Organic compounds and electronic devices containing them

Abstract

To provide an organic compound that selectively absorbs light in the green wavelength range and has excellent thermal safety, and an electronic element comprising the same.SOLUTION: The compound is represented by general formula (1) in the figure. In formula (1), R1, R2, R3 and R4 each independently represent a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms; at least one of A1 and A2 represents an aryl group or heteroaryl group including an at least 5-membered ring; and A3 is an aryl group or heteroaryl group including an at least 5-membered ring.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to organic compounds and electronic devices containing the same, and more particularly to organic compounds that selectively absorb light in the green wavelength region and electronic devices containing the same. [Background technology]

[0002] A photoelectric element is a device that converts light into an electrical signal using the photoelectric effect, and includes photodiodes and phototransistors, and can be applied to image sensors, solar cells, and the like.

[0003] On the other hand, as the resolution of image sensors, including photodiodes, increases, the size of the pixels is getting smaller and smaller. In the case of silicon photodiodes, which use silicon as the constituent material of such photodiodes, there is a problem that sensitivity decreases because the absorption area decreases as the pixel size decreases.

[0004] Therefore, research is being conducted on organic materials to replace silicon as a component of photodiodes. Organic materials have a high absorption coefficient and can selectively absorb light in specific wavelength ranges depending on their molecular structure, making them very advantageous for improving sensitivity and achieving high integration, as they can simultaneously replace both photodiodes and color filters. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-72270 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention has been made in view of the above-mentioned prior art, and the object of the present invention is to provide an organic compound that selectively absorbs light in the green wavelength region and has excellent thermal safety, and an electronic element containing the same.

Means for Solving the Problem

[0007] An organic compound according to one embodiment of the present invention made to achieve the above object is represented by the following general formula (1).

Chemical Formula

[0008] An organic compound according to one embodiment is represented by the following general formula (1) and has a maximum absorption wavelength (λmax) of 530 nm to 560 nm.

Chemical Formula

[0009] An electronic element according to one aspect of the present invention, made to achieve the above objective, comprises a first electrode and a second electrode facing each other, and an active layer interposed between the first electrode and the second electrode, wherein the active layer contains an organic compound represented by the following general formula (1). [ka] (In the above general formula (1), R 1 , R 2 , R 3 , and R 4 Each of these independently represents a substituted or unsubstituted alkyl (alkyl) group having 1 to 4 carbon atoms, and A 1 and A 2 At least one of them represents an aryl group or heteroaryl group containing at least a 5-membered ring, A 3 This represents an aryl group or heteroaryl group containing at least a 5-membered ring. Specific details of other embodiments are included in the detailed description and drawings. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide an organic compound that selectively absorbs light in the green wavelength region and has excellent thermal safety, and to provide an organic photoelectric element having improved photoelectric conversion efficiency and stable external quantum efficiency (EQE), as well as an image sensor and electronic element including the organic photoelectric element. [Brief explanation of the drawing]

[0011] [Figure 1] This is a cross-sectional view illustrating an example of an organic photoelectric element according to one embodiment. [Figure 2] This is a cross-sectional view illustrating another example of an organic photoelectric element according to one embodiment. [Figure 3] This is a conceptual diagram illustrating an example of an image sensor according to one embodiment. [Figure 4]This is a cross-sectional view illustrating an example of an image sensor according to one embodiment. [Figure 5] This is a cross-sectional view illustrating another example of an image sensor according to one embodiment. [Figure 6] This is a cross-sectional view illustrating yet another example of an image sensor according to one embodiment. [Figure 7] This is a conceptual diagram illustrating another example of an image sensor according to one embodiment. [Figure 8] This is a block diagram illustrating an example of an electronic element according to one embodiment. [Figure 9] This is a block diagram illustrating another example of an electronic element according to one embodiment. [Modes for carrying out the invention]

[0012] The following describes an organic compound according to one embodiment, with reference to examples, manufacturing examples, and comparative examples. However, these are illustrative, and the technical idea of ​​the present invention is not limited to such embodiments.

[0013] An organic compound according to one embodiment is represented by the following general formula (1).

[0014] [ka]

[0015] In the above general formula (1), R 1 , R 2 , R 3 , and R 4Each of these independently represents a substituted or unsubstituted C1-C4 alkyl group, a substituted or unsubstituted C1-C4 alkoxy group, or a substituted or unsubstituted C1-C4 alkylthio group. Examples of C1-C4 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl groups.

[0016] In one embodiment, R 1 , R 2 , R 3 , and R 4 It does not include a ring structure. In one embodiment, R 1 , R 2 , R 3 , and R 4 Each of these is independently a substituted or unsubstituted alkyl (alkyl) group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0017] In one embodiment, R 1 , R 2 , R 3 , and R 4 These each indicate the same substituent. For example, R 1 , R 2 , R 3 , and R 4 These are all methyl groups.

[0018] In the above general formula (1), A 1 and A 2 At least one of them represents an aryl group or heteroaryl group containing at least a 5-membered ring. For example, A 1 and A 2At least one of these represents a heteroaryl group containing a thiophene ring, or an aryl group containing a benzene ring.

[0019] In one embodiment, A 1 and A 2 At least one of these represents a substituted or unsubstituted thienyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzothienyl group.

[0020] For example, A 1 and A 2 At least one of the following groups represents one selected from 2-thienyl, 5-methyl-2-thienyl, phenyl, 4-methylphenyl, 2-naphthyl, 5-methyl-2-benzothienyl, 5-(2-thienyl)-2-thienyl, and 2,4,6-trimethylphenyl. For example, A 1 and A 2 At least one of these represents one of the substituents selected from those represented by the following general formula (2).

[0021] [ka]

[0022] Preferably, A 1 and A 2 These are, respectively, a methylphenyl group (or a tolyl group). More preferably, A 1 and A 2 These are, respectively, a 4-methylphenyl group (or a p-tolyl group).

[0023] In the above general formula (1), A 3 This represents an aryl group or heteroaryl group containing at least a 5-membered ring.

[0024] In one embodiment, A 3 This represents a heteroaryl group comprising a ring with at least 5 members containing a sulfur atom. The ring with at least 5 members containing a sulfur atom includes, for example, monocyclic aromatic compounds or fused ring aromatic compounds containing at least one thiophene ring. Monocyclic aromatic compounds containing a thiophene ring include, but are not limited to, thiophene, thiazole, and thiadiazole. Fused ring aromatic compounds containing a thiophene ring include, but are not limited to, benzothiophene, dibenzothiophene, dithienothiophene, benzodithiophene, thienothiophene, and dithienopyrrole.

[0025] In one embodiment, A 3 This indicates an aryl group containing at least a 6-membered ring. The at least 6-membered ring includes, for example, monocyclic aromatic compounds or fused-ring aromatic compounds containing at least one benzene ring. Fused-ring aromatic compounds containing a benzene ring include, but are not limited to, naphthalene and anthracene.

[0026] For example, A 3 This indicates one of the substituents selected from the following:

[0027] [ka] [ka] [ka] [ka] [ka]

[0028] In one embodiment, the number of rings in the organic compound represented by the general formula (1) is 5 to 8. When the number of rings in the organic compound represented by the general formula (1) is 9 or more, the stability of the organic compound decreases due to steric hindrance.

