Compounds, films, photodiodes, organic sensors, and electronic devices

Abstract

Disclosed are compounds, films, photodiodes, organic sensors, and electronic devices, wherein the compounds are represented by Chemical Formula 1. In Chemical Formula 1, X 1 , X 2 , Y 1 , Y 2 ,Ar,L 1 , L 2 , R 1 , R 4 , and n are the same as those defined in the specification. [Chemical Formula 1]

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2018-0127734, filed on October 24, 2018, and Korean Patent Application No. 10-2019-0128862, filed on October 17, 2019, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Compounds, films, photodiodes, organic sensors, and electronic devices are disclosed. Background Art

[0004] Imaging devices are used in digital cameras, camcorders, etc. to capture images and store the captured images as electrical signals, and the imaging devices include image sensors that can separate incident light into separate components defined by separate wavelength spectra and convert each separate component into electrical signals.

[0005] Recently, photodiodes configured to detect light in the near infrared and infrared wavelength spectrum have been investigated to improve the sensitivity of sensors in low light environments or for use in biometric devices. Summary of the invention

[0006] Some example embodiments provide compounds that are chemically tuned to exhibit good light absorption characteristics over a selected wavelength spectrum, such as the near infrared spectrum.

[0007] Some example embodiments provide films including the compounds.

[0008] Some example embodiments provide a photodiode including the compound.

[0009] Some example embodiments provide an organic sensor including the compound or the photodiode.

[0010] Some example embodiments provide an electronic device including the photodiode or the organic sensor.

[0011] According to some example embodiments, a compound represented by Chemical Formula 1 is provided.

[0012] [Chemical formula 1]

[0013]

[0014] in,

[0015] X 1 and X 2 are independently O, S, Se, or Te,

[0016] Y 1 and Y 2 are independently O, S, Se, Te, or C(CN) 2 ,

[0017] Ar is a substituted or unsubstituted C6-C30 aromatic ring, a substituted or unsubstituted C3-C30 heteroaromatic ring, or a combination thereof,

[0018] L 1 and L 2 are independently substituted or unsubstituted C3-C20 heteroarylene,

[0019] R 1 For-NR 2 R 3 , where R 2 and R 3 are independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted silyl, halogen, or a combination thereof, wherein R 2 and R 3 may exist independently or be connected to each other to form a ring,

[0020] R 4 is hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof, and

[0021] n is 0 or 1.

[0022] Ar may be substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted tetracene, substituted or unsubstituted pyrene, substituted or unsubstituted thiophene, substituted or unsubstituted furan, substituted or unsubstituted selenophene, substituted or unsubstituted tellurophene, or a condensed ring of two or more of these.

[0023] L 1 and L 2 Each may independently be a heteroarylene group including O, S, Se, Te, N, Si, or a combination thereof.

[0024] L 1 and L 2 Each independently may include at least one of the groups listed in Group 1 which may be substituted or unsubstituted.

[0025] [Group 1]

[0026]

[0027] in,

[0028] Z 1 and Z 2 O, S, Se, Te, NR a , or SiR b R c ,

[0029] Z 3 -Z 6 N or CR independently d ,

[0030] Z 3 -Z 6 At least one of them is N,

[0031] Where R a -R d are independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof, wherein R b and R c may exist independently or be linked to each other to form a ring, and

[0032] * indicates the connection point.

[0033] R 1 It may be represented by one of Chemical Formulae A-1 to A-3.

[0034]

[0035] W 1 Single bond, O, S, Se, NR e , CR f R g , or SiR h R i ,

[0036] W 2 O, S, Se, NR e , CR f R g or SiR h R i ,

[0037] R 20 -R 25and R e -R i are independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof,

[0038] R 20 and R 21 may exist independently or be connected to each other to form a ring,

[0039] R 22 and R 23 may exist independently or be connected to each other to form a ring,

[0040] R 24 and R 25 may exist independently or be connected to each other to form a ring,

[0041] R f and R g may exist independently or be connected to each other to form a ring,

[0042] R h and R i may exist independently or be connected to each other to form a ring,

[0043] In Chemical Formula A-1, Chemical Formula A-2, or Chemical Formula A-3, at least one hydrogen in the ring structure may be replaced by 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 C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof, and

[0044] * indicates the connection point.

[0045] R 4 Can be obtained by -NR 5 R 6 Indicates that R 5 and R 6 may be each independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted silyl, halogen, or a combination thereof, wherein R 5 and R 6 They may exist independently of each other or be linked to each other to form a ring.

[0046] R4 It may be represented by one of Chemical Formulas B-1 to B-3.

[0047]

[0048] In Chemical Formulas B-1 to B-3,

[0049] W 3 Single bond, O, S, Se, NR j , CR k R l or SiR m R n ,

[0050] W 4 O, S, Se, NR j , CR k R l or SiR m R n ,

[0051] R 26 -R 31 and R j -R n are independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof,

[0052] R 26 and R 27 may exist independently or be connected to each other to form a ring,

[0053] R 28 and R 29 may exist independently or be connected to each other to form a ring,

[0054] R 30 and R 31 may exist independently or be connected to each other to form a ring,

[0055] R k and R l may exist independently or be connected to each other to form a ring,

[0056] R m and R n may exist independently or be connected to each other to form a ring,

[0057] In Chemical Formula B-1, Chemical Formula B-2, or Chemical Formula B-3, at least one hydrogen in the ring structure may be replaced by 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 C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof, and

[0058] * indicates the connection point.

[0059] The compound may be represented by one of Chemical Formulas 1-J to 1-Z2.

[0060]

[0061]

[0062] In chemical formulae 1-J to 1-Z2,

[0063] X 1 and X 2 are independently O, S, Se, or Te,

[0064] Y 1 and Y 2 are independently O, S, Se, Te, or C(CN) 2 ,

[0065] Ar is a substituted or unsubstituted C6-C30 aromatic ring, a substituted or unsubstituted C3-C30 heteroaromatic ring, or a combination thereof,

[0066] Z 1 and Z 2 O, S, Se, Te, NR a , or SiR b R c ,

[0067] W 1 Single bond, O, S, Se, NR e , CR f R g , or SiR h R i ,

[0068] W 2 O, S, Se, NR e , CR f R g , or SiR h R i ,

[0069] W 3 Single bond, O, S, Se, NRj , CR k R l , or SiR m R n ,

[0070] W 4 O, S, Se, NR j , CR k R l , or SiR m R n ,

[0071] R 20 -R 31 and R a -R n are independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof,

[0072] R b and R c may exist independently or be connected to each other to form a ring,

[0073] R f and R g may exist independently or be connected to each other to form a ring,

[0074] R h and R i may exist independently or be connected to each other to form a ring,

[0075] R k and R l may exist independently or be connected to each other to form a ring,

[0076] R m and R n may exist independently or be linked to each other to form a ring, and

[0077] m1 and m2 are independently integers of 1-5.

[0078] The peak absorption wavelength of the compound may be within a wavelength spectrum of about 700 nm to about 3000 nm.

[0079] According to another embodiment, a film including the compound is provided.

[0080] According to some example 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 includes the compound represented by Chemical Formula 1.

[0081] According to some example embodiments, there is provided an organic sensor including the photodiode.

[0082] According to some example embodiments, there is provided an electronic device including the photodiode or the organic sensor.

[0083] The compound may have good light absorption characteristics in the near-infrared wavelength spectrum and thus may be effectively used in photodiodes and / or organic sensors. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] Figure 1 is a schematic diagram showing an example of a pixel array of a sensor according to some example embodiments.

[0085] Figure 2 To show a cross-sectional view of a photodiode according to some example embodiments,

[0086] Figure 3 To show a cross-sectional view of an organic sensor according to some example embodiments,

[0087] Figure 4 To show a cross-sectional view of an organic sensor according to some example embodiments,

[0088] Figure 5 To show a cross-sectional view of an organic sensor according to some example embodiments,

[0089] Figure 6 is a schematic cross-sectional view of an organic sensor according to some example embodiments,

[0090] Figure 7 is a schematic cross-sectional view of an organic sensor according to some example embodiments,

[0091] Figure 8 To show a cross-sectional view of an organic sensor according to some example embodiments,

[0092] Fig. 9 is a perspective view of an organic sensor according to some example embodiments,

[0093] Fig.10 To illustrate some example embodiments Fig. 9 Schematic cross-sectional view of an organic sensor,

[0094] Fig.11is a schematic cross-sectional view of an organic sensor according to some example embodiments,

[0095] Fig.12 is a perspective view of an organic sensor according to some example embodiments,

[0096] Fig.13 To illustrate some example embodiments Fig.12 Schematic cross-sectional view of an organic sensor,

[0097] Fig.14 is a schematic diagram of an electronic device according to some example embodiments, and

[0098] Fig.15 is a graph showing the photoelectric conversion efficiency of the photodiode according to the embodiment. DETAILED DESCRIPTION

[0099] Example implementations will be described in detail below and can be easily performed by persons having ordinary knowledge in the relevant field. However, the structure of actual applications may be embodied in many different forms and is not to be construed as limited to the exemplary implementations set forth herein.

[0100] In the drawings, the thickness of layers, films, panels, etc. are not drawn to scale and are exaggerated for clarity.

[0101] When the term "about" or "substantially" is used in this specification with respect to a numerical value, it is intended that the relevant numerical value includes a deviation of ±10% around the stated numerical value. When a range is stated, the range includes all values ​​therebetween, for example in increments of 0.1%.

