Novel spiro compounds and their applications in organic electroluminescent devices

Abstract

This invention relates to the field of organic electroluminescent materials, specifically to novel spiro compounds and their application in organic electroluminescent devices. The novel spiro compounds provided by this invention exhibit excellent hole mobility, good thermal stability, and are not easily crystallized, making them effective as hole transport layer materials in the fabrication of organic electroluminescent devices. Furthermore, the novel spiro compounds provided by this invention possess excellent electron transport properties and can be well-matched with hole transport materials to form a good hole-electron balance, achieving optimal efficiency and luminescence lifetime, thus making them effective as electron transport layer materials in the fabrication of organic electroluminescent devices. Finally, the novel spiro compounds provided by this invention have suitable energy levels, can form good energy transfer, and possess high chemical stability, making them effective as host luminescent layer materials in the fabrication of organic electroluminescent devices.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent materials, specifically to novel spiro compounds and their application in organic electroluminescent devices. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are widely used in various displays due to their self-emissive, solid-state, flexible, and high-efficiency characteristics. While many excellent electroluminescent materials have emerged for OLEDs, there is still significant room for improvement in their efficiency and lifespan when applied to OLEDs. Hole transport materials, as materials for transporting holes, require excellent hole mobility, good thermal stability, and resistance to crystallization. The host light-emitting material requires the compound to have suitable energy levels, enabling good energy transfer, and possessing high chemical stability. Electron transport materials require good electron transport performance and the ability to complement hole transport materials to achieve a good hole-electron balance, resulting in optimal efficiency and luminescent lifetime.

[0003] Chinese patent CN102257097B discloses an asymmetric aromatic amine derivative, its preparation method, corresponding thin film materials, and an organic electroluminescent device. Applied to the fabrication of the light-emitting layer material for organic electroluminescent devices, it exhibits excellent luminous efficiency and good lifetime characteristics. However, its application in the fields of electron transport materials and hole transport materials is limited. Chinese patent CN113809251A discloses an organic electroluminescent device and an amine compound for use in the organic electroluminescent device. Applied to the electron transport region of the organic electroluminescent device, it enables OLEDs to exhibit high luminous efficiency, but it cannot achieve a good balance between high luminous efficiency and luminous lifetime. Therefore, providing novel electron transport materials and hole transport materials with high thermal stability and high mobility, as well as light-emitting host materials with suitable energy levels and excellent energy transfer, is a problem urgently needing to be solved by those skilled in the art. Summary of the Invention

[0004] This invention provides a novel spiro-containing compound having the following structural formula:

[0005] Where X1 is either O or S;

[0006] R1 and R2 groups are each independently selected from hydrogen, deuterium, substituted or unsubstituted straight-chain or branched alkyl groups having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms, or R1 and R2 linked together to form a ring.

[0007] R3-R10 Each group is independently selected from hydrogen, deuterium, fluorine, carbide, cyano, nitro, substituted or unsubstituted straight-chain or branched alkyl groups having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups having 6-30 carbon atoms, substituted or unsubstituted heteroaromatic hydrocarbon groups having 5-30 carbon atoms, or two or more adjacent groups connected to each other to form a ring;

[0008] Group A is selected from substituted or unsubstituted aromatic hydrocarbon groups having 6-60 carbon atoms, substituted or unsubstituted heteroaromatic hydrocarbon groups having 5-60 carbon atoms, and N(R) a R b R c ), C(=O)R a R b Si(R) a R b R c R d ), P(=O)(R a R b R c ), B(R) a R b R c ), S(=O)2(R a R b ), where R a The carbon atom attached to the aforementioned spiroring is selected from substituted or unsubstituted C6–C60 arylene and substituted or unsubstituted C5–C30 heteroarylene; R b R c and R d Each is independently selected from hydrogen, deuterium, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C5–C30 heteroaryl, substituted or unsubstituted C6–C30 amino, substituted or unsubstituted C6–C30 carbazole, or R. a R b R c and R d Any two atoms can be linked together to form a ring, and the heteroatoms are selected from O, N, S, P, Si, Se or B.