[0029] The organic compound represented by the above general formula (1) selectively absorbs light in the green wavelength region. In one embodiment, the organic compound represented by the above general formula (1) has a maximum absorption wavelength (λmax) of about 530 nm to about 560 nm in a thin film state. Also in one embodiment, the organic compound represented by the above general formula (1) exhibits an absorption curve with a full width at half maximum (FWHM) of about 50 nm to about 110 nm in a thin film state.

[0030] In one embodiment, the external quantum efficiency (G-EQE) in the green wavelength region of an organic photoelectric element manufactured using the organic compound represented by the general formula (1) is approximately 40% or higher. Preferably, the external quantum efficiency (G-EQE) in the green wavelength region of an organic photoelectric element manufactured using the organic compound represented by the general formula (1) is approximately 50% or higher, more preferably approximately 60% or higher.

[0031] The technical concept of the present invention will be described in more detail below with reference to the following examples, experimental examples, and comparative examples. The following examples, experimental examples, and comparative examples are for illustrative purposes only, and the technical concept of the present invention is not limited thereto.

[0032] [Experimental Example 1] - Synthesis of Chemical Formula 1

[0033] [ka]

[0034] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-2,8-bis(5-methylthiophen-2-yl)-10-(4-(5-methylthiophen-2-yl)phenyl)-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0035] The compound of chemical formula 1 above was synthesized according to reaction formula 1 below.

[0036] [Reaction Equation 1]

[0037] [ka]

[0038] Raw material compound 5,5-difluoro-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was prepared using a reagent manufactured by Tokyo Chemical Industry Co., Ltd.

[0039] In a 30 ml flask, add 5,5-difluoro-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4λ 4,5λ 4 A solution containing 1.0 g (2.2 mmol) of -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine and 20 g of N,N-Dimethylformamide was cooled to 5°C, and 0.86 g (4.8 mmol) of N-Bromosuccinimide was added and the mixture was stirred for 4 hours. Subsequently, the solution was washed, and the oil layer was concentrated under reduced pressure to obtain 1.0 g of a red solid.

[0040] Subsequently, 1.0 g of the obtained red solid was mixed with 0.74 g (5.2 mmol) of 5-Methyl-2-thiopheneboronic Acid, 0.15 g (0.26 mmol) of Bis(dibenzylideneacetone)palladium, 0.15 g (0.51 mmol) of Tri-tert-butylphosphonium tetrafluoroborate, 2.1 g (15.3 mmol) of Potassium carbonate, 10 g of Tetrahydrofuran, and 5.0 g of water, and heated under reflux and stirred for 8 hours. Subsequently, the solution was cooled to room temperature, washed with toluene and water, and the oil layer was concentrated under reduced pressure and then purified by sublimation to obtain 0.19 g of the compound of chemical formula 1.

[0041] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 1 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.47(s,6H),2.48(s,6H),2.53(s,3H),2.60(s,6H),6.63(d,J=3.6Hz,2H),6.71(dd,J=3.2,1.2 Hz,2H),6.77(d,J=2.4Hz,1H),7.22(d,J=3.6Hz,1H),7.30(d,J=8.0Hz,2H),7.69(d,J=8.4Hz,2H)

[0042] [Experimental Example 2] - Synthesis of Chemical Formula 2

[0043] [ka]

[0044] (IUPAC name:5,5-difluoro-1,3,7,9-tetramethyl-2,8-di(thiophen-2-yl)-10-(4-(thiophen-2-yl)phenyl)-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0045] The compound of chemical formula 2 was synthesized in the same manner as in Experimental Example 1, except that 5-Methyl-2-thiopheneboronic Acid was replaced with 2-thiopheneboronic Acid. That is, the compound of chemical formula 2 was synthesized according to the following reaction equation 2.

[0046] [Reaction Equation 2]

[0047] [ka]

[0048] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 2 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.48(s,6H),2.61(s,6H),6.86(dd,J=3.6,0.8Hz,2H),7.06-7.10(m,2H),7. 10-7.14(m,1H),7.32-7.36(m,5H),7.43(d,J=3.6Hz,1H),7.78(d,J=8.0Hz,2H)

[0049] [Experimental Example 3] - Synthesis of Chemical Formula 3

[0050] [ka]

[0051] (IUPAC name:2-([2,2'-bithiophen]-5-yl)-5,5-difluoro-1,3,7,9-tetramethyl-10-(4-(5-methylthiophen-2-yl)phenyl)-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0052] The compound of chemical formula 3 above was synthesized according to reaction formula 3 below.

[0053] [Reaction Equation 3]

[0054] [ka]

[0055] Raw material compound 5,5-difluoro-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was prepared using a reagent manufactured by Tokyo Chemical Industry Co., Ltd.

[0056] In a 30 ml flask, add 5,5-difluoro-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine 1.0 g (2.2 mmol), 5-Methyl-2-thiopheneboronic Acid 0.45 g (3.2 mmol), Bis(dibenzylideneacetone)palladium 65 mg (0.11 mmol), Tri-tert-butylphosphonium tetrafluoroborate 65 mg (0.22 mmol), Potassium carbonate 0.80 g (5.8 mmol), Tetrahydrofuran 10 g, and water 5.0 g were added and heated under reflux and stirred for 8 hours. Subsequently, the solution was cooled to room temperature and washed with toluene and water, and the oil layer was concentrated under reduced pressure to obtain 0.90 g of a red solid.

[0057] Subsequently, 0.90 g of the obtained red solid was mixed with 20 g of N,N-Dimethylformamide, and the solution was cooled to 5°C. 0.39 g (2.2 mmol) of N-Bromosuccinimide was added and the mixture was stirred for 4 hours. The solution was then washed with water, and the oil layer was concentrated to obtain 0.9 g of red solid.

[0058] Subsequently, 0.9 g of the obtained red solid was mixed with 0.68 g of 5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolane-2-yl)-2,2'-bithiophene, 0.052 g (0.09 mmol) of Bis(dibenzylideneacetone)palladium, 0.052 g (0.18 mmol) of Tri-tert-butylphosphonium tetrafluoroborate, 0.75 g (5.4 mmol) of Potassium carbonate, 10 g of Tetrahydrofuran, and 5.0 g of water, and heated under reflux and stirred for 8 hours. Subsequently, the solution was cooled to room temperature, washed with toluene and water, and the oil layer was concentrated under reduced pressure and then purified by sublimation to obtain 0.3 g of the compound of chemical formula 3 described above.

[0059] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 3 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.49(s,3H),1.50(s,3H),2.54(s,3H),2.59(s,3H),2.63(s,3H),6.04 (s,1H),6.74(d,J=3.6Hz,1H),6.77(d,J=2.4Hz,1H),6.98-7.02(m,1H), 7.13(d,J=3.6Hz,1H),7.14(dd,J=3.6,1.2Hz,1H),7.20(dd,J=5.2,1.2Hz,1H),7.23(d,J=3.6Hz,1H),7.28(d,J=8.4Hz,2H),7.70(d,J=8.4Hz,2H)

[0060] [Experimental Example 4] - Synthesis of Chemical Formula 4

[0061] [ka]

[0062] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-10-(4-(5-methylthiophen-2-yl)phenyl)-2,8-di-p-tolyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0063] The compound of chemical formula 4 was synthesized in the same manner as in Experimental Example 3, except that 5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolane-2-yl)-2,2'-bithiophene was replaced with 4-Methylphenylboronic Acid. That is, the compound of chemical formula 4 was synthesized according to the following reaction equation 4.