[0102] It will be understood that when an element such as a layer, film, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0103] As used herein, when no definition is otherwise provided, "substituted" means that a hydrogen of a compound or group is replaced by a substituent selected from the group consisting of a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a silyl group, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C30 aryl group, a C7-C30 aralkyl group, a C1-C30 alkoxy group, a C1-C20 heteroalkyl group, a C3-C20 heteroaryl group, a C3-C20 heteroaralkyl group, a C3-C30 cycloalkyl group, a C3-C15 cycloalkenyl group, a C6-C15 cycloalkynyl group, a C3-C30 heterocycloalkyl group, and combinations thereof.

[0104] As used herein, when no definition is otherwise provided, “hetero” means including 1 to 4 heteroatoms selected from N, O, S, Se, Te, Si, and P.

[0105] As used herein, when no definition is otherwise provided, "aromatic ring" refers to a functional group in which all atoms in the cyclic functional group have p-orbitals, wherein the p-orbitals are conjugated. In some example embodiments, the aromatic ring may be a C6-C30 aryl group or a C2-C30 heteroaryl group.

[0106] As used herein, when no definition is provided in addition, "aryl" refers to a group comprising at least one aromatic hydrocarbon portion. All elements of the aromatic hydrocarbon portion have a p-orbital forming a conjugation, such as phenyl, naphthyl, etc., two or more aromatic hydrocarbon portions may be connected by a σ bond and may be, for example, biphenyl, terphenyl, quaterphenyl, etc., and two or more aromatic hydrocarbon portions may be fused directly or indirectly to provide a non-aromatic fused ring such as fluorenyl. The aryl may include a monocyclic, polycyclic or fused polycyclic (i.e., a ring sharing adjacent carbon atom pairs) functional group.

[0107] As used herein, when no definition is otherwise provided, "heteroaryl" includes at least one heteroatom selected from N, O, S, Se, Te, P, and Si in the ring instead of carbon (C). When the heteroaryl is a condensed ring, at least one of the rings constituting the heteroaryl may have a heteroatom, for example, each ring may have a heteroatom.

[0108] As used herein, when no definition is provided in addition, "ring" refers to an aromatic ring, a non-aromatic ring, a heteroaromatic ring, a heteronon-aromatic ring, a condensed ring, and / or a combination thereof. The aromatic ring may be a C6-C30 aryl or a C2-C30 heteroaryl, and the non-aromatic ring may be a C3-C30 cycloalkyl, a C3-C30 cycloalkenyl, a C3-C30 cycloalkynyl, a C3-C30 heterocycloalkyl, a C3-C30 heterocycloalkenyl, or a C3-C30 heterocycloalkynyl.

[0109] Hereinafter, compounds according to embodiments are described.

[0110] The compound according to the embodiment may be represented by Chemical Formula 1.

[0111] [Chemical formula 1]

[0112]

[0113] In Chemical Formula 1,

[0114] X 1 and X 2 are each independently O, S, Se or Te,

[0115] Y 1 and Y 2 Each independently is O, S, Se, Te or C(CN) 2 ,

[0116] Ar is a substituted or unsubstituted C6-C30 aromatic ring, a substituted or unsubstituted C3-C30 heteroaromatic ring, or a combination thereof,

[0117] L 1 and L 2 are each independently a substituted or unsubstituted C3-C20 heteroarylene group,

[0118] R 1 For-NR 2 R 3 , where R 2 and R 3 are each independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted silyl, halogen, or a combination thereof, wherein R 2 and R 3 Each exists independently or is connected to each other to form a ring,

[0119] R 4 is hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof, and

[0120] n is 0 or 1.

[0121] By combining a substituted or unsubstituted amine group having electron donating properties with a core of a conjugated structure having electron accepting properties via a heteroarylene group as a linker, the compound can have good electrical properties as well as light absorption properties configured to efficiently absorb light in the near-infrared wavelength spectrum.

[0122] The peak absorption wavelength (λ 最大 ) may be, for example, greater than or equal to about 700 nm. The peak absorption wavelength of the compound may be, for example, within a wavelength spectrum of about 700 nm to about 3000 nm.

[0123] In some example embodiments, X 1 and X 2 Can be the same.

[0124] In some example embodiments, X 1and X 2 Can be different from each other.

[0125] In some example embodiments, X 1 and X 2 can be O or S independently.

[0126] In some example embodiments, Y 1 and Y 2 Can be the same.

[0127] In some example embodiments, Y 1 and Y 2 Can be different from each other.

[0128] In some example embodiments, Y 1 and Y 2 can be independently O, S, or C(CN) 2 .

[0129] In some example embodiments, X 1 With Y 1 Can be the same as X 2 With Y 2 Can be the same.

[0130] In some example embodiments, X 1 With Y 1 can be different from each other, and X 2 With Y 2 Can be different from each other.

[0131] In some example embodiments, Ar may be substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted tetracene, substituted or unsubstituted pyrene, substituted or unsubstituted thiophene, substituted or unsubstituted furan, substituted or unsubstituted selenophene, substituted or unsubstituted tellurophene, or a fused ring of two or more of these.

[0132] In some example embodiments, L 1 and L 2 The groups may be the same as or different from each other and may each independently be a heteroarylene group including O, S, Se, Te, N, Si, or a combination thereof.

[0133] In some example embodiments, L 1 and L 2 One or more rings may be included, and in the case where two or more rings are included, at least one of the two or more rings may include a heteroatom.

[0134] In some example embodiments, when L 1 and L 2When one or more rings may be included, and in the case of including two or more rings that are the same as or different from each other, the two or more rings may be fused to each other or not.

[0135] In some example embodiments, L 1 and L 2 Each independently may include at least one of the groups listed in Group 1 which may be substituted or unsubstituted.

[0136] [Group 1]

[0137]

[0138] In Group 1,

[0139] Z 1 and Z 2 Can be independently O, S, Se, Te, NR a , or SiR b R c ,

[0140] Z 3 -Z 6 Each independently is N or CR d ,

[0141] Z 3 -Z 6 At least one of them is N,

[0142] R a -R d are independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof, wherein R b and R c They exist independently or are linked to each other to form a ring.

[0143] Each group in group 1 may be unsubstituted or substituted with one or more substituents. Here, the substituent may be, for example, 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 C6-C30 aryl, a substituted or unsubstituted C3-C30 heteroaryl, a substituted or unsubstituted amine, a substituted or unsubstituted silyl, a halogen, or a combination thereof, but is not limited thereto.

[0144] In some example embodiments, L 1 and L 2Each may independently include at least one of the substituted or unsubstituted groups listed in Group 2, but is not limited thereto.

[0145] [Group 2]

[0146]

[0147] In Group 2,

[0148] R a -R c are each independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof, wherein R b and R c They exist independently or are linked to each other to form a ring.

[0149] In some example embodiments, according to L 1 and L 2 , the compound may be represented by one of Chemical Formulae 1-A to 1-F, but is not limited thereto.

[0150]

[0151] In Chemical Formulas 1-A to 1-F,

[0152] X 1 , X 2 , Y 1 , Y 2 , Ar, Z 1 , Z 2 , R 1 , and R 4 Same as described above, and

[0153] m1 and m2 may each independently be an integer of 1-5.

[0154] In some example embodiments, R 1 It may be represented by one of Chemical Formulae A-1 to A-3.

[0155]

[0156]

[0157] In Chemical Formulas A-1 to A-3,

[0158] W 1 Single bond, O, S, Se, NR e , CRf R g , or SiR h R i ,

[0159] W 2 O, S, Se, NR e , CR f R g , or SiR h R i ,

[0160] R 20 -R 25 and R e -R i are each independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof,

[0161] R 20 and R 21 may exist independently or be connected to each other to form a ring,

[0162] R 22 and R 23 may exist independently or be connected to each other to form a ring,

[0163] R 24 and R 25 may exist independently or be connected to each other to form a ring,

[0164] R f and R g may exist independently or be connected to each other to form a ring,

[0165] R h and R i may exist independently or be linked to each other to form a ring, and

[0166] * indicates the connection point.

[0167] In Chemical Formula A-1, Chemical Formula A-2, or Chemical Formula A-3, at least one hydrogen in the ring structure may be replaced by 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 C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof.

[0168] In some example embodiments, the compound may include two amine groups, namely, R 1 and R 4 Each is independently a substituted or unsubstituted amine group. In some example embodiments, R 4 Can be by-NR 5 R 6 represents a substituted or unsubstituted amine group, wherein R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted silyl, halogen, or a combination thereof, wherein R 5 and R 6 They may exist independently of each other or be linked to each other to form a ring.

[0169] In some example embodiments, R 4 It may be represented by one of Chemical Formulas B-1 to B-3.

[0170]

[0171]

[0172] In Chemical Formulas B-1 to B-3,

[0173] W 3 Single bond, O, S, Se, NR j , CR k R l , or SiR m R n ,

[0174] W 4 O, S, Se, NR j , CR k R l , or SiR m R n ,

[0175] R 26 -R 31 and R j -R n are each independently hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted amine, substituted or unsubstituted silyl, halogen, or a combination thereof,

[0176] R 26and R 27 may exist independently or be connected to each other to form a ring,

[0177] R 28 and R 29 may exist independently or be connected to each other to form a ring,

[0178] R 30 and R 31 may exist independently or be connected to each other to form a ring,

[0179] R k and R l may exist independently or be connected to each other to form a ring,

[0180] R m and R n may exist independently or be linked to each other to form a ring, and

[0181] * indicates the connection point.

[0182] In Chemical Formula B-1, Chemical Formula B-2, or Chemical Formula B-3, at least one hydrogen in the ring structure may be replaced by 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 C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted silyl group, a halogen, or a combination thereof.

