphosphine)palladium(O) and 2.21 g (20.83 mmol) of potassium carbonate were added sequentially, and the mixture was stirred at 110 °C for 24 hours. When the reaction was complete, after cooling to room temperature, 500 mL of ethyl acetate was added for dilution. The organic layer was washed with saturated aqueous NaHCO3 solution (150 mL × 2) and saturated NaCl solution (100 mL × 2), dried over MgSO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / hexane = 1:3 v / v) to obtain 2.3 g of intermediate I-13. The yield was 89%.

[0395] The compound was identified using LC-MS.

[0396] LC-MS m / z = 394.30(M+H)+

[0397] Synthesis of intermediate I-14

[0398] 5.3 g (7.64 mmol) of ethyl 6-bromo-2-(4-(dimethylamino)phenyl)-4H-thieno[3,2-b]pyrrole-5-carboxylate (intermediate I-13) and 1.5 g (6.94 mmol) of (4-(trifluoromethyl)phenyl)boronic acid were placed in a flask, and 150 mL of a toluene / ethanol / water mixture (3:1:1, v / v) was added under a nitrogen stream. Subsequently, 0.4 g (0.35 mmol) of tetrakis(triphenylphosphine)palladium(O) and 2.21 g (20.83 mmol) of potassium carbonate were added sequentially, and the mixture was stirred at 120 °C for 24 h. When the reaction was complete, after cooling to room temperature, 500 mL of ethyl acetate was added for dilution. The organic layer was washed with saturated aqueous NaHCO3 solution (150 mL × 2) and saturated NaCl solution (100 mL × 2), dried over MgSO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / hexane = 1:3 v / v) to obtain 2.3 g of intermediate I-14. The yield was 37%.

[0399] The manufactured compound was confirmed by LC-MS.

[0400] LC-MS m / z = 459.50(M+H)+

[0401] Synthesis of intermediate I-15

[0402] 1.0 g (2.18 mmol) of ethyl 4-(dimethylamino)phenyl)-6-(4-(trifluoromethyl)phenyl)-4H-thieno[3,2-b]pyrrole-5-carboxylate (intermediate I-14) was added to 10 mL of ethylene glycol and stirred at room temperature. 6.1 g (108.73 mmol) of potassium hydroxide was added and the mixture was stirred at 130 °C for 24 hours. When the reaction was complete, after cooling to room temperature, 500 mL of ethyl acetate was added for dilution. The organic layer was washed with saturated aqueous NaHCO3 solution (150 mL × 2) and saturated aqueous NaCl solution (100 mL × 2), dried over MgSO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / hexane = 1:3 v / v) to obtain 0.5 g of intermediate I-15. The yield was 59%.

[0403] The manufactured compound was confirmed by LC-MS.

[0404] LC-MS m / z = 387.11(M+H)+

[0405] Synthesis of intermediate I-16

[0406] 0.80 g (2.07 mmol) of N,N-dimethyl-4-(6-(4-(trifluoromethyl)phenyl)-4H-thieno[3,2-b]pyrrolo-2-yl)aniline (intermediate I-15) was added to a 2.0 mL / 1.0 mL mixture of acetic acid and acetic anhydride. After cooling to 0 °C, 1.60 g (2.31 mmol) of sodium nitrite (NaNO2) was added and the mixture was stirred for 15 minutes. Subsequently, another 0.80 g (2.07 mmol) of N,N-dimethyl-4-(6-(4-(trifluoromethyl)phenyl)-4H-thieno[3,2-b]pyrrolo-2-yl)aniline (intermediate I-15) was added. The reaction solution was then heated to 80 °C and stirred for 3 hours. After cooling to room temperature, the resulting solid was filtered and washed with n-hexane to obtain 0.70 g of intermediate I-16. Its yield is 43%.

[0407] The manufactured compound was confirmed by LC-MS.

[0408] LC-MS m / z = 784.19(M+H)+

[0409] Synthesis of Compound 35

[0410] Under a nitrogen atmosphere, 0.70 g (0.89 mmol) of (Z)-2-(4-(dimethylamino)phenyl)-N-(2-(4-(dimethylamino)phenyl)-6-(4-(trifluoromethyl)phenyl)-5H-thieno[3,2-b]pyrrolo-5-yl-diene)-6-(4-(trifluoromethyl)phenyl)-4H-thieno[3,2-b]pyrrolo-5-amine (intermediate I-16) was placed in a flask and dissolved in 3.0 mL of toluene, and 1.0 mL of triethylamine was added. 0.3 mL of boron trifluoride diethyl ether complex was slowly added dropwise, and the mixture was stirred at 80 °C for 3 hours. When the reaction was complete, the precipitate was collected after cooling to room temperature and washed with ethanol. The residue was purified by column chromatography (dichloromethanol / hexane = 1:3 v / v) to obtain 0.2 g of compound 35. Its yield is 27%.

