Heavy isotope substituted organic semiconductor material and organic electroluminescent device comprising same

Abstract

The invention relates to the technical field of organic semiconductor materials and organic light-emitting diodes, in particular to a heavy isotope substituted organic semiconductor material and an organic light-emitting device comprising the same. The organic semiconductor compound comprises a chromophore, the chromophore has a chemical formula I: (Cx1Hx2Nx3Ox4Sx5Six6MyRz) n, when C atoms, N atoms, O atoms, S atoms and Si atoms appear in the chromophore, the C atoms, the N atoms, the O atoms, the S atoms and the Si atoms are respectively and independently substituted by corresponding 13C atoms, 15N atoms, 18O atoms, 34S atoms, 29Si atoms and 30Si atoms partially or completely, and at least one atom is substituted. The performance of the organic semiconductor material substituted by the heavy element is improved, such as higher luminous efficiency and better stability. Correspondingly, the organic electroluminescent device containing the organic semiconductor material has higher luminous efficiency and longer service life.

Description

Technical Field

[0001] This invention relates to the field of organic semiconductor materials and organic light-emitting diodes, and in particular to a heavily isotope-substituted organic semiconductor material and an organic electroluminescent device containing the same. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have become the most competitive next-generation display and lighting technology due to their advantages such as high color saturation, wide field of view, high response speed, solid-state operation, high brightness, low power consumption, and flexibility. In particular, breakthroughs in organic semiconductor optoelectronic materials technology, through iterations from traditional fluorescent materials (first generation), organometallic phosphorescent materials (second generation), and thermally activated delayed fluorescence materials (third generation), have made OLED technology more mature. This has led to OLEDs rapidly dominating the panel display and lighting market in recent years, becoming an essential feature in small-to-medium-sized high-end display products, such as iPhones, Samsung flagship phones, and Huawei flagship phones.

[0003] The rapid expansion of the OLED display market has led to a continuous increase in the requirements for OLED performance, such as the increasing demands on OLED device efficiency, lifespan, and voltage. Consequently, the performance requirements for organic semiconductor optoelectronic materials are also becoming more stringent. Summary of the Invention

[0004] The purpose of this invention is to provide a heavily isotope-substituted organic semiconductor material and an organic electroluminescent device containing the same.

[0005] To achieve the above objectives, the present invention provides the following solution: One of the technical solutions of this invention is an organic semiconductor compound comprising a chromophore, said chromophore having chemical formula I: (C x1 H x2 N x3 O x4 S x5 Si x6 M y R z ) n Furthermore, when C, N, O, S, and Si atoms appear in the chromophore, each is independently affected by its corresponding... 13 C 15 N、 18 O、 34 S, 29 Si、 30 Si is partially or completely substituted, and at least one atom is substituted; The chromophore is selected from at least one of aromatic rings, fused aromatic rings, aromatic heterocycles, fused aromatic heterocycles, organometallic complexes or organometallic semiconductor materials, chain conjugated organic compounds or polymers; Where x1, x2, x3, x4, x5, x6, y, z, and n are natural numbers, and x1 and x2 are each independently selected from natural numbers from 3 to 500, x3, x4, x5, x6, y, and z are each independently selected from natural numbers from 0 to 50, and n ≥ 0; M is an element other than C, H, N, O, S, and Si, selected from at least one of Li, Na, K, Be, Mg, Ca, Ti, Cr, Mo, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd, B, Al, Ga, In, P, Se, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Y; R represents one or more substitutions that satisfy the number of chromophore valence bonds, selected from tritium, halogen, cyano, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 fluoroalkyl, substituted or unsubstituted C1-C12 deuterylalkyl, substituted or unsubstituted C1-C18 silyl, substituted or unsubstituted phenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted selenophenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraquinyl, fluorenyl, substituted or unsubstituted carbazoyl, and substituted or unsubstituted fused aromatic heteroyl containing N, O, S or Se. The substituents in R that can be substituted are selected from one or more of the following: deuterium, halogen, cyano, C1-12 alkyl, C3-12 cycloalkylmethyl, C1-12 alkoxy, C6-16 aryl, and C4-16 heteroaryl containing one or more heteroatoms. The heteroatom is selected from one or more of oxygen, sulfur, selenium, or nitrogen atoms.

[0006] The organic semiconductor compound can be any known organic semiconductor material containing C, N, O, S, or Si atoms, wherein each of the C, N, O, S, or Si atoms is independently... 13 C 15 N、 18 O、 34 S, 29 Si、 30 Si is partially or completely substituted, and at least one atom is substituted.

[0007] The organic semiconductor compound has one or more of the following functions: light emission, energy transfer, carrier injection, carrier transport, carrier blocking, exciton blocking, etc., and can be used as a light-emitting material, host material, sensitizing material, carrier injection material, carrier transport material, carrier blocking material, exciton blocking material, etc. Organic semiconductor compounds, when used as luminescent materials, can be traditional organic fluorescent materials, thermally activated delayed fluorescent materials, multiple resonance thermally activated delayed fluorescent materials, organometallic complex phosphorescent materials, and organometallic complex rare earth luminescent materials. The emitted light can be a full spectrum of colors, including red, yellow, green, blue, violet, infrared, and ultraviolet light.

[0008] In some embodiments of the present invention, the organic semiconductor compound contains, but is not limited to, at least one of the following groups or segments:

[0009]

[0010]

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019] ; The C, N, O, S, Si atoms in the above-mentioned groups or segments can each be independently converted to their respective atoms. 13 C 15 N、 18 O、 34 S, 29 Si、 30 Si is partially or completely replaced; The dashed lines represent the bond sites where the above groups or segments are combined with other groups or segments, which can be one or more bonding sites that satisfy valence bonds; R in the above groups or fragments 1 R2 R 3 R 4 Each of the following is independently selected from hydrogen, tritium, halogen, cyano, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 fluoroalkyl, substituted or unsubstituted C1-C12 deuterylalkyl, substituted or unsubstituted C1-C18 silyl, substituted or unsubstituted phenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthraquinone, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazole, substituted or unsubstituted fused aromatic heterogroups containing N, O, S or Se, with two adjacent R 1 R 2 R 3 or R 4 It can fused into rings; m is an integer between 0 and 30.