[0183] In some example embodiments, depending on R 1 and R 4 , the compound may be represented by one of Chemical Formulae 1-G to 1-I, but is not limited thereto.

[0184]

[0185] [Chemical Formula 1-I]

[0186]

[0187] In the chemical formulas 1-G to 1-I, X 1 , X 2 , Y 1 , Y 2 , Ar, Z 1 , Z 2 , L 1 , L 2 , W 1 -W 4 , and R 20 -R 31 Same as described above.

[0188] In some example embodiments, the compound may be represented by Chemical Formulae 1-J to 1-Z2, but is not limited thereto.

[0189]

[0190]

[0191]

[0192] In the chemical formulae 1-J to 1-Z2, X 1 , X 2 , Y 1 , Y 2 , Ar, Z 1 , Z 2 , W 1 -W 4 , R 20 -R 31 , m1, and m2 are the same as described above.

[0193] The compound may be a light absorbing material and may, for example, be configured to absorb light in the near infrared wavelength spectrum. In some example embodiments, the peak absorption wavelength of the compound may be greater than or equal to about 700 nm. In some example embodiments, the peak absorption wavelength of the compound may be within a wavelength spectrum of about 700 nm to about 3000 nm.

[0194] The compound may exhibit good charge transport (transfer) characteristics and thus have good photoelectric conversion characteristics for absorbing light and converting it into an electrical signal, so that the compound can be effectively used as a photoelectric conversion material for a photodiode.

[0195] The compound has good heat resistance, which can prevent or reduce thermal decomposition during deposition, and thus can be repeatedly deposited. The compound can be thermally or vacuum deposited and can be deposited, for example, by sublimation. For example, deposition by sublimation can be confirmed by thermogravimetric analysis (TGA), and when thermogravimetric analysis is performed at a pressure of less than or equal to about 10 Pa, the temperature at which a 10% weight loss occurs relative to the initial weight can be less than or equal to about 450°C and the temperature at which a 50% weight loss occurs relative to the initial weight can be less than or equal to about 500°C.

[0196] In some example embodiments, upon thermogravimetric analysis of the compound at a pressure of less than or equal to about 10 Pa, for example, the temperature at which a 10% weight loss relative to the initial weight occurs may be about 230° C. to about 450° C. and the temperature at which a 50% weight loss relative to the initial weight occurs may be about 300° C. to about 500° C.

[0197] The compound can be manufactured as a film.

[0198] The film can be applied to various fields requiring light absorption properties, such as near-infrared absorption / cutoff films.

[0199] Since the compound has both light absorption properties and photoelectric properties, the compound can be effectively used as a photoelectric conversion material.

[0200] Figure 1 is a schematic diagram showing an example of a pixel array of a sensor according to some example embodiments.

[0201] The organic sensor 200 according to some example embodiments includes a plurality of pixels (PX) and the plurality of pixels (PX) may have a matrix array repeatedly arranged along rows and columns. The plurality of pixels (PX) may form ("at least partially include") a unit pixel group (A) of, for example, a 2×2 pixel array. However, the arrangement of the pixels is not limited thereto but may be variously adjusted, and in addition to the 2×2 array, the unit pixel group (A) may be variously adjusted to different pixel arrays, including a 3×3 array, a 4×4 array, etc.

[0202] Figure 2 is a cross-sectional view of a photodiode according to some example embodiments.

[0203] Reference Figure 2 , the photodiode 100 according to some example embodiments 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. A substrate (not shown) may be provided at the side of the first electrode 10 or the second electrode 20. The substrate may be made of, for example, an inorganic material such as glass or a silicon wafer; an organic material such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyether sulfone, or any combination thereof; or an organic-inorganic hybrid material. The substrate may also be omitted.

[0204] One of the first electrode 10 and the second electrode 20 is an anode and the other is a cathode. In some example embodiments, the first electrode 10 may be an anode and the second electrode 20 may be a cathode.

[0205] 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). In some example embodiments, the first electrode 10 and the second electrode 20 may all be light-transmitting electrodes. In some example embodiments, the second electrode 20 may be a light-receiving electrode disposed at the light-receiving side.

[0206] The organic layer 30 may include an active layer.

[0207] The active layer is a layer including a p-type semiconductor and an n-type semiconductor to provide a PN junction, which is a layer that generates excitons by receiving electromagnetic radiation and then separates holes and electrons from the generated excitons.

[0208] The p-type semiconductor and the n-type semiconductor may independently be light absorbing materials configured to absorb light in at least a portion of a wavelength spectrum, and the aforementioned compound may be a p-type semiconductor or an n-type semiconductor. In some example embodiments, the aforementioned compound may be used for a p-type semiconductor and fullerene or a fullerene derivative may be included as an n-type semiconductor.

[0209] The active layer may include an intrinsic layer, in which the aforementioned p-type semiconductor and the n-type semiconductor including the fullerene derivative may be co-deposited. Here, the p-type semiconductor and the n-type semiconductor may be included in a relative volume ratio of about 1:9 to about 9:1, such as 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.

[0210] 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. In some example embodiments, the active layer may include various combinations of p-type layer / I layer, I layer / n-type layer, p-type layer / I layer / n-type layer, etc.

[0211] By including the above-mentioned compound, the organic layer 30 can effectively absorb light in the wavelength spectrum of incident light (e.g., near-infrared wavelength spectrum) and can photoelectrically convert it (i.e., the absorbed light wavelength spectrum) into an electrical signal. To reiterate, the organic layer 30 can be or include a film including a composition according to any example embodiment described herein, such that the organic layer 30 includes a compound according to any example embodiment as described herein. For example, in some example embodiments, the peak absorption wavelength of the organic layer 30 can be greater than or equal to about 700 nm.

[0212] The peak absorption wavelength of the organic layer 30 may be within a wavelength spectrum of, for example, about 700 nm to about 3000 nm, 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.

[0213] The organic layer 30 may further include a charge auxiliary 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 auxiliary layer may allow holes and electrons separated in the active layer to be more easily transferred and may improve efficiency.

[0214] The charge auxiliary layer may include at least one of: a hole injection layer (HIL) for facilitating hole injection, a hole transport layer (HTL) for facilitating hole transport, an electron blocking layer (EBL) for preventing electron transport, an electron injection layer (EIL) for facilitating electron injection, an electron transport layer (ETL) for facilitating electron transport, and a hole blocking layer (HBL) for preventing hole transport.

[0215] The charge auxiliary layer may include, for example, an organic material, an inorganic material, or an organic / inorganic material. The organic material may be an organic material having hole or electron injection, transport, or blocking properties, and the inorganic material may be, for example, a metal oxide such as molybdenum oxide, tungsten oxide, or nickel oxide.

[0216] The charge auxiliary layer may include, for example, the aforementioned compound.

[0217] The photodiode 100 may further include an anti-reflection layer (not shown) on the first electrode 10 or the second electrode 20. The anti-reflection layer is disposed at the light incident side and may reduce light reflection of the incident light and thereby light absorption rate may be further improved. In some example embodiments, when light enters the upper surface of the first electrode 10, the anti-reflection layer may be disposed on the upper surface of the first electrode 10, and when light enters the lower surface of the second electrode 20, the anti-reflection layer may be disposed below the lower surface of the second electrode 20.

[0218] The anti-reflection layer may include, for example, a material having a refractive index of about 1.6 to about 2.5 and may include, for example, at least one of a metal oxide, a metal sulfide, and an organic material having a refractive index within the range. The anti-reflection layer may include, for example, a metal oxide such as an oxide containing aluminum, an oxide containing molybdenum, an oxide containing tungsten, an oxide containing vanadium, an oxide containing rhenium, an oxide containing niobium, an oxide containing tantalum, an oxide containing titanium, an oxide containing nickel, an oxide containing copper, an oxide containing cobalt, an oxide containing manganese, an oxide containing chromium, an oxide containing tellurium, or a combination thereof; a metal sulfide such as zinc sulfide; or an organic material such as an amine derivative, but is not limited thereto.

[0219] In the photodiode 100, when light enters from the first electrode 10 or the second electrode 20 and the organic layer 30 absorbs the light in a predetermined wavelength spectrum, excitons may be generated inside thereof. The excitons are separated into holes and electrons in the organic layer 30, and the separated holes are transferred to an anode as one of the first electrode 10 and the second electrode 20 and the separated electrons are transferred to a cathode as the other of the first electrode 10 and the second electrode 20 to allow current to flow.

[0220] The photodiode 100 may be applied to a solar cell, an image sensor, a photodetector, a photo sensor, and a light emitting diode (LED), but is not limited thereto.

[0221] The photodiode may be applied to an organic sensor, for example. The organic sensor may be an organic CMOS sensor, for example, an organic CMOS infrared sensor or an organic CMOS image sensor.

[0222] Figure 3 is a cross-sectional view showing an organic sensor according to some example embodiments.

[0223] The organic sensor 300 according to some example embodiments includes a semiconductor substrate 110 , an insulating layer 80 , and a photodiode 100 .

[0224] The semiconductor substrate 110 may be a silicon substrate and is integrated with a transfer transistor (not shown) and a charge storage 55. The charge storage 55 may be integrated in each pixel. The charge storage 55 is electrically connected to the photodiode 100 to be described later and information of the charge storage 55 may be transferred through the transfer transistor.

[0225] A wire (not shown) and a pad (not shown) are formed on the semiconductor substrate 110. In order to reduce signal delay, the wire and the pad may be made of a material having a low resistivity, in some example embodiments, aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but not limited thereto. In addition, it is not limited to the structure, and the wire and the pad may be disposed below the semiconductor substrate 110.