[0411] The compound was identified using LC-MS.

[0412] LC-MS m / z = 832.19(M+H)+

[0413] Synthesis Example 2: Synthesis of Compound 99

[0414] Reaction Scheme 2

[0415]

[0416] Synthesis of intermediate I-21

[0417] Intermediate I-21 was obtained according to the aforementioned method for synthesizing intermediate I-12.

[0418] Synthesis of intermediate I-22

[0419] 1.0 g (2.83 mmol) of ethyl 2,6-dibromo-4H-thieno[3,2-b]pyrrole-5-carboxylic acid (intermediate I-21) was dissolved in 50 mL of toluene and then placed in an ice bath to lower the temperature. 3.0 mL of tributyl(thieno-2-yl)stanane was slowly added dropwise, and the resulting mixture was heated to room temperature and, after 30 minutes, refluxed and stirred at 120 °C for 24 hours. When the reaction was complete, after lowering the temperature to room temperature, 500 mL of ethyl acetate was added for dilution. The organic layer was washed with saturated aqueous NaHCO3 solution (150 mL × 2) and saturated aqueous NaCl solution (100 mL × 2), dried over MgSO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / hexane = 1:3 v / v) to obtain 0.5 g of intermediate I-22. The yield was 49%.

[0420] The compound was identified using LC-MS.

[0421] LC-MS m / z = 360.49(M+H)+

[0422] Synthesis of intermediate I-23

[0423] 1.0 g (2.78 mmol) of ethyl 2,6-bis(thiophen-2-yl)-4H-thiopheno[3,2-b]pyrrole-5-carboxylic acid (intermediate I-22) was placed in 30 mL of ethylene glycol and stirred at room temperature. 7.8 g (139.0 mmol) of potassium hydroxide was added, and the mixture was stirred at 130 °C for 24 hours. When the reaction was complete, after cooling to room temperature, 500 mL of ethyl acetate was added for dilution. The organic layer was washed with saturated aqueous NaHCO3 solution (150 mL × 2) and saturated NaCl solution (100 mL × 2), dried over MgSO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / hexane = 1:3 v / v) to obtain 0.4 g of intermediate I-23. The yield was 50%.

[0424] The manufactured compound was confirmed by LC-MS.

[0425] LC-MS m / z = 287.99(M+H)

[0426] Synthesis of intermediate I-24

[0427] 0.5 g (1.74 mmol) of 2,6-bis(thiophen-2-yl)-4H-thieno[3,2-b]pyrrole (intermediate I-23) was added to a 2.0 mL / 1.0 mL mixture of acetic acid and acetic anhydride. Then, after lowering the temperature to 0 °C, 1.32 g (1.91 mmol) of sodium nitrite (NaNO2) was added and the mixture was stirred for 15 minutes. 0.5 g (1.74 mmol) of 2,6-bis(thiophen-2-yl)-4H-thieno[3,2-b]pyrrole (intermediate I-23) was added. The reaction solution was then heated to 80 °C and stirred for 3 hours. The reaction solution was cooled to room temperature, and the resulting solid was filtered and washed with ethanol to obtain 0.45 g of intermediate I-24. The yield was 44%.

[0428] The manufactured compound was confirmed by LC-MS.

[0429] LC-MS m / z = 585.98(M+H)+

[0430] Synthesis of Compound 99

[0431] 0.4 g (0.7 mmol) of (Z)-N-(2,6-bis(thiophen-2-yl)-5H-thieno[3,2-b]pyrrolo-5-yl-diene)-2,6-bis(thiophen-2-yl)-4H-thiophenno[3,2-b]pyrrolo-5-amine (intermediate I-24) was placed in a flask under a nitrogen atmosphere and dissolved in 3.0 mL of toluene, and 1.0 mL of triethylamine was added. 0.2 mL of boron trifluoride diethyl ether complex was slowly added dropwise, and the mixture was stirred at 80 °C for 3 hours. When the reaction was complete, the precipitate was collected after cooling to room temperature, washed with ethanol, and the residue was purified by column chromatography (dichloromethanol / hexane = 1:3 v / v) to obtain 0.1 g of compound 99. The yield was 23%.

[0432] The manufactured compound was confirmed by LC-MS.