[0009] As a preferred technical solution, the novel spiro compound has the following structural formula:

[0010] Where: X is selected from O or S; X1 and X2 are each independently selected from O, S or CR. e R f , where R e R fEach is independently selected from hydrogen, deuterium, fluorine, trifluoride carbonyl, cyano, nitro, substituted or unsubstituted straight-chain or branched alkyl with 1-10 carbon atoms, or substituted or unsubstituted cycloalkyl with 3-20 carbon atoms;

[0011] R1-R8 are each independently selected from hydrogen, deuterium, fluorine, carbide, cyano, nitro, substituted or unsubstituted straight-chain or branched alkyl with 1-10 carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 carbon atoms, substituted or unsubstituted heteroalkyl with 1-10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon with 6-30 carbon atoms, substituted or unsubstituted heteroaromatic hydrocarbon with 5-30 carbon atoms, or two or more adjacent groups connected to each other to form a ring;

[0012] Group A is selected from substituted or unsubstituted aromatic hydrocarbon groups having 6-60 carbon atoms, substituted or unsubstituted heteroaromatic hydrocarbon groups having 5-60 carbon atoms, and N(R) a R b R c ), C(=O)R a R b Si(R) a R b R c R d ), P(=O)(R a R b R c ), S(=O)2(R a R b ), where R a The carbon atom attached to the aforementioned spiroring is selected from substituted or unsubstituted C6–C60 arylene and substituted or unsubstituted C5–C30 heteroarylene; R b R c and R d Each is independently selected from hydrogen, deuterium, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C5–C30 heteroaryl, substituted or unsubstituted C6–C30 amino, substituted or unsubstituted C6–C30 carbazole, or R. a R b R c and R d Any two atoms can be linked together to form a ring, and the heteroatoms are selected from O, N, S, P, Si, Se or B.

[0013] As a preferred technical solution, the structural formula of the novel spiro compound is any one of the following A, B, C, and D:

[0014]

[0015] Where: X is selected from O or S; X1 and X2 are each independently selected from O, S or CR. e R f , where R e R f Each is independently selected from hydrogen, deuterium, fluorine, carbide, cyano, nitro, straight-chain or branched alkyl with 1-10 carbon atoms, substituted or unsubstituted C3-C20 cycloalkyl;

[0016] R1-R8 are each independently selected from hydrogen, deuterium, fluorine, carbide, cyano, nitro, substituted or unsubstituted straight-chain or branched alkyl groups having 6-60 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups having 6-30 carbon atoms, substituted or unsubstituted heteroaromatic hydrocarbon groups having 5-30 carbon atoms, or two or more adjacent groups connected to each other to form a ring.

[0017] L1, L2, and L3 are each independently selected from single-bonded, substituted or unsubstituted aryl groups with 6-30 carbon atoms, or substituted or unsubstituted heteroaryl groups with 5-30 carbon atoms.

[0018] Y1, Y2, and Y3 are each independently selected from substituted or unsubstituted aromatic hydrocarbon groups with 6-60 carbon atoms, substituted or unsubstituted heteroaromatic hydrocarbon groups with 5-60 carbon atoms, and N(R a R b R c ), C(=O)R a R b Si(R) a R b R c R d ), P(=O)(R a R b R c ), S(=O)2(R a R b ), where R a The carbon atom attached to the aforementioned spiroring is selected from substituted or unsubstituted C6–C60 arylene and substituted or unsubstituted C5–C30 heteroarylene; R b R c and R d Each is independently selected from hydrogen, deuterium, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C5–C30 heteroaryl, substituted or unsubstituted C6–C30 amino, substituted or unsubstituted C6–C30 carbazole, or R. a R b R c and Rd Any two atoms can be linked together to form a ring, and the heteroatoms are selected from O, N, S, P, Si, Se or B;

[0019] As a preferred technical solution, in the general formula of the novel spiro compound, L1-L3 are selected from any one or a combination of the following groups:

[0020] Where Z is either C or N.

[0021] As a preferred technical solution, in the general formula of the novel spiro compound, Y1-Y3 are selected from any one or a combination of the following groups:

[0022] Wherein: Ar is selected from substituted or unsubstituted C6–C30 arylene, or substituted or unsubstituted C5–C30 heteroarylene; A a and A b Each is independently selected from hydrogen, deuterium, fluorine, -CF3, -CN, -NO2, substituted or unsubstituted C6–C20 aryl, substituted or unsubstituted C5–C20 heteroaryl; X is selected from O or S; X1–X7 are each independently selected from O, S or CR e R f , where R e R f Each is independently selected from hydrogen, deuterium, fluorine, trifluorinated carbonyl, cyano, nitro, straight-chain or branched alkyl with 1-10 carbon atoms, substituted or unsubstituted C3-C20 cycloalkyl.