[0226] An insulating layer 80 may be formed on the wires and pads. The insulating layer 80 may be made of an inorganic insulating material such as silicon oxide and / or silicon nitride, or a low dielectric constant (low-K) material such as SiC, SiCOH, SiCO, and SiOF. The insulating layer 80 has a trench 85 exposing the charge storage 55. The trench 85 may be filled with a filler.

[0227] The photodiode 100 may be formed on the insulating layer 80. As described above, the photodiode 100 includes the first electrode 10, the organic layer 30, and the second electrode 20. Although a structure in which the first electrode 10, the organic layer 30, and the second electrode 20 are sequentially stacked is shown in the figure as an example, the present disclosure is not limited to this structure, and the second electrode 20, the organic layer 30, and the first electrode 10 may be arranged in this order.

[0228] 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 selectively absorb light in the near-infrared wavelength spectrum. In the organic layer 30, incident light from the second electrode 20 side may be photoelectrically converted by mainly absorbing light in the near-infrared wavelength spectrum.

[0229] A focusing lens (not shown) may be further formed on the photodiode 100. The focusing lens may control the direction of incident light and converge the light in one area. The focusing lens may have a shape of a cylinder or a hemisphere in some example embodiments, but is not limited thereto.

[0230] The organic sensor according to the present embodiment may be an organic infrared light sensor, an iris sensor, or a depth sensor in some example embodiments.

[0231] The iris sensor authenticates a person by utilizing each person's unique iris characteristics and, in particular, taking an image of the user's eyes within an appropriate distance range, processing the image, and comparing it to his / her stored images.

[0232] The depth sensor identifies the shape and position of the object from the three-dimensional information of the object by capturing an image of the object within a suitable distance range from the user and processing the image. The depth sensor can be used as a facial recognition sensor, for example.

[0233] Figure 4 is a cross-sectional view showing an organic sensor according to another embodiment.

[0234] The organic sensor according to the present embodiment may include a plurality of sensors having different functions. In some example embodiments, at least one of the plurality of sensors having different functions may be a biometric sensor, and the biometric sensor may be, for example, an iris sensor, a depth sensor, a fingerprint sensor, a blood vessel distribution sensor, etc., but is not limited thereto. In some example embodiments, one of the plurality of sensors having different functions may be an iris sensor and another may be a depth sensor.

[0235] In some example embodiments, the plurality of sensors may include, for example, a plurality of sensors configured to sense a first wavelength (λ 1 ) in the infrared spectrum and a first infrared light sensor configured to sense light having a second wavelength (λ) in the infrared wavelength spectrum 2 )'s second infrared light sensor for light in the infrared spectrum.

[0236] The first wavelength (λ 1 ) and the second wavelength (λ 2 ) may be different, and for example at the first wavelength (λ 1 ) and the second wavelength (λ 2 ) 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.

[0237] In some example embodiments, the first wavelength (λ 1 ) and the second wavelength (λ 2 ) may be within a wavelength spectrum of about 780 nm to about 900 nm and the first wavelength (λ 1 ) and the second wavelength (λ 2 ) can be within a wavelength spectrum of about 830 nm to about 1000 nm.

[0238] In some example embodiments, the first wavelength (λ 1 ) and the second wavelength (λ 2) may be within a wavelength spectrum of about 780 nm to about 840 nm and the first wavelength (λ 1 ) and the second wavelength (λ 2 ) can be within a wavelength spectrum of about 910 nm to about 970 nm.

[0239] The organic sensor 400 according to the present embodiment includes a dual band pass filter 40, a first infrared light sensor 100A, an insulating layer 80, and a semiconductor substrate 110 integrated with a second infrared light sensor 120. The first infrared light sensor 100A and the second infrared light sensor 120 may be stacked.

[0240] The dual-band pass filter 40 may be disposed at the front side of the organic sensor 400 and may selectively transmit the first wavelength (λ 1 ) and the infrared light including the second wavelength (λ 2 ) and may block and / or absorb other light. Here, other light may include light in the ultraviolet (UV) and visible spectrum.

[0241] The first infrared light sensor 100A may be the photodiode 100 according to the aforementioned embodiment and details thereof are omitted.

[0242] 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 be integrated with the second infrared light sensor 120, the charge storage 55, and a transfer transistor (not shown).

[0243] The second infrared light sensor 120 may be a photodiode and may sense the incoming light, and the sensed information may be transmitted through the transmission transistor. Here, the light entering the second infrared light sensor 120 is the light that passes through the dual-band pass filter 40 and the first infrared light sensor 100A and may be the light that includes the second wavelength (λ 2 ) of the predetermined spectrum. 1 ) may be absorbed by the organic layer 30 and may not reach the second infrared light sensor 120, a separate filter having wavelength selectivity for light entering the second infrared light sensor 120 is not required. However, for when not all infrared light in the predetermined spectrum including the first wavelength (λ 1 ) 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.

[0244] The organic sensor according to the present embodiment may include two infrared light sensors that perform separate functions, and thus may work as a combined sensor. In addition, two sensors that perform separate functions are stacked in each pixel, and thus the number of pixels that perform the functions of each sensor is increased to two times while maintaining the size, and as a result, the sensitivity can be greatly improved.

[0245] Figure 5 is a cross-sectional view showing an example of an organic sensor according to some example embodiments.

[0246] The organic sensor according to some example embodiments may be an organic CMOS image sensor.

[0247] Reference Figure 5 , an organic sensor 500 according to some example embodiments includes a semiconductor substrate 110 integrated with light sensing devices 50a, 50b, and 50c, a transfer transistor (not shown), and a charge storage 55, a lower insulating layer 60, a color filter layer 70a, 70b, and 70c, an upper insulating layer 80, and a photodiode 100.

[0248] The semiconductor substrate 110 may be integrated with light sensing devices 50a, 50b, and 50c, a transfer transistor (not shown), and a charge storage 55. The light sensing devices 50a, 50b, and 50c may be photodiodes.

[0249] The light sensing devices 50a, 50b, and 50c, the transfer transistors, and / or the charge storage 55 may be integrated in each pixel (PX). For example, the light sensing device 50a may be included in a red pixel, the light sensing device 50b may be included in a green pixel, and the light sensing device 50c may be included in a blue pixel.

[0250] The light sensing devices 50a, 50b, and 50c sense light, and information sensed by the light sensing devices can be transmitted through the transfer transistors. The charge storage 55 is electrically connected to the photodiode 100 to be described later, and information of the charge storage 55 can be transmitted through the transfer transistors.

[0251] A wire (not shown) and a pad (not shown) are formed on the semiconductor substrate 110. In order to reduce signal delay, the wire and the pad may be made of a material having a low resistivity such as aluminum (Al), copper (Cu), silver (Ag), and an alloy thereof, but is not limited thereto. In addition, it is not limited to the structure, and the wire and the pad may be disposed under the light sensing devices 50a and 50b.

[0252] A lower insulating layer 60 may be formed on the lines and pads.

[0253] Color filters 70a, 70b, and 70c are formed on the lower insulating layer 60. The 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.

[0254] An upper insulating layer 80 may be formed on the color filters 70a, 70b, and 70c. The upper insulating layer 80 eliminates steps caused by the color filters 70a, 70b, and 70c and flattens the surface.

[0255] The photodiode 100 may be formed on the upper insulating layer 80. As described above, the photodiode 100 includes the first electrode 10, the organic layer 30, and the second electrode 20. Although a structure in which the first electrode 10, the organic layer 30, and the second electrode 20 are sequentially stacked is shown in the figure as an example, the present disclosure is not limited to this structure, and the second electrode 20, the organic layer 30, and the first electrode 10 may be arranged in this order.

[0256] 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 selectively absorb light in the near infrared wavelength spectrum.

[0257] In the organic layer 30, incident light from the second electrode 20 side may be photoelectrically converted by mainly absorbing light in the near-infrared wavelength spectrum. Light in the remaining wavelength spectrum may pass through the first electrode 10 and the color filters 70a, 70b, and 70c, light in the red wavelength spectrum passing through the color filter 70a may be sensed by the light sensing device 50a, light in the green wavelength spectrum passing through the color filter 70b may be sensed by the light sensing device 50b, and light in the blue wavelength spectrum passing through the color filter 70c may be sensed by the light sensing device 50c.

[0258] The organic sensors may be applied to various electronic devices, for example, the electronic devices may include, for example, cameras, video cameras, mobile phones, display devices, security devices, or medical devices having them therein, but are not limited thereto.

[0259] Figure 6 is a schematic cross-sectional view of an organic sensor according to some example embodiments.

[0260] Reference Figure 6 , an organic sensor 600 according to some example embodiments includes a semiconductor substrate 110 integrated with light sensing devices 50a, 50b, and 50c, a transfer transistor (not shown), and a charge storage 55, a lower insulating layer 60, a color filter layer 70 including color filters 70a, 70b, and 70c, and an optoelectronic device 100. Figure 6As shown in FIG. 1 , the optoelectronic device 100 may be between the semiconductor substrate 110 and the color filter layer 70, such that the color filter layer 70 is away from the light sensing devices 50a, 50b, and 50c relative to the optoelectronic device 100. Figure 5 The same as the organic sensor.

[0261] In some example embodiments, the color filter layer 70 may include color filters configured to filter a mixture of wavelength spectra of light (eg, a mixture of colors). Figure 5 In or 6, color filter 70a may be configured to filter magenta light, color filter 70b may be configured to filter cyan light, and color filter 70b may be configured to filter yellow light, while light sensing device 50a may be configured to detect ("sense") blue light and light sensing device 50b may be configured to detect red light.