[0064] [Reaction Equation 4]

[0065] [ka]

[0066] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 4 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.39(s,6H),2.37(s,6H),2.52(s,3H),2.53(s,6H),6.75(dd,J=3.6,0.9Hz,1H),7.05(d,J=1 0.0Hz,4H),7.20(d,J=10.0Hz,4H),7.22(s,1H),7.32(d,J=10.0Hz,2H),7.68(d,J=10.0Hz,2H)

[0067] [Experimental Example 5] - Synthesis of Chemical Formula 5

[0068] [ka]

[0069] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-10-(4-(thiophen-2-yl)phenyl)-2,8-di-p-tolyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0070] The compound of chemical formula 5 was synthesized in the same manner as in Experimental Example 4, except that 5-Methyl-2-thiopheneboronic Acid was replaced with 2-thiopheneboronic Acid. That is, the compound of chemical formula 5 was synthesized according to the following reaction equation 5.

[0071] [Reaction Equation 5]

[0072] [ka]

[0073] 1Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 5 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.39(s,6H), 2.37(s,6H),2.54(s,6H),7.06(d,J=8.4Hz,4H),7.10-7.13(m,1H),7.20(d,J=7.6Hz,4H) ),7.33(d,J=5.2Hz,1H),7.36(d,J=8.4Hz,2H),7.42(d,J=3.6,1H),7.76(d,J=8.4Hz,2H)

[0074] [Experimental Example 6] - Synthesis of Chemical Formula 6

[0075] [ka]

[0076] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-10-(4-(5-methylthiophen-2-yl)phenyl)-2,8-diphenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0077] The compound of chemical formula 6 was synthesized in the same manner as in Experimental Example 4, except that 4-Methylphenylboronic Acid was replaced with Phenylboronic Acid. That is, the compound of chemical formula 6 was synthesized according to the following reaction equation 6.

[0078] [Reaction Equation 6]

[0079] [ka]

[0080] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 6 described above was produced. 1H-NMR (CDCl3, ppm): δ = 1.40 (s, 6H), 2.52 (s, 6H), 2.54 (s, 3H), 6.76 (d, J = 2.4 Hz, 1H), 7.15 - 7.18 (m, 4H), 7.21 (d, J = 3.6 Hz, 1H), 7.30 - 7.44 (m, 8H), 7.69 (d, J = 8.0 Hz, 2H)

[0081] [Experimental Example 7] - Synthesis of Chemical Formula 7

[0082] [Chem.]

[0083] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-... 4 ,5λ 4 -dipyrrolo[1,2-c:2’,1’-f][1,3,2]diazaborinine)

[0084] In the above Experimental Example 1, except that the raw material compound 5,5-difluoro-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 [[ID=...]]-dipyrrolo[1,2-c:2’,1’-f][1,3,2]diazaborinine was replaced with 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2’,1’-f][1,3,2]diazaborinine, and 5-Methyl-2-thiopheneboronic Acid was replaced with 4-Methylphenylboronic Acid, the compound of Chemical Formula 7 was synthesized in the same manner as in Experimental Example 1 above. The raw material compound 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4-Dipyrrolo[1,2-c:2’,1’-f][1,3,2]diazaborinine was synthesized using a reagent manufactured by Merck. That is, the compound of Chemical Formula 7 above was synthesized according to Reaction Formula 7 below.

[0085] [Reaction Formula 7]

[0086] [Chem.]

[0087] 1 Using 1H-NMR analysis, it was confirmed that the compound of Chemical Formula 7 above was produced. 1H-NMR (CDCl3, ppm): δ = 1.30 (s, 6H), 2.37 (s, 6H), 2.53 (s, 6H), 7.05 (d, J = 8.1 Hz, 4H), 7.19 (d, J = 7.7 Hz, 4H), 7.35 (dd, J1 = 7.5 Hz, J2, = 1.9 Hz, 2H), 7.45 - 7.52 (m, 3H)

[0088] [Experimental Example 8] - Synthesis of Chemical Formula 8

[0089] [Chem.] [[ID=3l]] <000059l>

[0090] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-10-(o-tolyl)-2,8-di-p-tolyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2’,1’-f][1,3,2]diazaborinine)

[0091] " In Experimental Example 7 above, the starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine 5,5-difluoro-1,3,7,9-tetramethyl-10-(o-tolyl)-5H-4λ 4 ,5λ 4 The compound of chemical formula 8 was synthesized in the same manner as in Experimental Example 7, except that -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was substituted. Starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-(o-tolyl)-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was synthesized by the method described in the literature (Journal of the American Chemical Society, 129(17), 5597-5604 (2007)). That is, the compound of chemical formula 8 above was synthesized according to reaction formula 8 below.

[0092] [Reaction Equation 8]

[0093] [ka]

[0094] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 8 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.29(s,6H),2.28(s,3H),2.37(s,6H),2.54(s,6H),7.06(d,J=10.0Hz,4H),7.20(d,J=10.0Hz,4H),7.21-7.38(m,4H)

[0095] [Experimental Example 9] - Synthesis of Chemical Formula 9

[0096] [ka]

[0097] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-10-(m-tolyl)-2,8-di-p-tolyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0098] In Experimental Example 7 above, the starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine 5,5-difluoro-1,3,7,9-tetramethyl-10-(m-tolyl)-5H-4λ 4 ,5λ 4 The compound of chemical formula 9 was synthesized in the same manner as in Experimental Example 7, except that -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was substituted. Starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-(m-tolyl)-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was synthesized by substituting m-tolualdehyde for o-tolualdehyde using the method described in the literature (Journal of the American Chemical Society, 129(17), 5597-5604 (2007)). That is, the compound of chemical formula 9 above was synthesized according to reaction formula 9 below.

[0099] [Reaction Equation 9]

[0100] [ka]

[0101] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 9 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.32(s,6H),2.37(s,6H),2.39(s,3H),2.53(s,6H),7.05(d,J=10.0Hz,4H),7.19(d,J=10.0Hz,4H),7.12-7.39(m,4H)

[0102] [Experimental Example 10] - Synthesis of Chemical Formula 10

[0103] [ka]

[0104] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-tri-p-tolyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0105] In Experimental Example 7 above, the starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine 5,5-difluoro-1,3,7,9-tetramethyl-10-(p-tolyl)-5H-4λ 4 ,5λ 4 The compound of chemical formula 10 was synthesized in the same manner as in Experimental Example 7, except that -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was substituted. Starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-(p-tolyl)-5H-4λ 4 ,5λ 4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was synthesized by substituting p-tolualdehyde for o-tolualdehyde using the method described in the literature (Journal of the American Chemical Society, 129(17), 5597-5604 (2007)). That is, the compound of chemical formula 10 above was synthesized according to reaction formula 10 below.