[0020] In some embodiments of the present invention, the organic semiconductor compound has or includes the structure shown in Formula II: Formula II; In Formula II, Ar1, Ar2, and Ar3 are each independently selected from substituted or unsubstituted six-membered benzene rings, substituted or unsubstituted six-membered aromatic heterocycles, substituted or unsubstituted five-membered aromatic heterocycles, or bonds or fused aromatic rings or aromatic heterocycles of five-membered and / or six-membered aromatic rings and / or aromatic heterocycles with no more than 30 substituted or unsubstituted carbon atoms. X1 and X2 are each independently selected from single bonds, S, Se, or ; or X1 and X2 can be selected independently as NR 4 It contains O and Si or P atoms in its structure; R 1 R 2 R 3 Each of the following groups is independently selected from hydrogen, tritium, halogen, cyano, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 fluoroalkyl, substituted or unsubstituted C1-C12 deuterylalkyl, substituted or unsubstituted C1-C18 silyl, substituted or unsubstituted phenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthraquinone, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazole, or substituted or unsubstituted fused aromatic heterogroups containing N, O, S, or Se. The two adjacent R groups...1 R 2 or R 3 It can fused into rings; m1, m2, and m3 are integers between 0 and 30; R 4 -R 8 Each is independently selected from substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 silyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazole, substituted or unsubstituted fused aromatic heterogroups containing N, O, S or Se, R 5 and R 6 , and / or, R 7 and R 8 It can fused into rings; Preferably, Ar1, Ar2, and Ar3 are selected from substituted or unsubstituted phenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted selenphene, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzoselenphene, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzoselenphene, substituted or unsubstituted carbazoyl, substituted or unsubstituted naphthinyl; substituted or unsubstituted pyridyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted naphthiophene, substituted or unsubstituted naphthiophene, substituted or unsubstituted naphthinphene; When C, N, O, S, Si atoms appear in the structure shown in Equation II, each is independently controlled by its corresponding atoms. 13 C 15 N、 18 O、 34 S, 29 Si、 30 Si is partially or completely substituted, and at least one atom is substituted.

[0021] In some embodiments of the present invention, the organic semiconductor compound has or includes the structure shown in Formula III: Formula III; In Formula III, M is a metal selected from at least one of Li, Na, K, Be, Mg, Ca, Ti, Cr, Mo, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd, B, Al, Ga, In, P, Se, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Y; preferably, M is selected from Ir or Pt. L represents other ligands that can coordinate with M; A and B are each independently selected from substituted or unsubstituted six-membered benzene rings, substituted or unsubstituted six-membered aromatic heterocycles, substituted or unsubstituted five-membered aromatic heterocycles, or bonds or fused aromatic rings or aromatic heterocycles of five-membered and / or six-membered aromatic rings and / or aromatic heterocycles with no more than 30 substituted or unsubstituted carbon atoms. Y is selected from single bond, O, S, Se, BR 9 BR 10 R 11 NR 12 PR 13 C=O, S=O, SO2, C=NR 14 C=CR 15 R 16 CR 17 R 18 SiR 19 R 20 At least one of alkyl, cycloalkyl; Z1 and Z2 are each independently selected from C or N; R A R B Each of the following groups is independently selected from hydrogen, tritium, halogen, cyano, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 fluoroalkyl, substituted or unsubstituted C1-C12 deuterylalkyl, substituted or unsubstituted C1-C18 silyl, substituted or unsubstituted phenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthraquinone, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazole, or substituted or unsubstituted fused aromatic heterogroups containing N, O, S, or Se. The two adjacent R groups... A and R B Filamentable rings; adjacent R A L can fuse into a ring; adjacent R B L can fuse into a ring; m A m B Integers between 0 and 30; n1 is an integer from 1 to 5; n2 is an integer from 0 to 5; R 9 -R 20 Each of the following is independently selected from substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 fluoroalkyl, substituted or unsubstituted C1-C12 deuterylalkyl, substituted or unsubstituted C1-C18 silyl, substituted or unsubstituted phenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthraquinone, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazole, or substituted or unsubstituted fused aromatic heterogroups containing N, O, S, or Se, with two adjacent R 10 and R 11 R 15 and R 16 R 17 and R 18 , and / or R 19 and R 20 It can fused into rings; When C, N, O, S, Si atoms appear in the structure shown in Equation III, each is independently controlled by its corresponding atoms. 13 C 15 N、 18 O、 34 S, 29 Si、 30 Si is partially or completely substituted, and at least one atom is substituted.

[0022] The second technical solution of the present invention is an organic light-emitting diode, comprising a cathode, an anode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer comprises the aforementioned organic semiconductor compound.

[0023] In some embodiments of the present invention, the organic thin film layer comprises a light-emitting layer, a carrier injection layer, a carrier transport layer, a carrier blocking or exciton blocking layer, and at least one of the layers comprises the organic semiconductor compound.

[0024] In some embodiments of the present invention, the organic light-emitting diodes are combined to form a single-junction OLED light-emitting device, or to form a double-layer or multi-layer OLED device.

[0025] The third technical solution of the present invention is a display panel, which includes the above-mentioned organic light-emitting diode.

[0026] The present invention discloses the following technical effects: By appropriately modifying the C, N, O, S, Si atoms in the molecular structure of organic semiconductor materials...13 C 15 N、 18 O、 34 S, 29 Si、 30 When organic semiconductor materials are partially or completely substituted with heavy isotopes such as Si, their properties are improved, resulting in higher luminous efficiency and better stability. Consequently, organic electroluminescent devices containing such organic semiconductor materials exhibit higher luminous efficiency and longer lifetime. Attached Figure Description

[0027] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 This is a schematic diagram of the structure of an OLED device in an application example of the present invention. 101 is the anode, 102 is the hole injection layer, 103 is the hole transport layer, 104 is the electron blocking layer, 105 is the light-emitting layer, 106 is the electron transport layer, 107 is the electron injection layer, and 108 is the cathode.