[0262] Figure 7 is a schematic cross-sectional view of an organic sensor according to some example embodiments.

[0263] Reference Figure 7 According to some example embodiments, an organic image sensor 700 includes a semiconductor substrate 110 integrated with light sensing devices 50a, 50b, and 50c, a transfer transistor (not shown) and a charge storage device 55, a lower insulating layer 60, an upper insulating layer 80 and a color filter layer 70 on the semiconductor substrate 110, and an optoelectronic device 100 below the semiconductor substrate 110.

[0264] like Figure 7 As shown in FIG. 1 , the optoelectronic device 100 may be below the semiconductor substrate 110 so that the color filter layer 70 is away from the optoelectronic device 100 relative to the light sensing devices 50a, 50b, and 50c. Figure 5 The same as the organic sensor.

[0265] Figure 8 is a cross-sectional view showing an organic sensor according to some example embodiments.

[0266] The organic sensor 800 according to some example embodiments includes a semiconductor substrate 110 integrated with light sensing devices 50a, 50b, and 50c, a transfer transistor (not shown), and a charge storage 55, an insulating layer 60 having a groove 85, and a photoelectric device 100. In the organic sensor 800 according to some example embodiments, the light sensing devices 50a, 50b, and 50c are stacked in a vertical direction and the color filter layer 70 is omitted. The light sensing devices 50a, 50b, and 50c are electrically connected to the charge storage (not shown) and their information can be transmitted through the transfer transistor. The light sensing devices 50a, 50b, and 50c can selectively absorb light in each wavelength spectrum of light depending on the stacking depth. Other structures and Figure 5 The same as the organic sensor.

[0267] Fig. 9 is a perspective view of an organic sensor according to some example embodiments. Fig.10 To illustrate some example embodiments Fig. 9 Schematic cross-sectional view of an organic sensor.

[0268] like Fig. 9 As shown, the organic sensor 900 according to some example embodiments includes an infrared / near-infrared optoelectronic device configured to selectively absorb light in the infrared / near-infrared wavelength spectrum of light, a red optoelectronic device configured to selectively absorb light in the red wavelength spectrum of incident light and convert it (into an electrical signal), a green optoelectronic device configured to selectively absorb light in the green wavelength spectrum of incident light and convert it (into an electrical signal), and a blue optoelectronic device configured to selectively absorb light in the blue wavelength spectrum of incident light and convert it (into an electrical signal), and they are arranged horizontally. Fig.10 , the organic sensor 900 may include an optoelectronic device 100 including a plurality of optoelectronic devices 100a, 100b, 100c, and 100d on a semiconductor substrate 110, wherein the plurality of optoelectronic devices 100a, 100b, 100c, and 100d are respectively configured to absorb different light (i.e., different wavelength spectra of incident light) of blue light, green light, red light, and infrared light and convert them into electrical signals. Fig.10 , an organic CMOS image sensor 800 according to some example embodiments includes a semiconductor substrate 110 integrated with charge storages 55a-55d and transfer transistors (not shown), an insulating layer 60, and optoelectronic devices 100a-100d. Figure 9-10 As shown in , the organic sensor 900 may include an optoelectronic device 100 on a semiconductor substrate 110, the optoelectronic device 100 itself including a plurality of optoelectronic devices 100a-100d, wherein the plurality of optoelectronic devices 100a-100d are respectively configured to absorb different light (i.e., different wavelength spectra of incident light) of blue light, green light, red light, and infrared light and convert them into electrical signals.

[0269] like Fig.10As shown in , the individual optoelectronic devices 100a-100d may be arranged horizontally on the semiconductor substrate 110 so that the optoelectronic devices 100a-100d partially overlap each other in a direction extending parallel to the top surface 110a of the semiconductor substrate 110. As shown, each individual optoelectronic device 100a-100d is connected to an individual charge storage 55 integrated into the semiconductor substrate 110 via an individual trench 85. Each optoelectronic device 100a-100d may be any of the optoelectronic devices described herein. In some example embodiments, the individual optoelectronic devices 100a-100d may include different portions of a common continuous layer that extends continuously between two or more of the optoelectronic devices 100a-100d.

[0270] In some example embodiments, the optoelectronic devices 100a-100d may share a common counter electrode 20. In another example, two or more of the optoelectronic devices 100a-100d may have different photoelectric conversion layers 30a, 30b, 30c, and 30d configured to absorb different wavelength spectra of incident light. Figure 4 The same as the organic sensor.

[0271] Fig.11 is a schematic cross-sectional view of an organic sensor according to some example embodiments.

[0272] Reference Fig.11 , the organic CMOS image sensor 1100 includes a semiconductor substrate 110 integrated with a charge storage and a transfer transistor (not shown), an intermediate insulating layer 60, a first photoelectric device 1190, a second photoelectric device 1190a, a third photoelectric device 1190b, and a fourth photoelectric device 1190c. The first photoelectric device 1190, which may be an infrared / near-infrared photoelectric device and thus may be configured to absorb infrared and / or near-infrared light, may be formed on the entire surface of the second to fourth photoelectric devices 1190a-1190c. The second to fourth photoelectric devices 1190a, 1190b, and 1190c may be configured to absorb and convert different lights (i.e., different wavelength spectra of incident light) of blue light, green light, and red light, respectively. For example, as shown, the second to fourth optoelectronic devices 1190a, 1190b, and 1190c may share a continuous counter electrode 1120 and may include separate, respective pixel electrodes 1110 and may further each include separate, respective photoelectric conversion layers 1130a, 1130b, and 1130c, which may be configured to absorb and convert separate, respective wavelength spectra of light (e.g., red light, green light, and blue light, respectively). Other structures and Figure 4 The image sensor is the same.

[0273] Reference Fig.11 , the first optoelectronic device 1190 may be stacked on the second to fourth optoelectronic devices 1190a-1190c to at least partially overlap them in a direction extending perpendicular to the top surface 110a of the semiconductor substrate 110, and wherein the second to fourth optoelectronic devices 1190a-1190c overlap in a direction extending parallel to the top surface 110a of the semiconductor substrate 110. It will be appreciated that in some example embodiments, the second to fourth optoelectronic devices 1190a-1190c include a plurality of horizontally arranged optoelectronic devices configured to absorb different wavelength spectra of light, while the first optoelectronic device 1190 is limited to a single optoelectronic device configured to absorb a single wavelength or a customized spectrum of light.

[0274] In some example embodiments, including Fig.11 In the example embodiment shown in , the entire first optoelectronic device 1190 overlaps limited portions of the second to fourth optoelectronic devices 1190a-1190c in a direction extending perpendicular to the top surface 110a, and the remaining portions of the first optoelectronic device 1190 exposed by the second to fourth optoelectronic devices 1190a-1190c are covered by the insulating layer 80. However, it will be understood that in some example embodiments, the entire first optoelectronic device 1190 overlaps limited portions of the second to fourth optoelectronic devices 1190a-1190c in a direction extending perpendicular to the top surface 110a.

[0275] Fig.12 is a perspective view of an organic sensor according to some example embodiments, and Fig.13 To illustrate some example embodiments Fig.12 Schematic cross-sectional view of an organic sensor.

[0276] like Fig.12 As shown in , the organic sensor 1200 according to some example embodiments includes an infrared / near-infrared optoelectronic device configured to selectively absorb light in the infrared / near-infrared wavelength spectrum of light, a red optoelectronic device configured to selectively absorb light in the red wavelength spectrum of incident light and convert it (into an electrical signal), a green optoelectronic device configured to selectively absorb light in the green wavelength spectrum of incident light and convert it (into an electrical signal), and a blue optoelectronic device configured to selectively absorb light in the blue wavelength spectrum of incident light and convert it (into an electrical signal), and they are stacked. Fig.13As shown in , an organic sensor 1200 according to some example embodiments includes a semiconductor substrate 110, a lower insulating layer 80a, an intermediate insulating layer 80b, another intermediate insulating layer 80c, an upper insulating layer 80d, a first optoelectronic device 1200a, a second optoelectronic device 1200b, a third optoelectronic device 1200c, and a fourth optoelectronic device 1200d. As shown, the first to fourth optoelectronic devices 1200a-1200d are vertically stacked on the semiconductor substrate 110 so that the first to fourth optoelectronic devices 1200a-1200d overlap each other in a direction perpendicular to the top surface 110a of the semiconductor substrate 110.

[0277] The semiconductor substrate 110 may be a silicon substrate, and integrated with a transfer transistor (not shown) and charge storages 55a, 55b, 55c, and 55d. The first photoelectric device 1200a may be formed on the lower insulating layer 80a.

[0278] The first optoelectronic device 1200a includes a first electrode 10a and a second electrode 20a facing each other and a photoelectric conversion layer 30a between the first electrode 10a and the second electrode 20a. The first electrode 10a, the second electrode 20a, and the photoelectric conversion layer 30a are the same as described above, and the photoelectric conversion layer 30a can selectively absorb light in one of the infrared, red, blue, and green wavelength spectra of the incident light and convert it (into an electrical signal). For example, the first optoelectronic device 1200a can be a blue optoelectronic device. In the figure, the first electrode 10a, the photoelectric conversion layer 30a, and the second electrode 20a are stacked sequentially, but the present disclosure is not limited thereto, and for example, they can be stacked in the order of the second electrode 20a, the photoelectric conversion layer 30a, and the first electrode 10a.