[0106] [Reaction Equation 10]

[0107] [ka]

[0108] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 10 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.32(s,6H),2.37(s,6H),2.42(s,3H),2.53(s,6H),7.05(d,J=10.0Hz,4H),7.19(d,J=10.0Hz,4H),7.18-7.30(m,4H)

[0109] [Experimental Example 11] - Synthesis of Chemical Formula 11

[0110] [ka]

[0111] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-10-(naphthalen-1-yl)-2,8-di-p-tolyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0112] In Experimental Example 7 above, the starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine 5,5-difluoro-1,3,7,9-tetramethyl-10-(naphthalen-1-yl)-5H-4λ 4 ,5λ 4 The compound of chemical formula 11 was synthesized in the same manner as in Experimental Example 7, except that -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was substituted. Starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-(naphthalen-1-yl)-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was synthesized by substituting o-tolualdehyde with 1-naphthaldehyde using the method described in the literature (Journal of the American Chemical Society, 129(17), 5597-5604 (2007)). That is, the compound of chemical formula 11 above was synthesized according to the reaction formula 11 below.

[0113] [Reaction Equation 11]

[0114] [ka]

[0115] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 11 described above was produced. 1H-NMR (CDCl3, ppm): δ=0.98(s,6H),2.34(s,6H),2.57(s,6H),7.01(d,J=7.9Hz,4H),7.15(d,J=7.9Hz,4H ),7.46-7.54(m,3H),7.57(t,J=7.6Hz,1H),7.88(d,J=7.3Hz,1H),7.91-7.96(m,2H)

[0116] [Experimental Example 12] - Synthesis of Chemical Formula 12

[0117] [ka]

[0118] (IUPAC name: 10-(anthracen-9-yl)-5,5-difluoro-1,3,7,9-tetramethyl-2,8-di-p-tolyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0119] In Experimental Example 7 above, the starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine 10-(anthracen-9-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 The compound of chemical formula 12 was synthesized in the same manner as in Experimental Example 7, except that -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was substituted. Starting compound 10-(anthracen-9-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was synthesized by substituting o-Tolualdehyde with Anthracene-9-carbaldehyde using the method described in the literature (Journal of the American Chemical Society, 129(17), 5597-5604 (2007)). That is, the compound of chemical formula 12 above was synthesized according to the reaction formula 12 below.

[0120] [Reaction Equation 12]

[0121] [ka]

[0122] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 12 described above was produced. 1H-NMR (CDCl3, ppm): δ=0.58(s,6H),2.31(s,6H),2.61(s,6H),6.95(d,J=8.0Hz,4H),7.10(d,J=8.0Hz,4H),7.48(m,4H),8.03(s,4H),8.57(s,1H)

[0123] [Experimental Example 13] - Synthesis of Chemical Formula 13

[0124] [ka]

[0125] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-10-(5-methylthiophen-2-yl)-2,8-di-p-tolyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0126] In Experimental Example 7 above, the starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine 5,5-difluoro-1,3,7,9-tetramethyl-10-(5-methylthiophene-2-yl)-5H-4λ 4 ,5λ 4 The compound of chemical formula 13 was synthesized in the same manner as in Experimental Example 7, except that -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was substituted. Starting compound 5,5-difluoro-1,3,7,9-tetramethyl-10-(5-methylthiophene-2-yl)-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine was synthesized by substituting o-tolualdehyde with 5-methylthiophene-2-carboxaldehyde using the method described in the literature (Journal of the American Chemical Society, 129(17), 5597-5604 (2007)). That is, the compound of chemical formula 13 above was synthesized according to the reaction formula 13 below.

[0127] [Reaction Equation 13]

[0128] [ka]

[0129] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 13 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.60(s,6H),2.39(s,6H),2.52(s,6H),2.55(s,3H),6.75-6.80(m,2H),7.08(d,J=8Hz,4H),7.21(d,J=8Hz,4H)

[0130] [Experimental Example 14] - Synthesis of Chemical Formula 14

[0131] [ka]

[0132] (IUPAC name: 5,5-difluoro-2,8-dimesityl-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0133] The compound of chemical formula 14 was synthesized in the same manner as in Experimental Example 7, except that 4-Methylphenylboronic Acid was replaced with 2,4,6-Trimethylphenylboronic Acid. That is, the compound of chemical formula 14 was synthesized according to the following reaction equation 14.

[0134] [Reaction Equation 14]

[0135] [ka]

[0136] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 14 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.09(s,6H),1.96(s,12H),2.29(s,6H),2.31(s,6H),7.38-7.42(m,2H),7.44-7.49(m,3H)

[0137] [Experimental Example 15] - Synthesis of Chemical Formula 15

[0138] [ka]

[0139] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-2,8-bis(5-methylbenzo[b]thiophen-2-yl)-10-phenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0140] The compound of chemical formula 15 was synthesized in the same manner as in Experimental Example 7, except that 4-Methylphenylboronic Acid was replaced with 5-Methylbenzo[b]thiophene-2-boronic Acid. That is, the compound of chemical formula 15 was synthesized according to the following reaction equation 15.

[0141] [Reaction Equation 15]

[0142] [ka]

[0143] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 15 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.26(s,6H),2.45(s,6H),2.47(s,6H),7.18-7.22(m,5H),7.24(s,1H),7.36-7.54(m,5H),7.77(d,J=8.8Hz,2H)

[0144] [Experimental Example 16] - Synthesis of Chemical Formula 16

[0145] [ka]

[0146] (IUPAC name: 5,5-difluoro-1,3,7,9-tetramethyl-2,8-bis(5-methylbenzo[b]thiophen-2-yl)-10-(p-tolyl)-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)

[0147] The compound of chemical formula 16 was synthesized in the same manner as in Experimental Example 10, except that 4-Methylphenylboronic Acid was replaced with 5-Methylbenzo[b]thiophene-2-boronic Acid. That is, the compound of chemical formula 16 was synthesized according to the following reaction equation 16.

[0148] [Reaction Equation 16]

[0149] [ka]

[0150] 1 Using 1H-NMR analysis, it was confirmed that the compound of chemical formula 16 described above was produced. 1H-NMR (CDCl3, ppm): δ=1.28(s,6H),2.41(s,3H),2.45(s,6H),2.47(s,6H),7.18-7.23(m,5H),7.23-7.33(m,5H),7.77(d,J=8.4Hz,2H)

[0151] [Comparative Example 1]

[0152] [ka]

[0153] [Comparative Example 2]

[0154] [ka]

[0155] [Comparative Example 3]

[0156] [Chemical Formula]

[0157] [Comparative Example 4]

[0158] [Chemical Formula]

[0159] [Evaluation of Absorption Characteristics]≪

[0160] In order to evaluate the absorption characteristics of the above Experimental Examples 1 to 16 and the above Comparative Examples 1 to 4, the maximum absorption wavelength (λmax), full width at half maximum (FWHM), and extinction coefficient were measured in the thin film state and shown in Table 1 below.

[0161] [Table 1]

[0162] As shown in Table 1 above, Experimental Examples 1 to 16 have a maximum absorption wavelength (λmax) of about 530 nm to about 560 nm in the thin film state and show an absorption curve with a relatively narrow full width at half maximum of about 50 nm to about 110 nm in the thin film state. That is, Experimental Examples 1 to 16 show excellent selective absorbance for light in the green wavelength region.