[0029] Figure 2 The UV-Vis absorption spectra and photoluminescence spectra (PL) of compounds A1 and A2 are shown.

[0030] Figure 3 The fluorescence decay of compounds A1, A2, and A0 after continuous irradiation with a 425 nm LED (30 W) at a distance of 10 cm from the sample for 30 minutes is shown.

[0031] Figure 4 The EQE-brightness curves of the device using compounds E1 and E0 from Example 8 are shown.

[0032] Figure 5 The electroluminescence spectra of the devices using compounds E1 and E0 from Example 8 are shown. Detailed Implementation

[0033] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0034] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0035] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0036] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0037] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0038] This invention provides a heavily isotopically substituted organic semiconductor compound or polymer and its applications. Particularly, it relates to a method for correspondingly substituting C, N, O, S, Si, and other atoms in the molecular structure of known organic semiconductor materials. 13 C 15 N、 18 O、 34 S, 29 Si、 30 Effective modification through partial or complete substitution of Si heavy isotopes. Compared to known organic semiconductor materials, the photoelectric properties of organic semiconductor materials modified by heavy isotope substitution are significantly improved.

[0039] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0040] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field, and the reagents or raw materials used are all purchased from commercial channels or are publicly available unless otherwise specified.

[0041] Example 1: Preparation of compound A1

[0042] Synthesis of intermediate A1-1

[0043] Add iodobenzene (1.53 g, 7.5 mmol), cuprous iodide (143 mg, 0.75 mmol), 1,10-phenoxyline (135 mg, 0.75 mmol), sodium tert-butoxide (3.6 g, 37.5 mmol), and water to a 100 mL dry reaction flask. 18 O (98 atom%) 18 O, 2.5 mL), then add dry DMSO (12.5 mL). React at 100 °C for 16 h under nitrogen. Cool the reaction solution to room temperature, add 20 mL of water, acidify with dilute hydrochloric acid to pH=1, filter, extract the filtrate three times with ethyl acetate, combine the organic phases, concentrate, and purify by column chromatography (PE / EA = 5 / 1) to give Al-1 (94 atom%). 18 O) 655 mg of pale yellow solid, yield 91%. MS m / z [M] + calcd. for C6H6 18 O: 96.05, found: 96.22 Synthesis of intermediate A1-2

[0044] Al-1 (624 mg, 6.5 mmol), 5-bromo-2-chloro-1,3-difluorobenzene (2.22 g, 9.75 mmol), cesium carbonate (3.177 g, 9.75 mmol), and NMP (N-methylpyrrolidone, 20 mL) were added to a 100 mL reaction flask. The reaction mixture was reacted at 170 °C for 12 h under nitrogen protection. The reaction mixture was cooled to room temperature, poured into 50 mL of water, extracted three times with ethyl acetate, and the organic phases were combined and concentrated. The organic phases were purified by column chromatography (PE / EA = 20 / 1) to give 1.5 g of Al-2, with a yield of 76%.

[0045] MS m / z [M] + calcd. for C 12 H7BrClF 18 O: 301.94, 303.94, found: 301.89,303.91 Synthesis of intermediate A1-3

[0046] Al-2 (1.46 g, 4.8 mmol), 3,6-di-tert-butylcarbazole (2.72 g, 9.75 mmol), cesium carbonate (4.24 g, 13.0 mmol), and NMP (20 mL) were added to a 100 mL reaction flask. The reaction mixture was reacted at 170 °C for 12 h under nitrogen protection. The reaction mixture was cooled to room temperature, poured into 50 mL of water, extracted three times with ethyl acetate, and the organic phases were combined and concentrated. The organic phases were purified by column chromatography (PE / DCM = 4 / 1) to give 1.84 g of Al-3, with a yield of 68%.

[0047] MS m / z [M] + calcd. for C 32 H 31 BrClN 18 O: 561.13, 563.13, found: 561.18,563.15 Synthesis of intermediate A1-4

[0048] Add A1-3 (1.8 g, 3.2 mmol) and THF (10 mL) to a dry reaction flask, cool to -78 ºC, and add n-BuLi (1.6 M in hexane, 2.1 mL) dropwise under nitrogen protection. After the addition is complete, continue the reaction at -78 ºC for 2 h. Then, slowly add a THF solution (5 mL) of triphenylchlorosilane (991 mg, 3.36 mmol) to the reaction flask. After the addition is complete, continue the reaction at this temperature for 30 min, then raise the temperature to room temperature and continue the reaction for 2 h. Quench with 30 mL of water, extract with ethyl acetate, concentrate, and purify by silica gel column chromatography (PE / DCM = 10 / 1) to obtain 1.81 g of B1-2, yield 76%.

[0049] MS m / z [M] + calcd. for C 50 H 46 ClN 18 OSi: 741.31, found: 741.45 Synthesis of compound A1

[0050] Al-4 (1.5 g, 2.02 mmol) was added to a dry reaction tube, and nitrogen was purged three times. Then, under nitrogen protection, dry tert-butylbenzene (20 mL) was injected into the tube using a syringe. The tube was cooled to -30 °C, and tert-butyllithium solution (1.3 M in pentane, 3.1 mL) was added dropwise. The tube was then transferred to 60 °C and reacted for 2 h. The n-pentane was removed under vacuum, and the tube was transferred to -30 °C. Boron tribromide (607 mg, 2.42 mmol) was added dropwise. After the addition was complete, the tube was transferred to room temperature and reacted for 1 h. Then, DIPEA (522 mg, 4.04 mmol) was added dropwise at -30 °C, and the reaction was continued for 15 min. Finally, the temperature was raised to 140 °C and reacted for 16 h. After the reaction was complete, tert-butylbenzene was removed by vacuum distillation. Recrystallization from DCM / MeOH yielded 303 mg of Al, a bright yellow solid with an HPLC purity of 99.5% and a yield of 21%.