[0023] More preferably, the novel spiro compound is selected from one or more of the following chemical structures:

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035] The method for synthesizing the novel spiro compound includes at least the following steps:

[0036] (1) Synthetic intermediate M;

[0037] (2) Synthesize novel spiro compounds A, B, C, and D.

[0038] As a preferred technical solution, the intermediate M is synthesized from raw material 1 and raw material 2 according to the following general formula:

[0039]

[0040] As a preferred technical solution, the raw material 1 is selected from any one of the following:

[0041] A is selected from aryl, heteroaryl, and alkyl groups.

[0042] As a preferred technical solution, the raw material 2 is selected from any one of the following:

[0043]

[0044] As a preferred technical solution, the intermediate M is any one of the following:

[0045]

[0046]

[0047] As a preferred technical solution, the intermediate M synthesized from raw materials 1 and 2 is specifically shown in Table 1.

[0048] Table 1

[0049]

[0050]

[0051]

[0052]

[0053] As a preferred technical solution, the general formula for synthesizing the novel spiro-containing compound A is as follows:

[0054]

[0055] As a preferred technical solution, the general formula for synthesizing the novel spiro compound B is as follows:

[0056]

[0057] As a preferred technical solution, the general formula for synthesizing the novel spiro compounds C and D is as follows: (1)

[0059] (2)

[0061]

[0062] The bromide intermediate M was converted into boride MC in a two-step synthesis, and then reacted with Cl-Y to synthesize novel spiro compounds C and D.

[0063] Another aspect of the present invention provides the application of a novel spiro compound in organic electroluminescent devices, used in the fabrication of such devices. The organic electroluminescent device includes at least a substrate, a first electrode, a hole transport layer, a light-emitting layer, an electron transport layer, and a second electrode. Any one of the hole transport layer, electron transport layer, and light-emitting layer in the organic electroluminescent device comprises one or more of the novel spiro compound. The organic electroluminescent device includes a top-emitting device and a bottom-emitting device.

[0064] The top-emitting device comprises, from top to bottom, a capping layer 110, a cathode-Ag 109, an electron transport layer 108, a hole blocking layer 107, a light-emitting layer 106, a second hole transport layer 105, a first hole transport layer 104, a hole injection layer 103, an anode 102, and a substrate 101. For details, please refer to the appendix. Figure 1 .

[0065] The bottom-emitting device, from top to bottom, includes a cathode-Ag 109, an electron transport layer 108, a hole blocking layer 107, a light-emitting layer 106, a second hole transport layer 105, a first hole transport layer 104, a hole injection layer 103, an anode 102, and a substrate 101. See the attached diagram for the specific structure. Figure 2 .

[0066] The following description is provided for the materials of each layer in the organic electroluminescent device:

[0067] anode

[0068] The anode material is selected from one or more combinations of indium tin oxide alloy, tin oxide, indium zinc oxide, gold, silver, platinum, copper, carbon nanotubes, carbon nanowires, and graphene.

[0069] The anode layer is prepared by one of the following methods: vapor deposition, sputtering, or coating.

[0070] The thickness of the anode layer is used in the range of 10nm~20μm, 20nm~100nm, 100nm~300nm, 300nm~500nm, and 500nm~800nm.

[0071] Hole injection layer

[0072] The thickness of the hole injection layer is in the range of 3nm~20nm, 3nm~10nm, 10nm~15nm, and 15nm~20nm;

[0073] The hole injection layer material is a metal oxide or an organic material; the metal oxide is one of molybdenum oxide, vanadium oxide, and tungsten oxide; the organic material is one of 4,4',4”-((1E,1'E,1”E)-cyclopropane-1,2,3-trimethylenetris(cyanoformyl))tris(2,3,5,6-tetrafluorobenzyl) (PD1, CAS No.: 1224447-88-4), tetracyanoquinone dimethyl (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinone dimethyl (F4-TCNQ), and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN).

[0074] A display or lighting device including the aforementioned organic electroluminescent device; an electronic device including the aforementioned organic electroluminescent device.