[0279] The intermediate insulating layer 80b may be formed on the first optoelectronic device 1200a. The second optoelectronic device 1200b may be formed on the intermediate insulating layer 80b. The second optoelectronic device 1200b may include a first electrode 10b and a second electrode 20b facing each other and a light absorbing layer 30b (e.g., a photoelectric conversion layer 30b) between the first electrode 10b and the second electrode 20b. The first electrode 10b, the second electrode 20b, and the photoelectric conversion layer 30b are the same as described above, and the photoelectric conversion layer 30b may selectively absorb light in one of the infrared, red, blue, and green wavelength spectra of the incident light and convert it (into an electrical signal). For example, the second optoelectronic device 1200b may be a green optoelectronic device. In the figure, the first electrode 10b, the photoelectric conversion layer 30b, and the second electrode 20b are stacked sequentially, but the present disclosure is not limited thereto, and for example, they can be stacked in the order of the second electrode 20b, the photoelectric conversion layer 30b, and the first electrode 10b.

[0280] Another intermediate insulating layer 80c may be formed on the second optoelectronic device 1200b. The third optoelectronic device 1200c may be formed on the intermediate insulating layer 80c. The third optoelectronic device 1200c includes a first electrode 10c and a second electrode 20c facing each other and a light absorbing layer 30c (e.g., a photoelectric conversion layer 30c) between the first electrode 10c and the second electrode 20c. The first electrode 10c, the second electrode 20c, and the photoelectric conversion layer 30c may be the same as described above, and the photoelectric conversion layer 30c may selectively absorb light in one of the infrared, red, blue, and green wavelength spectra of the incident light and convert it (into an electrical signal). For example, the third optoelectronic device 1200c may be a red optoelectronic device. In the figure, the first electrode 10c, the photoelectric conversion layer 30c, and the second electrode 20c are stacked sequentially, but the present disclosure is not limited thereto, and for example, they can be stacked in the order of the second electrode 20c, the photoelectric conversion layer 30c, and the first electrode 10c. The upper insulating layer 80d may be formed on the third optoelectronic device 1200c. The lower insulating layer 80a, the intermediate insulating layers 80b and 80c, and the upper insulating layer 80d have a plurality of through holes that expose the charge storages 55a, 55b, 55c, and 55d. The fourth optoelectronic device 1200d may be formed on the upper insulating layer 80d. The fourth optoelectronic device 1200d includes a first electrode 10d and a second electrode 20d facing each other and a light absorbing layer 30d (e.g., a photoelectric conversion layer 30d) between the first electrode 10d and the second electrode 20d. The first electrode 10d, the second electrode 20d, and the photoelectric conversion layer 30d may be the same as described above, and the photoelectric conversion layer 30d may selectively absorb light in one of the infrared, red, blue, and green wavelength spectra of light and convert it (into an electrical signal). For example, the fourth optoelectronic device 1200d may be an infrared / near-infrared optoelectronic device. In the drawing, the first electrode 10d, the photoelectric conversion layer 30d, and the second electrode 20d are sequentially stacked, but the present disclosure is not limited thereto, and for example, they may be stacked in the order of the second electrode 20d, the photoelectric conversion layer 30d, and the first electrode 10d.

[0281] A focusing lens 1300 may be further formed on the fourth optoelectronic device 1200d. The focusing lens 1300 may control the direction of incident light and converge the light in one area. The focusing lens 1300 may have a shape such as a cylinder or a hemisphere, but is not limited thereto.

[0282] In the drawing, the first photoelectric device 1200a, the second photoelectric device 1200b, the third photoelectric device 1200c, and the fourth photoelectric device 1200d are sequentially stacked, but the present disclosure is not limited thereto, and they may be stacked in various sequences.

[0283] As described above, the first photoelectric device 1200 a , the second photoelectric device 1200 b , the third photoelectric device 1200 c , and the fourth photoelectric device 1200 d have a stacked structure, and thus the size of the image sensor may be reduced to implement a miniaturized image sensor.

[0284] Fig.14 is a schematic diagram of an electronic device according to some example embodiments.

[0285] like Fig.14 As shown in , the electronic device 1400 may include a processor 1420, a memory 1430, and an organic sensor 1440 electrically coupled together via a bus (bus bar) 1410. The organic sensor 1440 may be an organic sensor as described in any example embodiment herein, and the organic sensor included in the organic sensor 1440 may include any optoelectronic device described in this article according to any example embodiment of the inventive concept. The memory 1430, which may be a non-transitory computer-readable medium, may store a program of instructions. The processor 1420 may execute the stored instruction program to perform one or more functions.

[0286] In some example embodiments, the processor 1420 may be configured to process the electrical signal generated by the organic sensor 1440. The processor 1420 may be configured to generate an output (e.g., an image to be displayed on a display interface (interface)) based on processing the electrical signal. Although some example embodiments of the optoelectronic device shown herein include first and second electrodes 10 and 20 facing each other and an organic layer 30 therebetween, wherein the organic layer may include a compound according to any example embodiment herein, it will be understood that in some example embodiments, at least the first and second electrodes 10 and 20 may be omitted from the optoelectronic device.

[0287] Hereinafter, the embodiments are described in more detail with reference to Examples. However, these Examples are exemplary, and the present scope is not limited thereto.

[0288] Synthesis Example

[0289] Synthesis Example 1

[0290] [Reaction Scheme 1]

[0291]

[0292] Synthesis of Compound I-1

[0293] 3,7-Dibromobenzo[1,2-b:4,5-b′]dithiophene-2,6-dione (Compound I-1) was synthesized according to the method described in Chem. Lett., 905, 1983.

[0294] Synthesis of compound 1

[0295] 3,7-Dibromobenzo[1,2-b:4,5-b']dithiophene-2,6-dione (Compound I-1) (0.60 g, 1.59 mmol), N,N-diphenyl-5-(tributylstannyl)thiophene-2-amine (1.80 g, 3.33 mmol), and tetrakis(triphenylphosphine)palladium(0) (Pd(PPh 3 ) 4 ) (0.18 g, 0.16 mmol) was dissolved in 300 mL of toluene, and then stirred at 110° C. for 18 hours. When the reaction was completed, toluene was evaporated to concentrate the mixture and the resultant was separated with a dichloromethane:hexane (1:1 volume / volume) column, and then precipitated in 200 mL of methanol to obtain compound 1 (0.61 g). The yield was 53%.

[0296] NMR (300 MHz, CDCl 3 ): 7.81(d, 2H), 7.48(s, 2H), 7.39(t, 8H), 7.28(d, 8H), 7.21(t, 4H), 6.56(d, 2H).

[0297] Synthesis Example 2

[0298] [Reaction Scheme 2]

[0299]

[0300] Synthesis of Compound I-2

[0301] 10-(thiophene-2-yl)-10H-phenothiazine (1.0 g, 3.55 mmol) was added to 50 mL of THF, 2.5 M n-BuLi (1.56 mL, 3.91 mmol) was slowly added thereto at -78 °C, and the mixture was stirred for 4 hours. Subsequently, tributyltin chloride (1.27 g, 3.91 mmol) was slowly added thereto at room temperature, and the mixture was further stirred for 4 hours. When the reaction was complete, the resultant was extracted with 200 mL of chloroform to obtain 2 g of 10-(5-(tributylstannyl)thiophene-2-yl)-10H-phenothiazine (Compound I-2).

[0302] NMR (300MHz, CD 2 Cl 2): 7.25 (d, 1H), 7.22 (d, 1H), 7.05 (d, 2H), 6.99 (t, 2H), 6.90 (t, 2H), 6.67 (d, 2H), 1.65 (m, 6H), 1.40 (m, 6H), 1.20 (t, 6H), 0.94 (t, 9H).

[0303] Synthesis of compound 2

[0304] 3,7-Dibromobenzo[1,2-b:4,5-b']dithiophene-2,6-dione (Compound I-1) (0.30 g, 0.79 mmol), 10-(5-(tributylstannyl)thiophen-2-yl)-10H-phenothiazine (Compound I-2) (0.95 g, 1.67 mmol), and Pd(PPh 3 ) 4 (0.09 g, 0.08 mmol) was dissolved in 100 mL of toluene and then stirred at 110° C. for 18 hours. When the reaction was complete, toluene was evaporated to concentrate the mixture, and the resultant was separated with a dichloromethane: hexane (1:1 volume / volume) column and then precipitated in 100 mL of methanol to obtain compound 2 (0.30 g). The yield was 49%.

[0305] NMR (300 MHz, CDCl 3 ): 7.80(d, 2H), 7.53(s, 2H), 7.33(m, 8H), 7.21(d, 4H), 7.15(t, 4H), 6.82(d, 2H).

[0306] Synthesis Example 3

[0307] [Reaction Scheme 3]

[0308]

[0309] Synthesis of Compound I-3

[0310] 10,10-dimethyl-5-(thiophene-2-yl)-5,10-dihydrodibenzo[b,e][1,4]azasilin (azasiline) (1.0 g, 3.25 mmol) was added to 50 mL THF and 2.5 M n-BuLi (1.43 mL, 3.58 mmol) was slowly added thereto at -78 °C, and the mixture was stirred for 4 hours. Subsequently, tributyltin chloride (1.06 g, 3.91 mmol) was slowly added thereto at room temperature, and the mixture was further stirred for 4 hours. When the reaction was complete, the resulting product was extracted with 200 mL chloroform to obtain 1.9 g 10,10-dimethyl-5-(5-(tributylstannyl)thiophene-2-yl)-5,10-dihydrodibenzo[b,e][1,4]azasilin (Compound I-3).