[0051] MS m / z [M] + calcd. for C 50 H 44 BN 18 OSi: 715.33, found: 715.39 Example 2: Preparation of compound A2

[0052] With phenol- 13 Using C6 as the raw material, A2 was prepared according to the same preparation route as A1, ultimately yielding 30 mg of A2, a bright yellow solid with an HPLC purity of 99.5%.

[0053] MS m / z [M] + calcd. for C 44 13 C6H 44 BNOSi: 719.35, found: 719.40 Example 3: Preparation of compound B1

[0054] Synthesis of intermediate B1-1

[0055] Add aniline to a 100 mL dry reaction flask. 15N (1.00 g, 10.6 mmol), bromobenzene (1.67 g, 10.6 mmol), Pd2(dba)3 (194 mg, 0.2 mmol), BINAP (125 mg, 0.2 mmol), t-BuONa (2.04 g, 21.2 mmol), and dry toluene (40 mL) were added, purged with nitrogen three times, and refluxed under nitrogen protection for 16 h. The reaction was cooled to room temperature, filtered, concentrated, and purified by column chromatography (PE / DCM = 10 / 1) to give 1.62 g of pure B1-1, in 90% yield.

[0056] MS m / z [M] + calcd. for C 12 H 11 15 N: 170.09, found: 170.11 Synthesis of intermediate B1-2

[0057] 1,3-Dibromo-5-chlorobenzene (1.35 g, 5.0 mmol) and THF (20 mL) were added to a dry reaction flask. The mixture was cooled to -78 ºC, and n-BuLi (1.6 M in hexane, 3.28 mL) was added dropwise under nitrogen protection. After the addition was complete, the reaction was continued at -78 ºC for 2 h. Then, a THF solution (10 mL) of triphenylchlorosilane (1.55 g, 5.25 mmol) was slowly added to the reaction flask. After the addition was complete, the reaction was continued at this temperature for 30 min, then the temperature was raised to room temperature and the reaction was continued for 2 h. The mixture was quenched with 30 mL of water, extracted with ethyl acetate, concentrated, and purified by silica gel column chromatography (PE / DCM = 10 / 1) to obtain 1.37 g of B1-2, with a yield of 61%.

[0058] MS m / z [M] + calcd. for C 24 H 18 BrClSi: 448.00, 450.00, found: 448.05, 450.09 Synthesis of intermediate B1-3

[0059] Add 1.35 g (3.0 mmol) of B1-2 and 6 mL of dry THF to a dry reaction flask, cool to -78 ºC, and add LDA (2.0 M, 3.15 mL) dropwise under nitrogen protection and stirring. After the addition is complete, continue the reaction at this temperature for 3 h. Then, slowly add 6 mL of a THF solution containing 1.5 g (6.34 mmol) of hexachloroethane to the reaction flask, continue the reaction at this temperature for 30 min, raise the temperature to room temperature, and continue the reaction for 16 h. Quench with water, separate the organic phase, extract the aqueous phase with dichloromethane, combine the organic phases, concentrate, and purify by silica gel column chromatography (PE / DCM = 10 / 1) to obtain 1.1 g of B1-3, yield 76%.

[0060] MS m / z [M] + calcd. for C 24 H 17 BrCl2Si: 481.97, 483.96, found: 481.86,483.88 Synthesis of intermediate B1-4

[0061] Add B1-3 (1.05 g, 2.17 mmol), B1-1 (776 mg, 4.56 mmol), and Pd132 (46 mg, 0.065 mmol) to a dry reaction flask. t BuONa (521 mg, 5.43 mmol) and toluene (10 mL) were reacted under nitrogen-protected reflux for 20 h. 20 mL of dichloromethane was added, the mixture was filtered, and the filtrate was concentrated and purified by silica gel column chromatography (PE / DCM = 4 / 1) to give 952 mg B1-4, yield 62%.

[0062] MS m / z [M] + calcd. for C 48 H 37 Cl 15 N2Si: 706.24, found: 706.35 Synthesis of compound B1

[0063] Add B1-4 (900 mg, 1.27 mmol) to a dry reaction tube, purge with nitrogen three times, then inject dry tert-butylbenzene (12 mL) into the tube under nitrogen protection using a syringe. Cool to -40 °C, add tert-butyllithium solution (1.3 M in pentane, 2.0 mL) dropwise, transfer to 60 °C and react for 2 h. Remove n-pentane under vacuum, transfer to -40 °C, add boron tribromide (382 mg, 1.52 mmol) dropwise. After addition, transfer to room temperature and react for 1 h. Then add DIPEA (328 mg, 2.54 mmol) dropwise at -30 °C, continue reacting for 15 min, then raise the temperature to 120 °C and react for 3 h. After the reaction is complete, remove tert-butylbenzene by vacuum distillation, recrystallize from DCM / MeOH to give 216 mg of B1, a bright yellow solid with HPLC purity of 99.5% and a yield of 25%.

[0064] MS m / z [M] + calcd. for C 48 H 35 B 15 N2Si: 680.26, found: 680.29 Example 4: Preparation of compound C1

[0065] Synthesis of intermediate C1-1

[0066] Add PhMgCl (2M in THF, 10 mL, 20 mmol) to a 50 mL dry reaction flask, and slowly add it to the solution under a nitrogen atmosphere at room temperature. 34 S8 (680 mg, 20 mmol) was reacted for another 16 h at room temperature, then poured into 20 mL of ice water, extracted with dichloromethane, the organic phases were combined, washed with saturated NaCl solution, dried over anhydrous magnesium sulfate, filtered, and the organic phase was concentrated to give 808 mg of product C1-1, yield 36%.

[0067] MS m / z [M] + calcd. for C6H6 34 S: 112.01, found: 112.15 Synthesis of compound C1 Compound C1 was synthesized following a similar route and steps as in Example 1. The final product, C1, was 56 mg, a bright yellow solid with an HPLC purity of 99.5%.