[0163] In contrast, R 1 , R 2 , R 3 , and R 4In the case of Comparative Example 3, which uses the above chemical formula 19 having a hydrogen atom at the corresponding position, it can be seen that it has a maximum absorption wavelength (λmax) in the region of approximately 600 nm or more. That is, it can be seen that Comparative Example 3 exhibits absorption characteristics not only for light in the green wavelength region but also for light in other wavelength regions such as the red wavelength region.

[0164] Also, R 1 and R 4 R has a heteroaryl group at the corresponding position. 2 and R 4 In the case of Comparative Example 4, which uses the above chemical formula 20 having a hydrogen atom at the corresponding position, it can be seen that in the thin film state, it has a maximum absorption wavelength (λmax) in a region other than approximately 530 nm to approximately 560 nm. That is, it can be seen that Comparative Example 4 exhibits absorption characteristics not only for light in the green wavelength region but also for light in other wavelength regions such as the blue wavelength region or the red wavelength region.

[0165] [Evaluation of thermal safety]

[0166] To evaluate the thermal safety of Experimental Examples 1-16 and Comparative Examples 1 and 2, the transition temperature (Tm), sublimation temperature (Ts), and thermal degradation temperature (Td) were measured and are shown in Table 2 below.

[0167] [Table 2]

[0168] As shown in Table 2 above, experimental examples 1 to 16 generally exhibit high transition temperatures (Tm). Furthermore, the thermal decomposition temperatures (Td) of experimental examples 1 to 16 are significantly higher than the sublimation temperatures (Ts). This indicates that experimental examples 1 to 16 demonstrate excellent thermal safety.

[0169] ≪[Evaluation of element performance]≫

[0170] In order to evaluate the performance of the organic optoelectronic devices manufactured using the above Experimental Examples 1 to 16, and the above Comparative Examples 1 and 2, Production Examples 1 to 18 were manufactured as follows.

[0171] [Production Example 1]

[0172] A first electrode layer made of ITO was formed on a glass substrate. Subsequently, an electron blocking layer made of molybdenum oxide with a thickness of 30 nm was formed on the first electrode layer. Subsequently, the compound of Chemical Formula 1 and fullerene C60 (Frontier Carbon Company Ltd.) were co-deposited at a volume ratio of 3:2 to form an active layer with a thickness of 100 nm. Subsequently, an organic optoelectronic device was manufactured by forming a second electrode with a thickness of 100 nm by vacuum-depositing aluminum (Al) on the active layer.

[0173] [Production Examples 2 to 18]

[0174] An organic optoelectronic device was manufactured in the same manner as Production Example 1, except that Chemical Formula 1 was replaced with Chemical Formulas 2 to 18 in Production Example 1. Subsequently, the external quantum efficiency (G-EQE) in the green wavelength region, the external quantum efficiency (B-EQE) in the blue wavelength region, and the external quantum efficiency (R-EQE) in the red wavelength region of Production Examples 1 to 18 were measured and shown in Table 3 below.

[0175]

Table 3

[0176] As shown in Table 3 above, it can be seen that the organic optoelectronic devices of Production Examples 1 to 16 using Chemical Formulas 1 to 16 exhibit excellent external quantum efficiency (EQE) of about 40% or more in the green wavelength region.

[0177] In contrast, A 1 or A 2In the case of the above production example 17, which uses the above chemical formula 17 that does not have an aryl group or heteroaryl group at the corresponding position, it can be seen that it exhibits a relatively low external quantum efficiency (EQE) of about 29% in the green wavelength region compared to the organic photoelectric elements of production examples 1 to 16.

[0178] Also, A 3 In the case of the above manufacturing example 18, which uses the above chemical formula 18 that does not have an aryl group or heteroaryl group at the corresponding position, it can be seen that it exhibits a relatively lower external quantum efficiency (EQE) in the green wavelength region, approximately 30%, compared to the organic photoelectric elements of the above manufacturing examples 1 to 16.

[0179] This demonstrates that the above manufacturing examples 1 to 16 exhibit excellent selective absorbance for light in the green wavelength region.

[0180] An organic photoelectric element according to one embodiment will be described below with reference to examples and drawings. However, these are illustrative examples, and the technical concept of the present invention is not limited to such embodiments.

[0181] Figure 1 is a cross-sectional view illustrating an example of an organic photoelectric element according to one embodiment. For the sake of clarity, parts that overlap with the above-mentioned content will be briefly explained or omitted.

[0182] Referring to Figure 1, the organic photoelectric element according to this embodiment includes a first electrode 110, an active layer 120, and a second electrode 130.

[0183] The first electrode 110 and the second electrode 130 face each other. The active layer 120 is interposed between the first electrode 110 and the second electrode 130. One of the first electrode 110 and the second electrode 130 is the anode, and the other is the cathode.

[0184] In one embodiment, at least one of the first electrode 110 and the second electrode 130 is a light-transmitting electrode. The light-transmitting electrode includes, but is not limited to, at least one of ITO (Indium Tin Oxide), ZnO (Zinc Oxide), SnO2 (Tin Dioxide), ATO (Antimony-doped Tin Oxide), AZO (Aluminium-doped Zinc Oxide), GZO (Gallium-doped Zinc Oxide), TiO2 (Titanium Dioxide), FTO (Fluorine-doped Tin Oxide), and combinations thereof.

[0185] In one embodiment, at least one of the first electrode 110 and the second electrode 130 includes a single-layer or multi-layer metal film. In one embodiment, one of the first electrode 110 and the second electrode 130 is an opaque electrode. The opaque electrode includes, but is not limited to, aluminum (Al).

[0186] The active layer 120 contains a p-type semiconductor material and an n-type semiconductor material, forming a pn junction. The active layer 120 receives light from the outside to generate excitons and separates the generated excitons into holes and electrons.

[0187] The active layer 120 contains an organic compound represented by the general formula (1) above. For example, the active layer 120 contains compounds of chemical formulas 1 to 16 above as a p-type semiconductor material.

[0188] In one embodiment, the active layer 120 containing the organic compound represented by the general formula (1) has a maximum absorption wavelength (λmax) of approximately 530 nm to approximately 560 nm. Furthermore, the active layer 120 containing the organic compound represented by the general formula (1) exhibits an absorption curve with a full width at half maximum (FWHM) of approximately 50 nm to approximately 110 nm. As a result, the active layer 120 selectively absorbs light in the green wavelength region.

[0189] The active layer 120 consists of a single layer or multiple layers. In one embodiment, the active layer 120 consists of a single layer of an intrinsic layer, multiple layers including a p-type layer and an intrinsic layer, multiple layers including an intrinsic layer and an n-type layer, multiple layers including a p-type layer, an intrinsic layer and an n-type layer, or multiple layers including a p-type layer and an n-type layer, but is not limited thereto. As an example, the active layer 120 includes an intrinsic layer containing an organic compound represented by the above general formula (1). As another example, the active layer 120 includes a p-type layer containing an organic compound represented by the above general formula (1).