[0433] LC-MS m / z = 634.63(M+H)+

[0434] Evaluation I

[0435] The compounds from the synthesis examples were respectively used at 1×10 -5 The concentration of M was dissolved in dichloromethane to prepare a solution for evaluating the light absorption properties of the compound.

[0436] The peak absorption wavelength (λ) was measured using a Shimadzu UV-3600Plus UV-Vis-NIR (UV-Vis-NIR) spectrometer. 最大 To evaluate the light absorption properties.

[0437] The results are shown in Table 2.

[0438] Table 2

[0439] <![CDATA[λ 最大 (nm)]]> Synthesis Example 1 963 Synthesis Example 2 819

[0440] Referring to Table 2, the absorption spectra of the compounds in the synthesis examples are shown as the peak absorption wavelengths in the near-infrared wavelength spectrum.

[0441] Evaluation II

[0442] The deposition characteristics of the compounds from the synthetic examples were evaluated.

[0443] The deposition characteristics are evaluated by sublimating the compound under a high vacuum of 10 Pa or lower and measuring the weight loss of the compound depending on the temperature rise using thermogravimetric analysis.

[0444] The results are shown in Table 3.

[0445] Table 3

[0446] <![CDATA[T s (°C)(-10 wt%) <![CDATA[T s (°C)(-50 wt%) Synthesis Example 1 220℃ 280℃ Synthesis Example 2 200℃ 260℃

[0447] *T s (°C)(-10 wt%): The temperature at which the sample loses 10 wt% of its weight.

[0448] *T s (°C)(-50 wt%): The temperature at which the sample loses 50 wt% of its weight.

[0449] Referring to Table 3, the compounds in the synthetic examples exhibit satisfactory heat resistance and are formed into thin films through repeated thermal deposition.

[0450] Although this disclosure has been described with respect to exemplary embodiments which are now considered practical, it will be understood that the invention is not limited to the disclosed embodiments. Rather, it is intended to cover various variations and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. Compounds represented by chemical formula 1: Chemical Formula 1 in, In chemical formula 1, Ar 1 and Ar 2 Independently, it refers to substituted or unsubstituted thiophene, substituted or unsubstituted furan, substituted or unsubstituted selenophene, or substituted or unsubstituted tellurene, wherein "substituted" means that the hydrogen of the group is replaced by the following substituents: C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, or C1-C30 alkoxy. Z is N, L 1 and L 2 Independently, it is a substituted or unsubstituted C6-C30 arylene group, where "substituted" means that the hydrogen atoms of the group are replaced by substituents such as: C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, or C1-C30 alkoxy. R 1 For NR b R c , where R b and R c Independently, it is an unsubstituted C1-C30 alkyl group. R 2 For NR d R e , where R d and R e Independently, it is an unsubstituted C1-C30 alkyl group. R 3 and R 4 Independently, it is a substituted or unsubstituted C6-C30 aryl group, where "substituted" refers to the hydrogen atoms of the group being replaced by substituents such as halogen atoms, cyano, C1-C20 alkyl, C1-C20 haloalkyl, C2-C20 alkenyl, C2-C20 alkynyl, or C1-C30 alkoxy, and R 5 and R 6 It can be halogen or cyano group independently.

2. The compound of claim 1, wherein L 1 and L 2 Independently, it is a substituted or unsubstituted phenylene; a substituted or unsubstituted biphenylene; a substituted or unsubstituted naphthylene; a substituted or unsubstituted terphenylene; or a combination thereof.

3. The compound of claim 1, wherein R 3 and R 4 It can be a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group, on its own.

4. A compound represented by the chemical formula 1c-1: Chemical formula 1c-1 in, In chemical formula 1c-1, R b -R e Independently, it is an unsubstituted C1-C30 alkyl group. Y 3 and Y 4 Independently O, S, Se, or Te, and R 42 -R 45 Independently, it is hydrogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C2-C30 alkenyl, a substituted or unsubstituted C2-C30 alkynyl, a substituted or unsubstituted C1-C30 alkoxy, or a halogen. "Substituted" refers to the replacement of hydrogen atoms in a group by halogen atoms or cyano groups.

5. A membrane, comprising the compound as described in any one of claims 1-4.

6. Photodiode, including: The first and second electrodes facing each other, and An organic layer between the first electrode and the second electrode The organic layer thereof comprises the compound as described in any one of claims 1-4.

7. An organic sensor, comprising the photodiode as described in claim 6.

8. An electronic device, including the organic sensor of claim 7 or the photodiode of claim 6.

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