[0068] MS m / z [M] + calcd. for C 24 H 14 BN 34 S: 361.09, found: 361.01 Example 5: Preparation of compound D1

[0069] Synthesis of intermediate D1-1

[0070] Add bromobenzene to a 100 mL reaction flask 13 C6 (500 mg, 3.07 mmol), pinacol diboronate (934 mg, 3.68 mmol), Pd(OAc)2 (14 mg, 0.06 mmol), KOAc (603 mg, 6.14 mmol), and DMF (15 mL) were reacted under nitrogen protection at 80 °C for 16 h. The reaction solution was cooled to room temperature, poured into 50 mL of water, and extracted with dichloromethane (20 mL * 3). The organic phases were combined, concentrated, and purified by column chromatography (PE / DCM = 4 / 1) to give 548 mg of D1-1 as a white solid, in 85% yield.

[0071] MS m / z [M] + calcd. for C6 13 C6H 17 BO2: 210.15, found: 210.22 Synthesis of intermediate D1-2

[0072] D1-1 (520 mg, 2.48 mmol), 2-bromopyridine (588 mg, 3.72 mmol), Pd(OAc)2 (11 mg, 0.05 mmol), SPhos (62 mg, 0.15 mmol), K3PO4 (1.05 g, 4.96 mmol), and Tol / EtOH / H2O (10 mL / 5 mL / 10 mL) were added to a 100 mL reaction flask. The mixture was reacted under nitrogen protection and reflux for 12 h. The reaction solution was cooled to room temperature, poured into 50 mL of water, and extracted with ethyl acetate (20 mL * 3). The organic phases were combined, concentrated, and purified by column chromatography (PE / DCM = 4 / 1) to give 367 mg of D1-2 as an oily liquid, with a yield of 92%.

[0073] MS m / z [M] + calcd. for C5 13 C6H9N: 161.09, found: 161.15 Synthesis of intermediate D1-3

[0074] D1-2 (225 mg, 1.4 mmol), IrCl3•3H2O (247 mg, 0.7 mmol), 2-ethoxyethanol (3.0 mL), and deionized water (0.6 mL) were added to the reaction flask. The mixture was purged with nitrogen three times, heated to 130 °C, and reacted for 16 h. After cooling to room temperature, methanol was added and the mixture was filtered to obtain a solid. The solid was then slurried again with methanol to obtain another solid. The solid was dissolved in DCM, filtered through diatomaceous earth to obtain a red filtrate, concentrated, and slurried with methanol to obtain 288 mg of solid D1-3, with a yield of 75%.

[0075] MS m / z [M] + calcd. for C 20 13 C 24 H 32 Cl2Ir2N4: 1096.21, found: 1096.30 Synthesis of compound D1

[0076] D1-3 (274 mg, 0.25 mmol), D1-2 (121 mg, 0.75 mmol), K2CO3 (207 mg, 1.5 mmol), and glycerol (10 mL) were added to the reaction flask. The mixture was purged with nitrogen three times, heated to 200 °C, and reacted for 20 h. The mixture was then cooled to room temperature, and 20 mL of deionized water was added. A solid precipitated out. The solid was collected by filtration, and the filter cake was slurried with methanol. The solid was then recrystallized from methanol to obtain 205 mg of product D1, a yellow solid with a purity of 99.5% and a yield of 61%.

[0077] MS m / z [M] + calcd. for C 15 13 C 18 H 24 IrN3: 673.22, found: 673.33 Example 6: Preparation of compound E1

[0078] Synthesis of intermediate E1-1

[0079] D1-1 (500 mg, 2.38 mmol), 1-bromoisoquinoline (743 mg, 3.57 mmol), Pd(PPh3)4 (55 mg, 0.048 mmol), Na2CO3 (505 mg, 4.76 mmol), and Tol / EtOH / H2O (10 mL / 5 mL / 10 mL) were added to a 100 mL reaction flask. The mixture was reacted under nitrogen protection and reflux for 12 h. The reaction solution was cooled to room temperature, poured into 50 mL of water, and extracted with ethyl acetate (20 mL * 3). The organic phases were combined, concentrated, and purified by column chromatography (PE / DCM = 4 / 1) to give 467 mg of E1-1, with a yield of 93%.

[0080] MS m / z [M] + calcd. for C9 13 C6H 11 N: 211.11, found: 211.13 Synthesis of intermediate E1-2

[0081] E1-1 (450 mg, 2.13 mmol), IrCl3•3H2O (375 mg, 1.06 mmol), 2-ethoxyethanol (5.0 mL), and deionized water (1.0 mL) were added to the reaction flask. The mixture was purged with nitrogen three times, heated to 130 °C, and reacted for 16 h. The mixture was then cooled to room temperature, and methanol was added. The solid was filtered to obtain a solid. The solid was dissolved in DCM, filtered through diatomaceous earth to obtain a red filtrate, and concentrated. The filtrate was then slurried with methanol to obtain 529 mg of solid E1-2, with a yield of 77%.

[0082] MS m / z [M] + calcd. for C 36 13 C 24 H 40 Cl2Ir2N4: 1296.27, found: 1296.42 Synthesis of compound E1

[0083] E1-2 (518 mg, 0.4 mmol), acetylacetone (400 mg, 4.0 mmol), K2CO3 (553 mg, 4.0 mmol), and 2-ethoxyethanol (4 mL) were added to the reaction flask. The mixture was purged with nitrogen three times, heated to 130 °C, and reacted for 20 h. The mixture was then cooled to room temperature, and 20 mL of dichloromethane was added. The mixture was filtered, the filtrate was collected, concentrated, slurried with methanol, and then recrystallized from 2-ethoxyethanol to obtain 228 mg of product E1, a red solid with a purity of 99.5% and a yield of 40%.

[0084] MS m / z [M] + calcd. for C 23 13 C 12 H 27 IrN2O2: 712.21, found: 712.12 Example 7: Preparation of compound F1

[0085] Synthesis of intermediate F1-1

[0086] Add A1-1 (624 mg, 6.5 mmol), 3-bromo-4-fluorochlorobenzene (2.042 g, 9.75 mmol), cesium carbonate (3.177 g, 9.75 mmol), and NMP (20 mL) to a 100 mL reaction flask. React the solution under nitrogen protection at 170 °C for 12 h. Cool the reaction solution to room temperature, pour it into 50 mL of water, extract three times with ethyl acetate, combine and concentrate the organic phases, and purify by column chromatography (PE / EA = 20 / 1) to obtain 1.35 g of F1-1, yield 73%.