[0311] NMR (300MHz, CD 2 Cl 2 ): 7.58(d, 2H), 7.28(d, 1H), 7.23(t, 2H), 7.11(d, 1H), 7.03(t, 2H), 6.74 (d, 2H), 1.65 (m, 6H), 1.40 (m, 6H), 1.20 (t, 6H), 0.95 (t, 9H), 0.52 (s, 6H).

[0312] Synthesis of compound 3

[0313] 3,7-Dibromobenzo[1,2-b:4,5-b']dithiophene-2,6-dione (Compound I-1) (0.30 g, 0.79 mmol), 10,10-dimethyl-5-(5-(tributylstannyl)thiophen-2-yl)-5,10-dihydrodibenzo[b,e][1,4]azasilanol (Compound I-3) (0.99 g, 1.67 mmol), and Pd(PPh 3 ) 4 (0.09 g, 0.08 mmol) was dissolved in 100 mL of toluene and then stirred at 110° C. for 18 hours. When the reaction was complete, toluene was evaporated to concentrate the mixture and the resultant was separated with a dichloromethane: hexane (1:1 volume / volume) column and precipitated in 100 mL of methanol to obtain compound 3 (0.30 g). The yield was 45%.

[0314] Confirmation of molecular weight: LC-MS: 831.11 m / z.

[0315] Synthesis Example 4

[0316] [Reaction Scheme 4]

[0317]

[0318] 3,7-Dibromobenzo[1,2-b:4,5-b']dithiophene-2,6-dione (Compound I-1) (0.30 g, 0.79 mmol), 4-(5-(tributylstannyl)thiophen-2-yl)morpholine (0.76 g, 1.67 mmol) and Pd(PPh 3 ) 4 (0.09 g, 0.08 mmol) was dissolved in 100 mL of toluene and then stirred at 110° C. for 18 hours. When the reaction was complete, toluene was evaporated to concentrate the mixture, and the resultant was separated with a dichloromethane: hexane (1:1 volume / volume) column and then precipitated in 100 mL of methanol to obtain compound 4 (0.10 g). The yield was 22%.

[0319] Molecular weight confirmation: LC-MS: 555.07m / z

[0320] Synthesis Example 5

[0321] [Reaction Scheme 5]

[0322]

[0323] 3,7-Dibromobenzo[1,2-b:4,5-b']dithiophene-2,6-dione (Compound I-1) (0.30 g, 0.79 mmol), N,N-diphenyl-5-(tributylstannyl)furan-2-amine (0.87 g, 1.67 mmol), and Pd(PPh 3 ) 4 (0.09 g, 0.08 mmol) was dissolved in 100 mL of toluene and then stirred at 110° C. for 18 hours. When the reaction was complete, toluene was evaporated to concentrate the mixture, and then the resultant was separated with a dichloromethane: hexane (1:1 volume / volume) column and precipitated in 100 mL of methanol to obtain compound 5 (0.25 g). The yield was 46%.

[0324] NMR (300 MHz, CDCl 3 ): 7.49(d, 2H), 7.45(s, 2H), 7.42(d, 8H), 7.30(d, 8H), 7.23(t, 4H), 7.06(d, 2H).

[0325] Synthesis Example 6

[0326] [Reaction Scheme 6]

[0327]

[0328] Synthesis of Compound I-4

[0329] Diphenylamine (2 g, 11.82 mmol), 6-bromobenzo[b]thiophene (2.52 g, 11.82 mmol), 5 mol% Pd(dba) 2 、5 mol% P(tBu) 3 , and NaOtBu (1.36 g, 14.18 mmol) were dissolved in 100 mL of toluene, and then stirred at 110 ° C for 18 hours. When the reaction was completed, toluene was evaporated to concentrate the mixture, and the resultant was separated by a dichloromethane: hexane (1: 1 volume / volume) column to obtain 2.5 g of N, N-diphenylbenzo [b] thiophene-6-amine (compound I-4). The yield was 70%.

[0330] NMR (300 MHz, CDCl 3 ): 7.68(d, 1H), 7.55(s, 1H), 7.31(d, 1H), 7.28(d, 1H), 7.22(d, 4H), 7.15(d, 1H), 7.10(d, 4H), 7.01(t, 2H).

[0331] Synthesis of Compound I-5

[0332] N, N-diphenylbenzo [b] thiophene-6-amine (Compound I-4) (2.0 g, 6.64 mmol) was added to 60 mL THF, 2.5 M n-BuLi (2.92 mL, 7.30 mmol) was slowly added thereto at -78 ° C and the mixture was stirred for 4 hours. Subsequently, tributyltin chloride (2.38 g, 7.30 mmol) was slowly added thereto at room temperature and the mixture was further stirred for 4 hours. When the reaction was complete, the resultant was extracted with 200 mL chloroform to obtain 3.9 g N, N-diphenyl-2- (tributyl stannyl) benzo [b] thiophene-6-amine (Compound I-5).

[0333] NMR (300 MHz, CDCl 3 ): 7.67(d, 1H), 7.57(s, 1H), 7.31(s, 1H), 7.22(d, 4H), 7.13(d, 1H), 7.10 (d, 4H), 6.99 (t, 2H), 1.62 (m, 6H), 1.38 (m, 6H), 1.14 (t, 6H), 0.90 (t, 9H).

[0334] Synthesis of compound 6

[0335] 3,7-Dibromobenzo[1,2-b:4,5-b']dithiophene-2,6-dione (Compound I-1) (0.20 g, 0.53 mmol), N,N-diphenyl-2-(tributylstannyl)benzo[b]thiophene-6-amine (Compound I-5) (0.66 g, 1.11 mmol), and Pd(PPh 3 ) 4 (0.06 g, 0.05 mmol) was dissolved in 60 mL of toluene and then stirred at 110° C. for 18 hours. When the reaction was complete, toluene was evaporated to concentrate the mixture and the resultant was separated with a dichloromethane: hexane (1:1 volume / volume) column and precipitated in 100 mL of methanol to obtain compound 6 (0.2 g). The yield was 46%.

[0336] Confirmation of molecular weight: LC-MS: 819.11 m / z.

[0337] Synthesis Example 7

[0338] [Reaction Scheme 7]

[0339]

[0340] Synthesis of Compound I-6

[0341] Naphtho[1,2-b:5,6-b']dithiophene (2 g, 8.32 mmol) was dissolved in a THF / ether (100 mL / 100 mL) mixed solvent, 2.5 M n-BuLi (8.32 mL, 20.80 mmol) was added at 0°C, and the mixture was stirred for 4 hours. Subsequently, triisopropyl borate (7.83 g, 41.61 mmol) was slowly added thereto at room temperature and the mixture was further stirred for 4 hours. Then, 1 M HCl was slowly added thereto, the solvent was evaporated to concentrate the mixture, and the resultant was added to 300 mL of HCl. 2 O to precipitate it and filter it to obtain 2.7g of naphtho[1,2-b:5,6-b']dithiophene-2,7-diyldiboronic acid (Compound I-6).

[0342] NMR (300MHz, DMSO): 8.57 (s, 4H), 8.13 (s, 2H), 8.07 (s, 4H).

[0343] Synthesis of Compound I-7

[0344] Naphtho[1,2-b:5,6-b']dithiophene-2,7-diyldiboronic acid (Compound I-6) (2.7 g, 8.23 ​​mmol) and oxone (6.56 g, 21.35 mmol) were dissolved in 150 mL acetone and 40 mL H 2 O and stirred at room temperature for 48 h. When precipitation occurred, it was filtered and washed with acetone and H 2 O washing to obtain 1.7 g of naphtho[1,2-b:5,6-b′]dithiophene-2,7(1H,6H)-dione (I-7). The yield was 76%.

[0345] NMR (300 MHz, CDCl 3 ): 7.54(d, 2H), 7.51(d, 2H), 4.24(s, 4H).

[0346] Synthesis of Compound I-8

[0347] Naphtho[1,2-b:5,6-b']dithiophene-2,7(1H,6H)-dione (Compound I-7) (0.5 g, 1.84 mmol), N-bromosuccinimide (NBS) (1.63 g, 9.18 mmol), and azobisisobutyronitrile (AIBN) (0.03 g, 0.18 mmol) were dissolved in 150 mL of chloroform and stirred at 85 ° C for 18 hours. When the reaction was completed, the resultant was precipitated in 150 mL of MeOH to obtain 0.65 g of 1,1,6,6-tetrabromonaphtho[1,2-b:5,6-b']dithiophene-2,7(1H,6H)-dione (Compound I-8). The yield was 60%.

[0348] NMR (300 MHz, CDCl 3 ): 7.98(d, 2H), 7.66(d, 2H).

[0349] Synthesis of Compound I-9

[0350] 1,1,6,6-tetrabromonaphtho[1,2-b:5,6-b']dithiophene-2,7(1H,6H)-dione (Compound I-8) (0.43 g, 0.73 mmol) and sodium iodide (0.33 g, 2.19 mmol) were dissolved in 20 mL of acetonitrile and 40 mL of chloroform and stirred at room temperature for 18 hours. When the reaction was complete, the resultant was precipitated in 100 mL of acetone to obtain 0.15 g of 1,6-dibromonaphtho[1,2-b:5,6-b']dithiophene-2,7-dione (Compound I-9). The yield was 48%.

[0351] Molecular weight confirmation: MALDI-TOF-MS: 428.95 m / z.