[0190] In one embodiment, the active layer 120 further comprises an n-type semiconductor material. The n-type semiconductor material includes, but is not limited to, fullerene, fullerene derivatives, or combinations thereof. Fullerene is C60, but is not limited to that. Fullerene derivatives mean compounds having substituents on fullerene. Fullerene derivatives include, but are not limited to, substituents such as alkyl groups, aryl groups, and heterocyclic groups.

[0191] In one embodiment, the volume ratio of the organic compound represented by the general formula (1) to the fullerene in the active layer 120 is approximately 7:3 to approximately 3:7.

[0192] In one embodiment, the active layer 120 has a bulk heterojunction (BHJ) structure of an organic compound represented by the general formula (1) and an n-type semiconductor material.

[0193] In one embodiment, the active layer 120 has a thickness of approximately 50 nm to approximately 200 nm.

[0194] When light in a predetermined wavelength range passes through at least one of the first electrode 110 and the second electrode 130 and is absorbed by the active layer 120, an exciton is generated within the active layer 120. The generated exciton is separated into holes and electrons in the active layer 120. The separated holes move to the anode side, which is either the first electrode 110 or the second electrode 130, and the separated electrons move to the cathode side, which is the other of the first electrode 110 or the second electrode 130, causing an electric current to flow through the organic photoelectric element.

[0195] Figure 2 is a cross-sectional view illustrating another example of an organic photoelectric element according to one embodiment. For the sake of clarity, any overlap with the explanation using Figure 1 will be briefly explained or omitted.

[0196] Referring to Figure 2, the organic photoelectric element according to this embodiment further includes a first charge auxiliary layer 140 and a second charge auxiliary layer 150.

[0197] The first charge auxiliary layer 140 is interposed between the first electrode 110 and the active layer 120. The second charge auxiliary layer 150 is interposed between the second electrode 130 and the active layer 120. The first charge auxiliary layer 140 and the second charge auxiliary layer 150 perform the function of increasing the photoelectric conversion efficiency by facilitating the movement of holes and electrons separated from the active layer 120.

[0198] The first charge auxiliary layer 140 and the second charge auxiliary layer 150 each include, respectively, a hole injecting layer (HIL) for facilitating hole injection, a hole transporting layer (HTL) for facilitating hole transport, an electron blocking layer (EBL) for reducing or blocking electron movement, an electron injecting layer (EIL) for facilitating electron injection, an electron transporting layer (ETL) for facilitating electron transport, a hole blocking layer (HBL) for reducing or blocking hole movement, and at least one combination thereof.

[0199] The first charge auxiliary layer 140 and the second charge auxiliary layer 150 each contain at least one of an organic substance, an inorganic substance, and a combination thereof. The organic substance is, for example, an organic compound having hole or electron injection and / or transfer properties. The inorganic substance is, for example, a metal oxide. For example, the inorganic substance contains at least one of molybdenum oxide, tungsten oxide, nickel oxide, and a combination thereof.

[0200] The hole transport layer (HTL) and electron barrier layer (EBL) are, for example, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS, and polyaryleneamine, respectively. This includes, but is not limited to, at least one of the following: amine), poly(N-vinylcarbazole), polyaniline, polypyrrole, N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine (TPD), 4,4'-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl (α-NPD), m-MTDATA, 4,4',4'-tris(N-carbazolyl)-triphenylamine (TCTA), and combinations thereof.

[0201] The electron transport layer (ETL) and hole barrier layer (HBL) include, for example, at least one of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA), bathocuproine (BCP), LiF,Alq3 (tris(8-hydroxyquinolinato)aluminium), Gaq3 (tris(8-hydroxyquinoline)gallium), Inq3 (tris(8-hydroxyquinoline)indium), Znq2 (bis(8-hydroxyquinoline)zinc), Zn(BTZ)2 (bis(2-(2-hydroxyphenyl)benzothiazolate)zinc), BeBq2 (bis(10-hydroxybenzo[h]quinolinato)beryllium), and combinations thereof, respectively.

[0202] Figure 2 shows only the case where both the first charge auxiliary layer 140 and the second charge auxiliary layer 150 are formed, but this is illustrative. For example, an organic photoelectric element according to one embodiment does not include one of the first charge auxiliary layer 140 and the second charge auxiliary layer 150.

[0203] An organic photoelectric element according to one embodiment comprises an active layer 120 containing an organic compound represented by the general formula (1) above, and thus has improved photoelectric conversion efficiency and stable external quantum efficiency (EQE).

[0204] The organic photoelectric elements described above using Figures 1 and 2 can be applied to image sensors, solar cells, photodetectors, light sensors, and organic light-emitting diodes, but are not limited to these applications.

[0205] An image sensor according to one embodiment will be described below with reference to examples and drawings. However, these are illustrative examples, and the technical concept of the present invention is not limited to such embodiments.

[0206] Figure 3 is a conceptual diagram illustrating an example of an image sensor according to one embodiment. For the sake of explanation, parts that overlap with the above content will be briefly explained or omitted.

[0207] Referring to Figure 3, the image sensor according to this embodiment includes a first pixel PX1.

[0208] The first pixel PX1 is formed in an optical stack structure, comprising a stacked first layer 10 and a second layer 20. In this embodiment, the first layer 10 contains two red R unit pixels and two blue B unit pixels, and the second layer 20 contains a green G unit pixel.

[0209] In this embodiment, the second layer 20 contains an organic compound represented by the general formula (1) described above. Therefore, the image sensor according to this embodiment has improved photoelectric conversion efficiency and stable external quantum efficiency (EQE).

[0210] Figure 4 is a cross-sectional view illustrating an example of an image sensor according to one embodiment. For the sake of clarity, parts that overlap with the above-mentioned content will be briefly explained or omitted.

[0211] Referring to Figure 4, the image sensor according to this embodiment includes a substrate 210, a first photoelectric conversion layer 210B, a second photoelectric conversion layer 210R, a first interlayer insulating film 220, a second interlayer insulating film 230, a first color filter 240B, a second color filter 240R, a first electrode 110, an active layer 120, and a second electrode 130.

[0212] The substrate 210 is a semiconductor substrate containing a semiconductor material. For example, the substrate 210 is bulk silicon or SOI (silicon-on-insulator). The substrate 210 is a silicon substrate or contains other materials, such as silicon germanium, indium antimonide, lead tellurium compounds, indium arsenide, indium phosphide, gallium arsenide, or gallium antimonide. Alternatively, the substrate 210 is a base substrate on which an epitaxial layer is formed.

[0213] Various transistors (not shown) are formed on the substrate 210 for processing electrical signals, which are connected to the first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R, as described later. For example, transfer transistors, reset transistors, source follower transistors, or selection transistors are formed on the substrate 210, but are not limited to these.

[0214] In this embodiment, a storage node 215 is formed within the substrate 210. The storage node 215 is electrically connected to the active layer 120, which will be described later. The storage node 215 stores the charge generated from the active layer 120.

[0215] In one embodiment, metal wiring (not shown) and pads (not shown) are formed on a substrate 210. The metal wiring and pads are formed, for example, on the upper or lower surface of the substrate 210. The metal wiring and pads include, but are not limited to, metals having relatively low resistivity to prevent signal delay, such as aluminum (Al), copper (Cu), silver (Ag), or alloys thereof.