[0087] MS m / z [M] + calcd. for C 12 H8BrCl 18 O: 283.95, 283.95, found: 283.83, 283.87 Synthesis of intermediate F1-2

[0088] Add F1-1 (1.3 g, 4.55 mmol), Pd(OAc)2 (101 mg, 0.45 mmol), Na2CO3 (579 mg, 5.46 mmol), and DMAc (10 mL) to the reaction flask, purge with nitrogen three times, and heat to 170 ºC for 2 h. Cool to room temperature, pour into 50 mL of water, and a solid precipitates. Filter and collect the solid, recrystallize from ethanol to give 698 mg of F1-2, yield 75%.

[0089] MS m / z [M] + calcd. for C 12 H7Cl 18 O: 296.15, found: 204.18 Synthesis of intermediate F1-3

[0090] F1-2 (650 mg, 3.18 mmol), pinacol diboronate (969 mg, 3.82 mmol), Pd(OAc)2 (14 mg, 0.06 mmol), KOAc (624 mg, 6.36 mmol), and DMF (15 mL) were added to a 100 mL reaction flask. The reaction mixture was then subjected to nitrogen protection and reacted at 120 °C for 16 h. The reaction solution was cooled to room temperature, poured into 50 mL of water, and extracted with dichloromethane (20 mL * 3). The organic phases were combined, concentrated, and purified by column chromatography (PE / DCM = 5 / 1) to obtain 819 mg of F1-3, a pale yellow solid, in 87% yield.

[0091] MS m / z [M] + calcd. for C 18 H 19 BO2 18 O: 296.15, found: 296.22 Synthesis of compound F1

[0092] Add F1-3 (800 mg, 1.7 mmol), 9-bromo-10-(1-naphthyl)anthracene (652 mg, 1.7 mmol), Pd132 (18 mg, 0.026 mmol), and THF (6 mL) to the reaction flask, then add 3 mL of NaOH (238 mg, 6.0 mmol) aqueous solution. Replace the nitrogen gas three times, react at 60 °C for 1 h, concentrate under reduced pressure to remove the organic phase, extract with dichloromethane, concentrate, slurry with methanol, filter to obtain crude product, recrystallize from toluene to obtain 643 mg F1 with a purity of 99.6% and a yield of 80%.

[0093] MS m / z [M] + calcd. for C 36 H 22 18 O: 472.17, found: 472.23 Example 8: Preparation of compound F2

[0094] Synthesis of intermediate F2-1

[0095] Add phenol to the reaction flask 13 C6 (500 mg, 5.0 mmol), bromobenzene- 13 C6 (815 mg, 5.0 mmol), CuI (95 mg, 0.5 mmol), Cs₂CO₃ (3.26 g, 10.0 mmol), TMEDA (1.16 g, 10.0 mmol), and DMF (10 mL) were added, purged with nitrogen three times, and the mixture was heated to 130 ºC for 20 h. After cooling to room temperature, the mixture was diluted with ethyl acetate, filtered, and the filtrate was concentrated to obtain the crude product. The crude product was purified by column chromatography (PE / EtOAc = 15 / 1) to give 837 mg of F₂⁻, with a yield of 92%.

[0096] MS m / z [M] + calcd. for 13 C 12 H 10 O: 182.11, found: 182.19 Synthesis of intermediate F2-2

[0097] F2-1 (820 mg, 4.5 mmol), Pd(OAc)2 (51 mg, 0.225 mmol), K2CO3 (62 mg, 0.45 mmol), and PivOH (4.5 mL) were added to a reaction tube. The mixture was heated to 120 ºC and reacted for 42 h. After cooling to room temperature, the mixture was diluted with dichloromethane, washed with saturated Na2CO3 aqueous solution, dried over anhydrous MgSO4, filtered, concentrated, and purified by silica gel column chromatography (PE) to give 527 mg of F2-2, in 65% yield. MS m / z [M] + calcd. for 13 C 12 H8O: 180.10, found: 180.00 Synthesis of intermediate F2-3

[0098] F2-2 (510 mg, 2.8 mmol), liquid bromine (492 mg, 3.08 mmol), and CHCl3 (6 mL) were added to the reaction flask. The reaction was carried out at room temperature for 24 h. The organic solvent was removed under reduced pressure, and the product was recrystallized from dichloromethane / methanol to give 590 mg of F2-3 as a white solid, with a yield of 82%.

[0099] MS m / z [M] + calcd. for 13 C 12 H7BrO: 258.01, 260.01, found: 257.88, 259.92 Synthesis of compound F2 After obtaining intermediate F2-3, intermediate F2-4 and compound F2 were synthesized according to a similar route and steps as in Example 8. Finally, 709 mg of product F2 was obtained with an HPLC purity of 99.6%.

[0100] MS m / z [M] + calcd. for C 24 13 C 12 H 22 O: 482.21, found: 482.36 Following similar routes and procedures as in Examples 1-8, corresponding unsubstituted heavy isotope compounds A0, B0, C0, D0, E0, and F0 were synthesized for comparison:

[0101] The specific structures of the compounds used in the following device application examples are shown below:

[0102] Figure 2 The UV-Vis absorption (UV) and photoluminescence (PL) spectra of compounds A1 and A2 in toluene solution are shown. Figure 2 It can be seen that the UV and PL of the compound in solution remain unchanged after being substituted with heavy isotopes.

[0103] Figure 3 The fluorescence decay of compounds A1, A2, and A0 after continuous irradiation with a 425 nm LED (30 W) at a distance of 10 cm from the sample for 30 minutes is shown. Figure 3 It can be seen that the stability of the compound under light increases after being substituted with heavy isotopes.