[0075] Beneficial effects

[0076] 1. This invention provides a novel spiro-containing compound that can be used as an electron transport material, hole transport material, and light-emitting host material in the field of organic electroluminescent materials.

[0077] 2. The novel spiro-containing compound provided by this invention has very good hole mobility, good thermal stability and is not easy to crystallize, and can be effectively used as a hole transport layer material in the preparation of organic electroluminescent devices.

[0078] 3. The novel spiro-containing compound provided by this invention has good electron transport performance and can be well matched with hole transport materials to form a good hole-electron balance, achieving the best state of efficiency and luminescence lifetime. It can be effectively used as an electron transport layer material in the preparation of organic electroluminescent devices.

[0079] 4. The novel spiro-containing compound provided by this invention has suitable energy levels, can form good energy transfer, and has high chemical stability. It can be effectively used as a light-emitting host layer material in the preparation of organic electroluminescent devices. Attached Figure Description

[0080] Appendix Figure 1 This is a structural diagram of a top-emitting device.

[0081] Appendix Figure 2 This is a structural diagram of a bottom-emitting device. Detailed Implementation

[0082] Example 1

[0083] Example 1 of the present invention provides a novel spiro-containing compound, the general synthetic formula of which is as follows:

[0084]

[0085] The synthesis method of A1-3 is as follows: Take a three-necked flask and first add A1-1 (15 g, 161 mmol), A1-2 (18 g, 161 mmol), tris(dibenzylacetone)palladium (Pd2(dba)3, 2.8 g, 3.87 mmol), tri-tert-butylphosphine (t-Bu3P, 32.2 mL, 16 mmol), sodium tert-butoxide (NaOBu-t, 46 g, 483 mmol), then add toluene (200 mL). Purge the system with nitrogen, heat the reaction mixture to reflux, and stir for 180 min. Cool the reaction mixture to 60 °C and superheat it using a silica gel column. Concentrate the mother liquor to 100 mL, add 60 mL of ethanol, stir at room temperature for 1 h, and filter. Add 100 mL of toluene to the solid, reflux to dissolve, add 100 mL of petroleum ether, stir at room temperature for 2 h, and filter. Toluene and petroleum ether were separated by column chromatography in a 2:1 ratio. The solution was evaporated to dryness to give 20 g of a white solid, with a yield of 73%. The M / Z ratio was 169.0 as determined by LCMS (ESI ion source).

[0086] Where A1-4 correspond to intermediate monomer M1, and the general formula for the synthesis of intermediate monomer M1 is as follows:

[0087]

[0088] The synthesis method of the intermediate monomer M1 is as follows: Take a clean 250 mL three-necked flask, add M1-2 (15 g, 68.8 mmol), then add THF (110 mL), purge the system with nitrogen three times, heat the reaction solution to 3°C in an ice-water bath, add 2.5 mol / L butyllithium (28.9 mL, 72.24 mmol) dropwise, and maintain the temperature for 2 hours after the addition is complete. Finally, pour in M1-1. TLC plate analysis confirms the completeness of the reaction. Add 100 mL of water to quench the reaction, then add 100 mL of ethyl acetate, and allow to stand for phase separation. Pass the upper organic phase through a silica gel column, and concentrate the solvent using petroleum ether:toluene = 50:1 to obtain 21 g of solid, with a yield of 65%. Dissolve this solid in 20 mL of diethyl carbonate, heat the reaction solution to 3°C in an ice-water bath, and finally add boron trifluoride diethyl ether dropwise. After the addition is complete, remove the ice-water bath and react for 2 hours. TLC plate analysis confirms the completeness of the reaction. The solution was quenched with 20 mL of water and allowed to stand to separate into layers. The upper organic phase was passed through a silica gel column and washed with petroleum ether. The organic phases were combined, and the solvent was concentrated to give 13 g of crude product M1, with a yield of 64%. The overall yield of the two steps was 42%.

[0089] The synthesis method, excipients, and raw material molar equivalents of other intermediates M are exactly the same as those of M1, except for slight differences in the added raw materials. The different raw materials corresponding to the different intermediate products are shown in Table 1. Due to the consistency of the synthesis methods, detailed explanations are not provided.