[0352] Synthesis of compound 7

[0353] 1,6-dibromonaphtho[1,2-b:5,6-b']dithiophene-2,7-dione (Compound I-9) (0.15 g, 0.35 mmol), N,N-diphenyl-5-(tributylstannyl)thiophene-2-amine (0.40 g, 0.74 mmol), and Pd(PPh 3 ) 4 (0.04 g, 0.04 mmol) was dissolved in 150 mL of toluene and then stirred at 110° C. for 6 hours. When the reaction was complete, toluene was evaporated to concentrate the mixture and the resultant was separated by a dichloromethane: hexane (1:1 volume / volume) column and then precipitated in 100 mL of methanol to obtain compound 7 (0.05 g). The yield was 20%.

[0354] NMR (300 MHz, CDCl 3 ): 7.67(d, 2H), 7.40(d, 2H), 7.36(d, 8H), 7.30(t, 8H), 7.22(t, 4H), 7.16(d, 2H), 6.58(d, 2H).

[0355] Comparative Synthesis Example 1

[0356] [Reaction Scheme 8]

[0357]

[0358] 3,7-Dibromobenzo[1,2-b:4,5-b']dithiophene-2,6-dione (Compound I-1) (0.30 g, 0.79 mmol), 2-(tributylstannyl)thiophene (0.62 g, 1.67 mmol), and Pd(PPh 3 ) 4 (0.09 g, 0.08 mmol) was dissolved in 50 mL of toluene, and then stirred at 110° C. for 18 hours. When the reaction was completed, toluene was evaporated to concentrate the mixture and the resultant was precipitated in 100 mL of methanol to obtain Compound A (0.2 g). The yield was 66%.

[0359] Confirmation of molecular weight: LC-MS: 384.97 m / z.

[0360] Comparative Synthesis Example 2

[0361] [Reaction Scheme 9]

[0362]

[0363] 3,7-Dibromobenzo[1,2-b:4,5-b']dithiophene-2,6-dione (Compound I-1) (0.90 g, 2.38 mmol), 4-(diphenylamino)phenylboronic acid (1.45 g, 5.01 mmol) and Pd(PPh 3 ) 4 (0.14 g, 0.12 mmol) was dissolved in 100 mL of toluene, to which 10 mL of 1M K 2 CO 3 The solution was stirred at 100° C. for 18 hours. When the reaction was completed, the resultant was extracted with dichloromethane and separated with a dichloromethane:hexane (1:1 volume / volume) column, and precipitated in 100 mL of methanol to obtain compound B (0.7 g). The yield was 42%.

[0364] Confirmation of molecular weight: LC-MS: 707.11 m / z.

[0365] Evaluation I

[0366] The compounds of the synthesis examples and comparative examples were respectively -5 The concentration of M was dissolved in dichloromethane to prepare a solution, and the light absorption characteristics of the compound were evaluated.

[0367] The maximum absorption wavelength (λ) was measured by UV-Vis-NIR spectrometer (UV-3600 Plus, Shimadzu Corp.). 最大 ) to evaluate the light absorption characteristics.

[0368] The results are shown in Table 1.

[0369] Table 1

[0370] <![CDATA[λ 最大 (nm)]]> Synthesis Example 1 867 Synthesis Example 2 802 Synthesis Example 3 817 Synthesis Example 4 834 Synthesis Example 5 862 Synthesis Example 6 844 Synthesis Example 7 912 Comparative Synthesis Example 1 572 Comparative Synthesis Example 2 690

[0371] Referring to Table 1, the compound according to the Synthesis Example exhibited light absorption characteristics in a long wavelength spectrum of greater than or equal to about 700 nm, for example, greater than or equal to about 800 nm, compared with the compound according to the Comparative Synthesis Example.

[0372] Evaluation II

[0373] The compounds obtained in the synthetic examples were respectively -5 The concentration of M was dissolved in dichloromethane to prepare a solution and the light absorption characteristics of the compound were evaluated.

[0374] Light absorption characteristics were obtained by using a Shimadzu UV-3600 Plus UV-Vis-NIR spectrometer to obtain absorption spectra and determine the full width at half maximum (FWHM).

[0375] The results are shown in Table 2.

[0376] Table 2

[0377]

[0378] Referring to Table 2, the compounds according to the synthesis examples exhibited good wavelength selectivity in the near-infrared wavelength spectrum.

[0379] Evaluation III

[0380] The compounds of Synthesis Examples were evaluated for deposition characteristics.

[0381] The deposition characteristics were evaluated by sublimating the compound under a high vacuum of less than or equal to 10 Pa and measuring the weight loss with increasing temperature by a thermogravimetric analysis method.

[0382] The results are shown in Table 3.

[0383] Table 3

[0384] <![CDATA[T s (℃)(-10 wt%)]]> <![CDATA[T s (℃)(-50 wt%)]]> Synthesis Example 1 316 345 Synthesis Example 2 325 366 Synthesis Example 3 298 - Synthesis Example 4 261 - Synthesis Example 5 244 - Synthesis Example 6 348 -

[0385] *T s (°C) (-10 wt%): Temperature at which the sample exhibits a 10 wt% weight loss

[0386] *T s (°C) (-50 wt%): The temperature at which the sample exhibits a 50 wt% weight loss

[0387] Referring to Table 3, the compounds of Synthesis Examples have sufficient heat resistance.

[0388] Example

[0389] An anode of about 150 nm thick was formed by sputtering ITO on a glass substrate. Subsequently, a photoelectric conversion layer of 150 nm thick was formed by co-depositing the compound of Synthesis Example 1 and C60 at a volume ratio of 1:1 on the anode. On the photoelectric conversion layer, an auxiliary layer was formed by depositing C60. Then, a cathode of 7 nm thick was formed on the auxiliary layer by sputtering ITO. Then, alumina (Al2O3) was deposited on the cathode. 2 O 3 ) to form a 50nm thick anti-reflection layer, and it was sealed with a glass sheet to manufacture a photodiode.

[0390] Evaluation IV

[0391] The photoelectric conversion efficiency of the photodiode according to the embodiment was evaluated.

[0392] Photoelectric conversion efficiency can be measured by using an IPCE measurement system (TNE Tech Co., Ltd., Korea). First, the IPCE measurement system is calibrated by using a Si photodiode (Hamamatsu Photonics KK, Japan) and equipped with an organic photodiode to measure external quantum efficiency in a wavelength spectrum of about 550 nm to about 1200 nm.

[0393] Fig.15 is a graph showing the photoelectric conversion efficiency of the photodiode according to the embodiment.

[0394] Reference Fig.15 , the photodiode according to the embodiment exhibits good photoelectric conversion efficiency in the near-infrared wavelength spectrum greater than or equal to about 800 nm.

[0395] While the present disclosure has been described with respect to what are presently considered to be practical example embodiments, it is to be understood that the inventive concepts are not limited to the disclosed example embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A compound represented by chemical formula 1: [Chemical formula 1] in, X 1 and X 2 are each independently O or S, Y 1 and Y 2 For O, Ar is substituted or unsubstituted benzene, or substituted or unsubstituted naphthalene, L 1 and L 2 Each is independently a substituted or unsubstituted group listed in Group 1: [Group 1] in, Z 1 and Z 2 are each independently O or S, and * is the connection point, n is 1, R 1 Represented by one of the chemical formulas A-1 to A-3: in, W 1 O, S, CR f R g , or SiR h R i , W 2 O, S, CR f R g , or SiR h R i , R 20 -R 25 and R f -R i are each independently hydrogen, unsubstituted C1-C30 alkyl, or a combination thereof, and * is the connection point, R 4 Represented by one of the chemical formulas B-1 to B-3: in, W 3 O, S, CR k R l , or SiR m R n , W 4 O, S, CR k R l , or SiR m R n , R 26 -R 31 and R k -R n are each independently hydrogen, unsubstituted C1-C30 alkyl, or a combination thereof, and * is the connection point, and "Substituted" means that the hydrogen of the group is replaced by a substituent selected from the group consisting of C1-C20 alkyl, C1-C30 alkoxy, halogen, and combinations thereof.

2. The compound of claim 1, wherein the compound is represented by one of the chemical formulas 1-J, 1-L, 1-P, 1-R, 1-V, and 1-X: [Chemical Formula 1-J] [Chemical formula 1-L] [Chemical formula 1-P] [Chemical formula 1-R] [Chemical formula 1-V] [Chemical formula 1-X] in, X 1 and X 2 are each independently O or S, Y 1 and Y 2 For O, Ar is substituted or unsubstituted benzene, or substituted or unsubstituted naphthalene, Z 1 and Z 2 are each independently O or S, W 1 O, S, CR f R g , or SiR h R i , W 2 O, S, CR f R g , or SiR h R i , W 3 O, S, CR k R l , or SiR m R n , W 4 O, S, CR k R l , or SiR m R n , R 20 -R 31 , R f -R i , and R k -R n are each independently hydrogen, unsubstituted C1-C30 alkyl, or a combination thereof, m1 and m2 are each independently 1, and "Substituted" means that the hydrogen of the group is replaced by a substituent selected from the group consisting of C1-C20 alkyl, C1-C30 alkoxy, halogen, and combinations thereof.

3. The compound of claim 1, wherein the peak absorption wavelength of the compound is within the wavelength spectrum of 700 nm to 3000 nm.

4. A film comprising the compound according to any one of claims 1 to 3.

5. A photodiode comprising: a first electrode and a second electrode facing each other, and an organic layer between the first electrode and the second electrode, The organic layer comprises the compound according to any one of claims 1 to 3. The photodiode of claim 5 , wherein the organic layer further comprises fullerene or a fullerene derivative.

7. An organic sensor comprising the photodiode according to claim 5 or 6.

8. An electronic device comprising the photodiode according to claim 5 or 6 or the organic sensor according to claim 7.

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