[0104] Application Examples 1-6 and Comparative Examples I-III In Application Examples 1-6 and Comparative Examples I-III, a blue OLED device is provided, wherein the compounds of the present invention (A1, A2, B1, C1, F1, F2) and comparative materials (A0, B0, CO) are used as luminescent dopants or host materials for the luminescent layer. The evaporation process for the OLED device is as follows: in a base vacuum of 10... -5 In the multi-source evaporation OLED fabrication equipment of Pa, the following bottom-emission OLED device structure is adopted: anode ITO / hole injection layer HIL (50Å) / hole transport layer HTL (450Å) / electron blocking layer EBL (100Å) / emitting layer EML (Host: 1%~40% (200Å) of luminescent dopant) / electron transport layer ETL (350Å) / electron injection layer EIL (10Å) / Al cathode (e.g. Figure 1 As shown in the figure, the performance of each material applied to OLED devices was evaluated. The specific OLED device structure is ITO / hole injection layer (HATCN, 50 Å) / hole transport layer (NPB, 450 Å) / electron blocking layer (EB01, 100 Å) / body material: 2% doped material (200 Å) / ET01:LiQ (1:1, 350 Å) / LiQ (10 Å) / Al (1000 Å). The device performance at 1000 nits is shown in Table 1, where LT95 is the time for the constant current brightness to decrease by 5% at the initial brightness of 1000 nits.

[0105] Table 1

[0106] Application Example 7 and Comparative Example IV provide a green OLED device, wherein the compound D1 of the present invention and the comparative material D0 are used as luminescent dopant materials in the luminescent layer. The specific OLED device structure is ITO / hole injection layer (HATCN, 50 Å) / hole transport layer (NPB, 900 Å) / electron blocking layer (EB01, 100 Å) / GH01:GH02:doped material (56.4%:37.6%:6%, 350 Å) / ET01:LiQ (1:1, 350 Å) / LiQ (10 Å) / Al (1000 Å). The device performance at 1000 nits is shown in Table 2, where LT95 is the time for the constant current brightness to decrease by 5% at the initial 1000 nits brightness.

[0107] Table 2

[0108] Application Example 8 and Comparative Example V provide a red OLED device, wherein the compound E1 of the present invention and the comparative material E0 are used as the luminescent dopant materials of the luminescent layer. The specific OLED device structure is ITO / hole injection layer (HATCN, 50 Å) / hole transport layer (NPB, 1550 Å) / electron blocking layer (EB01, 100 Å) / RH01:2% dopant material (300 Å) / ET01:LiQ (1:1, 350 Å) / LiQ (10 Å) / Al (1000 Å). The device performance at 1000 nits is shown in Table 3, where LT95 is the time for the constant current brightness to decrease by 5% at the initial brightness of 1000 nits.

[0109] Table 3

[0110] As shown in Tables 1, 2, and 3, the organic semiconductors of the present invention with heavy isotope substitution exhibit improved luminous efficiency and luminous lifetime compared to the comparative compounds without heavy isotope substitution.

[0111] Figure 4 The EQE-brightness curves of the device using compounds E1 and E0 from Example 8 are shown. Figure 4 It can be seen that the electroluminescence efficiency of the material replaced by heavy isotopes is improved.

[0112] Figure 5 The electroluminescence spectra of the devices using compounds E1 and E0 from Example 8 are shown. Figure 5 It can be seen that the electroluminescence spectrum of the material remains basically unchanged after being replaced by heavy isotopes.

[0113] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. An organic semiconductor compound, characterized by, comprising a chromophore having the formula I: (C x1 H x2 N x3 O x4 S x5 Si x6 M y R z ) n and when C, N, O, S, Si atoms occur in the chromophore, each independently is partially or completely substituted by corresponding 13 C, 15 N, 18 O, 34 S, 29 Si, 30 Si moieties and at least one atom is substituted; The chromophore is selected from at least one of an aromatic ring, a fused aromatic ring, an aromatic heterocycle, a fused aromatic heterocycle, an organometallic complex or an organometallic semiconductor material, a chain conjugated organic compound or a polymer; wherein x1, x2, x3, x4, x5, x6, y, z, n are natural numbers, and x1, x2 are each independently selected from natural numbers of 3-500, x3, x4, x5, x6, y, z are each independently selected from natural numbers of 0-50, and n≥0; M is selected from at least one of Li, Na, K, Be, Mg, Ca, Ti, Cr, Mo, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd, B, Al, Ga, In, P, Se, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y; R is selected from tritium, halogen, cyano, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 fluorine-containing alkyl, substituted or unsubstituted C1-C12 deuterium-containing alkyl, substituted or unsubstituted C1-C18 silyl, substituted or unsubstituted phenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted selenophenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fused aromatic heterocycle containing N, O, S or Se; The substituents of the substitutable groups in R are optionally selected from one or more of deuterium, halogen, cyano, C1-12 alkyl, C3-12 cycloalkylmethyl, C1-12 alkoxy, C6-16 aryl, C4-16 heteroaryl containing one or more heteroatoms; The heteroatoms are optionally selected from one or more of oxygen atom, sulfur atom, selenium atom or nitrogen atom.

2. The organic semiconductor compound according to claim 1, characterized in that Containing, but not limited to, one or any combination of the following groups or fragments: ； The C, N, O, S, Si, etc. atoms in the above groups or fragments can each be independently replaced, in whole or in part, by corresponding 13 C, 15 N, 18 O, 34 S, 29 Si, 30 Si moieties. The dotted line represents the bonding site of the above group or fragment to other groups or fragments, which can be one or more bonding sites satisfying the valence; Rin the above groups or fragments 1 , R 2 , R 3 , R 4 each independently is selected from the group consisting of hydrogen, tritium, halogen, cyano, a substituted or unsubstituted C1-C18alkyl group, a substituted or unsubstituted C1-C12alkoxy group, a substituted or unsubstituted C3-C18cycloalkyl group, a substituted or unsubstituted C1-C18fluorinated alkyl group, a substituted or unsubstituted C1-C12deuterated alkyl group, a substituted or unsubstituted C1-C18silyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted selenolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fused aromatic hetero group containing N, O, S or Se, and two adjacent R 1 , R 2 , R 3 or R 4 may be fused into a ring; m is an integer of 0-30.