[0216] The first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R are formed within the substrate 210. The first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R are formed by doping the substrate 210 with impurities. For example, the first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R are formed by ion implantation of n-type impurities into a p-type substrate 210. The first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R generate charge in proportion to the amount of light supplied from the outside.

[0217] The first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R include, but are not limited to, at least one of a photodiode, phototransistor, photogate, pinned photodiode, organic photodiode, quantum dot, and combinations thereof, respectively.

[0218] In this embodiment, the first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R sense light in different wavelength regions. For example, the first photoelectric conversion layer 210B senses light in the blue wavelength region, and the second photoelectric conversion layer 210R senses light in the red wavelength region.

[0219] The first interlayer insulating film 220 and the second interlayer insulating film 230 are sequentially laminated on the substrate 210. The first interlayer insulating film 220 and the second interlayer insulating film 230 include, but are not limited to, at least one of silicon oxide, silicon nitride, SiC, SiCOH, SiCO, SiOF, and combinations thereof, respectively.

[0220] The first color filter 240B and the second color filter 240R are formed on the first interlayer insulating film 220. For example, the first color filter 240B and the second color filter 240R are formed within the second interlayer insulating film 230.

[0221] The first color filter 240B and the second color filter 240R are arranged to correspond to their respective photoelectric conversion layers (210B and 210R). For example, the first color filter 240B is arranged to overlap the first photoelectric conversion layer 210B, and the second color filter 240R is arranged to overlap the second photoelectric conversion layer 210R.

[0222] The first color filter 240B and the second color filter 240R have a variety of colors due to the photoelectric conversion layers 210B and 210R. For example, the first color filter 240B and the second color filter 240R each include a red filter, a green filter, or a blue filter. However, this is illustrative, and the first color filter 240B and the second color filter 240R each include a yellow filter, a magenta filter, and a cyan filter, and may further include a white filter. In one embodiment, the first color filter 240B is a blue B filter, and the second color filter 240R is a red R filter.

[0223] The first electrode 110, the active layer 120, and the second electrode 130 are formed sequentially on the second interlayer insulating film 230. The first electrode 110, the active layer 120, and the second electrode 130 are the same as described above in the explanation of Figure 1, so a detailed explanation will be omitted below.

[0224] In one embodiment, the first electrode 110 is electrically connected to the storage node 215 by a through-via 235. For example, the through-via 235 penetrates the first interlayer insulating film 220 and the second interlayer insulating film 230 to electrically connect the first electrode 110 and the storage node 215. As a result, the charge generated in the active layer 120 by light is transferred to the storage node 215.

[0225] In one embodiment, a microlens (not shown) is formed on the second electrode 130. The microlens has a convex shape and a predetermined radius of curvature. As a result, the microlens focuses the incident light. The microlens includes, but is not limited to, a light-transmitting resin.

[0226] In one embodiment, the image sensor in Figure 4 constitutes the first pixel PX1 in Figure 3. For example, the first photoelectric conversion layer 210B senses light in the blue wavelength region passing through the first color filter 240B and constitutes a blue B unit pixel of the first layer 10. The second photoelectric conversion layer 210R senses light in the red wavelength region passing through the second color filter 240R and constitutes a red R unit pixel of the first layer 10. Furthermore, as described above, the active layer 120 selectively absorbs light in the green wavelength region. Therefore, the active layer 120 constitutes a green G unit pixel of the second layer 20.

[0227] When light is incident towards the second electrode 130, the light in the green wavelength region is absorbed by the active layer 120 and converted into electricity. The light in the remaining wavelength region passes through the active layer 120 and the first electrode 110 and is absorbed by the first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R and converted into electricity.

[0228] The image sensor according to this embodiment includes an active layer 120 containing an organic compound represented by the general formula (1) above, and therefore has improved photoelectric conversion efficiency and stable external quantum efficiency (EQE).

[0229] Furthermore, the image sensor according to this embodiment can be miniaturized by having a structure in which the active layer 120 is stacked. This makes it possible to provide an image sensor with improved integration density.

[0230] Figure 5 is a cross-sectional view illustrating another example of an image sensor according to one embodiment. For the sake of clarity, parts that overlap with the above description will be briefly explained or omitted.

[0231] Referring to Figure 5, the image sensor according to this embodiment further includes a first charge auxiliary layer 140 and a second charge auxiliary layer 150.

[0232] The first charge auxiliary layer 140 and the second charge auxiliary layer 150 are the same as described above in the explanation of Figure 2, so a detailed explanation will be omitted below.

[0233] Figure 6 is a cross-sectional view illustrating yet another example of an image sensor according to one embodiment. For the sake of clarity, parts that overlap with the above description will be briefly explained or omitted.

[0234] Referring to Figure 6, in the image sensor according to this embodiment, the first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R are arranged to overlap.

[0235] Here, "overlapping" means overlapping in a vertical direction perpendicular to the surface of the substrate 210. For example, as shown in the figure, the first photoelectric conversion layer 210B is interposed between the active layer 120 and the second photoelectric conversion layer 210R.

[0236] The first photoelectric conversion layer 210B and the second photoelectric conversion layer 210R selectively absorb light in a predetermined wavelength range depending on the depth to which they are formed. For example, the first photoelectric conversion layer 210B senses light in the blue wavelength range, and the second photoelectric conversion layer 210R senses light in the red wavelength range.

[0237] Figure 7 is a conceptual diagram illustrating another example of an image sensor according to one embodiment. For the sake of explanation, parts that overlap with the above content will be briefly explained or omitted.

[0238] Referring to Figure 7, the image sensor according to this embodiment includes a second pixel PX2.

[0239] The second pixel PX2 is formed in an optical stacked structure, including the stacked third layer 15, fourth layer 25, and fifth layer 35.

[0240] In this embodiment, the third layer 15 consists of red R-unit pixels, the fourth layer 25 consists of blue B-unit pixels, and the fifth layer 35 consists of green G-unit pixels. Although only the case where the third layer 15, fourth layer 25, and fifth layer 35 are stacked in order is shown, this is illustrative. Of course, the stacking order of the third layer 15, fourth layer 25, and fifth layer 35 can be varied in various ways.

[0241] In this embodiment, the fifth layer 35 contains an organic compound represented by the general formula (1) described above. As a result, the image sensor according to this embodiment has improved photoelectric conversion efficiency and stable external quantum efficiency (EQE).

[0242] In one embodiment, the third layer 15 includes a pair of electrodes facing each other and an organic compound interposed between the pair of electrodes that selectively absorbs light of red wavelength. In another embodiment, the third layer 15 includes a pair of electrodes facing each other and an organic compound interposed between the pair of electrodes that selectively absorbs light of blue wavelength.

[0243] The image sensors described above, as shown in Figures 3 to 7, can be applied to a variety of electronic devices such as mobile phones, digital cameras, and biosensors, but are not limited to these.

[0244] An electronic element according to one embodiment will be described below with reference to examples and drawings. However, these are illustrative examples, and the technical concept of the present invention is not limited to such embodiments.

[0245] Figure 8 is a block diagram illustrating an example of an electronic element according to one embodiment. For the sake of convenience, parts that overlap with the above-mentioned content will be briefly explained or omitted.

[0246] Referring to Figure 8, the electronic element 1000 according to this embodiment constitutes an image sensor module.

[0247] For example, the electronic component 1000 includes a control unit 1100, a light source 1200, an image sensor 1300, a dual bandpass filter 1400, and a signal processing unit 1500.

[0248] The control unit 1100 controls the operation of the light source 1200 and the image sensor 1300. For example, the control unit 1100 generates a light source control signal LC to control the operation of the light source 1200. The control unit 1100 also generates a pixel array control signal DC to control the pixel array included in the image sensor 1300, thereby controlling the operation of the image sensor 1300.

[0249] The light source 1200 irradiates the object to be detected 1600 with pulsed light L_tr, i.e., light with controlled ON / OFF timing, according to the light source control signal LC. The pulsed light L_tr that is periodically irradiated onto the object to be detected 1600 is reflected by the object to be detected 1600.

[0250] The image sensor 1300 includes a pixel array containing multiple pixels. The image sensor 1300 includes the image sensor described above using Figures 3 to 7, or the configuration of an image sensor that is variously modified and changed from these within the scope of the technical idea of ​​the present invention.

[0251] The image sensor 1300 receives the light L_rf reflected by the object 1600 via the dual bandpass filter 1400. The dual bandpass filter 1400 selectively passes light in a predetermined wavelength range from the light L_rf reflected by the object 1600.

[0252] The image sensor 1300 receives light in a predetermined wavelength range selected from the light L_rf reflected by the object 1600, via a dual bandpass filter 1400. The image sensor 1300 also outputs a charge signal Vout based on the pixel array control signal DC received from the control unit 1100.

[0253] The signal processing unit 1500 outputs predetermined information, such as depth information DD or iris information ID, based on the charge signal Vout received from the image sensor 1300.

[0254] Figure 9 is a block diagram illustrating another example of an electronic element according to one embodiment. For the sake of convenience, parts that overlap with the above description will be briefly explained or omitted.

[0255] Referring to Figure 9, the electronic element 2000 according to this embodiment constitutes an image sensor package including a CMOS image sensor.

[0256] For example, the electronic component 2000 includes an image sensor chip 2100, a logic chip 2200, and a memory chip 2300. In one embodiment, the image sensor chip 2100, the logic chip 2200, and the memory chip 2300 are stacked and mounted on a package substrate (not shown). For example, the logic chip 2200 is mounted interposed between the memory chip 2300 and the image sensor chip 2100.

[0257] The image sensor chip 2100 includes a pixel array and wiring structure containing multiple unit pixels. The image sensor chip 2100 includes the image sensor described above using Figures 3 to 7, or the configuration of an image sensor that is varied and modified from these within the scope of the technical idea of ​​the present invention.

[0258] The logic chip 2200 is configured to process the pixel signals output from the image sensor chip 2100.

[0259] The memory chip 2300 is configured to store at least one of the pixel signals processed by the logic chip 2200 and the pixel signals output from the image sensor chip 2100. The memory chip 2300 is connected to the logic chip 2200 by at least one redistribution structure RDL. The memory chip 2300 is configured to be connected to the image sensor chip 2100 via the redistribution structure RDL and contact TSVs that penetrate the logic chip 2200.

[0260] Image data transferred from the pixel array of the image sensor chip 2100 is transferred to multiple analog-to-digital converters included in the logic chip 2200. Image data transferred from these multiple analog-to-digital converters to the memory chip 2300 is stored in the memory cell array of the memory chip 2300.

[0261] The image signal processed by the logic chip 2200 is transferred to the image processing unit 2500. The image processing unit 2500 includes at least one image signal processor (ISP) 2510 and a post-processing unit 2520.

[0262] The image processing unit 2500 outputs the video captured by the image sensor chip 2100 as a preview via a display (not shown). When a capture command is input by a user or other party, the video captured by the image sensor chip 2100 is saved to the memory chip 2300.

[0263] The post-processing unit 2520 performs various operations to provide a digital image signal from the image captured by the image sensor chip 2100. For example, the post-processing unit 2520 performs various post-processing algorithms that are not performed by the image signal processor 2510, such as improving contrast, sharpness, and noise. The output from the post-processing unit 2520 is provided to the video codec processing unit (not shown). The image after passing through the video codec processing unit is output to a display (not shown) or stored in the memory chip 2300.

[0264] Although embodiments of the present invention have been described in detail above with reference to the drawings, the present invention is not limited to the embodiments described above, and can be modified and implemented in various ways without departing from the technical spirit of the present invention. [Explanation of Symbols]

[0265] 110 1st electrode 120 Active layer 130 2nd electrode 140 1st charge auxiliary layer 150 Second charge auxiliary layer 210 circuit boards 210B First Photoelectric Conversion Layer 210R Second Photoelectric Conversion Layer 215 storage nodes 220 First interlayer insulating film 230 Second interlayer insulating film 235 Through Via 240B First Color Filter 240R 2nd Color Filter 1000, 2000 electronic elements 1100 Control Unit 1200 light source 1300 Image Sensor 1400 Dual Bandpass Filter 1500 Signal Processing Unit 1600 Objects to be detected 2100 Image Sensor Chip 2200 logic chips 2300 memory chips 2500 Image Processing Equipment 2510 Image Signal Processor (ISP) 2520 Post-processing

Claims

1. An organic compound characterized by being represented by the following general formula (1). 【G1】 (In the above general formula (1), R １ , R ２ , R ３ , and R ４ Each of these independently represents an unsubstituted alkyl group with 1 to 3 carbon atoms. A １ and A ２ These each represent a 4-methylphenyl group, A ３ This indicates a substituted heteroaryl group consisting of a 5-membered ring, or an aryl group consisting of a 6-membered ring substituted with a thiophene ring.

2. R １ , R ２ , R ３ , and R ４ The organic compound according to claim 1, characterized in that R , R , R , and R each represent the same substituent.

3. R １ , R ２ , R ３ , and R ４ The organic compound according to claim 2, characterized in that all of them are methyl groups.

4. A ３ The organic compound according to claim 1, characterized in that it represents a substituted heteroaryl group consisting of a 5-membered ring containing a sulfur atom.

5. The organic compound according to claim 4, characterized in that the 5-membered ring includes a thiophene ring.

6. The organic compound according to claim 1, characterized in that the number of rings contained in the organic compound is 5 to 8.

7. The organic compound according to claim 1, characterized in that the organic compound has a maximum absorption wavelength (λmax) of 530 nm to 560 nm in a thin film state and exhibits an absorption curve having a full width at half maximum (FWHM) of 50 nm to 110 nm in a thin film state.

8. A first electrode and a second electrode facing each other, The device has an active layer interposed between the first electrode and the second electrode, The electronic device is characterized in that the active layer contains an organic compound represented by the following general formula (1). 【G1】 (In the above general formula (1), R １ , R ２ , R ３ , and R ４ Each of these independently represents an unsubstituted alkyl group with 1 to 3 carbon atoms. A １ and A ２ These each represent a 4-methylphenyl group, A ３ This indicates a substituted heteroaryl group consisting of a 5-membered ring, or an aryl group consisting of a 6-membered ring substituted with a thiophene ring.

Images