3. The organic semiconductor compound according to claim 1, characterized in that Having or comprising a structure shown in formula II: Formula II; In formula II, Ar1, Ar2, Ar3 are each independently selected from substituted or unsubstituted six-membered benzene ring, substituted or unsubstituted six-membered aromatic heterocycle, substituted or unsubstituted five-membered aromatic heterocycle, substituted or unsubstituted five-membered and / or six-membered aromatic ring and / or aromatic heterocycle with a carbon atom number of not more than 30, and / or a bonded or fused aromatic ring or aromatic heterocycle; X1and X2are each independently selected from a single bond, S, Se, or ; or X1and X2are each independently selected from N-R 4 , O, and the structure contains a Si or P atom; R 1 , R 2 , R 3 are each independently selected from the group consisting of hydrogen, tritium, halogen, cyano, a substituted or unsubstituted C1-C18alkyl group, a substituted or unsubstituted C1-C12alkoxy group, a substituted or unsubstituted C3-C18cycloalkyl group, a substituted or unsubstituted C1-C18fluorinated alkyl group, a substituted or unsubstituted C1-C12deuterated alkyl group, a substituted or unsubstituted C1-C18silyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted selenolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted azyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fused aromatic hetero group containing N or O or S or Se, two adjacent R 1 , R 2 or R 3 may be fused into a ring; m1, m2, m3 are integers of 0-30; R 4 -R 8 each independently selected from substituted or unsubstituted C1-C18alkyl, substituted or unsubstituted C1-C12alkoxy, substituted or unsubstituted C3-C18cycloalkyl, substituted or unsubstituted C1-C18silyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted selenolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fused aromatic hetero group containing N, O, S or Se, R 5 and R 6 , and / or, R 7 and R 8 may be fused into a ring; when C, N, O, S, Si, etc. atoms are present in the structure of formula II, each is independently substituted, in part or in whole, with the corresponding 13 C, 15 N, 18 O, 34 S, 29 Si, 30 Si, and at least one of the atoms is substituted.

4. The organic semiconductor compound according to claim 1, characterized in that Having or comprising a structure shown in formula III: Formula III; In formula III, M is selected from at least one of Li, Na, K, Be, Mg, Ca, Ti, Cr, Mo, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd, B, Al, Ga, In, P, Se, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y; L is another ligand capable of coordinating to M; A and B are each independently selected from a substituted or unsubstituted six-membered aromatic ring, a substituted or unsubstituted six-membered aromatic heterocycle, a substituted or unsubstituted five-membered aromatic heterocycle, a substituted or unsubstituted five-membered and / or six-membered aromatic ring and / or aromatic heterocycle having not more than 30 carbon atoms, a bonded or fused aromatic ring or aromatic heterocycle; Y is selected from the group consisting of a single bond, O, S, Se, BR 9 , BR 10 R 11 , NR 12 , PR 13 , C=O, S=O, SO2, C=NR 14 , C=CR 15 R 16 , CR 17 R 18 , SiR 19 R 20 , at least one of alkyl, cycloalkyl; Z1and Z2are each independently selected from C or N; R A , R B are each independently selected from the group consisting of hydrogen, tritium, halogen, cyano, substituted or unsubstituted C1-C18alkyl, substituted or unsubstituted C1-C12alkoxy, substituted or unsubstituted C3-C18cycloalkyl, substituted or unsubstituted C1-C18fluorinated alkyl, substituted or unsubstituted C1-C12deuterated alkyl, substituted or unsubstituted C1-C18silylalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted selenolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted azinyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fused aromatic heterocycle containing N or O or S or Se, two adjacent R A and R B may be fused to form a ring; adjacent R A and L may be fused to form a ring; adjacent R B and L may be fused to form a ring; m A , m B is an integer from 0 to 30; n1is an integer from 1 to 5; n2is an integer from 0 to 5; R 9 -R 20 each independently is selected from the group consisting of a substituted or unsubstituted C1-C18alkyl, a substituted or unsubstituted C1-C12alkoxy, a substituted or unsubstituted C3-C18cycloalkyl, a substituted or unsubstituted C1-C18fluorinated alkyl, a substituted or unsubstituted C1-C12deuterated alkyl, a substituted or unsubstituted C1-C18silylalkyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted furanyl, a substituted or unsubstituted thienyl, a substituted or unsubstituted selenolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthryl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted fused aromatic heteroaryl group containing N, O, S or Se, two adjacent R 10 and R 11 , R 15 and R 16 , R 17 and R 18 , and / or R 19 and R 20 may be fused to form a ring; when C, N, O, S, Si, etc. atoms are present in the structure of formula III, each is independently substituted, in part or in whole, with the corresponding 13 C, 15 N, 18 O, 34 S, 29 Si, 30 Si, and at least one of the atoms is substituted.

5. An organic light emitting diode, characterized by, comprising a cathode, an anode and an organic thin film layer located between the anode and the cathode; the organic thin film layer comprising the organic semiconducting compound according to any one of claims 1 to 4.

6. The organic light emitting diode of claim 5, wherein the first organic layer comprises a first hole transport layer, a first light emitting layer, a second hole transport layer, and a second light emitting layer. The organic thin film layer comprises a light-emitting layer, a carrier injection layer, a carrier transport layer, a carrier blocking or exciton blocking layer, and wherein at least one layer comprises the organic semiconducting compound.

7. The organic light emitting diode of claim 5, wherein the first electrode comprises a first electrode layer and a second electrode layer, and the second electrode comprises a third electrode layer and a fourth electrode layer. The organic light-emitting diodes are combined into a single-junction OLED light-emitting device, or constitute a double- or multi-layer OLED device.

8. A display panel, characterized by, comprising the organic light-emitting diode according to any one of claims 5 to 7.

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