[0090] The synthesis method of A1 is as follows: Take a three-necked flask and first add A1-3 (15 g, 88.7 mmol), A1-4 (41 g, 88.7 mmol), tris(dibenzylacetone)palladium (Pd2(dba)3, 1.6 g, 1.77 mmol), tri-tert-butylphosphine (t-Bu3P, 17.66 mL, 8.8 mmol), sodium tert-butoxide (NaOBu-t, 25 g, 266 mmol), then add toluene (200 mL). Purge the system with nitrogen, heat the reaction mixture to reflux, and stir for 180 min. Cool the reaction mixture to 60 °C and superheat it using a silica gel column. Concentrate the mother liquor to 100 mL, add 50 mL of ethanol, stir at room temperature for 1 h, and filter. Add 150 mL of toluene to the solid, reflux to dissolve, add 100 mL of petroleum ether, stir at room temperature for 2 h, and filter. Toluene and petroleum ether were separated by column chromatography in a 2:1 ratio. The solution was evaporated to dryness to give 33 g of a white solid, with a yield of 67%. The M / Z ratio was 549.3 as determined by LCMS (ESI ion source).

[0091] The synthesis methods for other novel spiro compounds A and B are exactly the same as those for A1, except that the raw materials added are slightly different. In Examples 2-53, only raw material 1 is replaced with A1-1 in Example 1, raw material 2 is replaced with A1-2 in Example 1, intermediate 1 is replaced with A1-3 in Example 1, and raw material 3 is replaced with A1-4 in Example 1. Other excipients, operating methods, and molar ratios of raw materials and excipients are the same. For specific implementation schemes, please refer to Table 2.

[0092] Table 2

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] Example 54

[0099] Example 54 of the present invention provides a novel spiro-containing compound, the general formula of which is as follows:

[0100]

[0101] Wherein C2-2 corresponds to boride MC1, and the general formula for synthesizing boride MC1 is as follows:

[0102]

[0103] The synthesis method of the boride MC1 is as follows: MC1-1 (corresponding to M1 in the example, 15g, 32.5mmol), pinacol diborate (9.9g, 39mmol), potassium carbonate (6.4g, 65mmol), tris(dibenzylacetone)palladium (Pd2(dba)3, 1.0g, 1.1mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos, 1.3g, 3.25mmol), and 150mL of toluene are added sequentially to a 250mL reaction flask. The mixture is fully purged with nitrogen, heated to reflux for 2 hours, then cooled to approximately 90℃. 75mL of water is added, and the mixture is stirred for 10 minutes. After standing, the mixture is separated into liquid and solvent phases. The organic phase is evaporated to dryness for solvent removal. The product fraction is passed through a chromatography column in a hexane:toluene ratio of 5:1. The product fraction is collected and the liquid is evaporated to dryness to obtain 10.5g of white solid, with a yield of 71.9%.

[0104] The synthesis methods for converting other bromide intermediates into boride intermediates are consistent with this method, except that the bromide raw materials added are slightly different. As people in the field of chemical synthesis, we can understand that this illustrates the consistency of the synthesis methods. Therefore, the synthesis of other boride intermediates will not be further illustrated with examples.

[0105] The synthesis method of C2 is as follows: In a 500 mL three-necked flask, C2-1 (15 g, 43.6 mmol), C2-2 (18.5 g, 43.6 mmol), K2CO3 (12 g, 87.2 mmol), and tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (1.0 g, 0.87 mmol) were added sequentially. Then, 150 mL of toluene, 30 mL of ethanol, and 30 mL of water were added. The system was purged with nitrogen three times. The reaction solution was heated to reflux and stirred for 4 hours. The reaction solution was cooled to 70 °C, allowed to stand, and separated. The upper organic phase was washed with 60 mL of water, separated, and filtered through a silica gel column. The organic phase was concentrated to approximately 75 mL of toluene. 150 mL of petroleum ether was gradually added, resulting in the precipitation of a solid. The mixture was stirred for 2 hours, filtered, and the filter cake was washed with a small amount of petroleum ether. The mixture was then heated to 40°C and stirred for 2 hours with a solution of 50 mL toluene and 150 mL ethanol. The solid was filtered, and the mixture was then heated to 40°C and stirred for 2 hours with another solution of 50 mL toluene and 150 mL ethanol. The solid was filtered again and dried to obtain 22 g of compound C2, with a yield of 73%. The M / Z ratio was determined to be 689.3 by LCMS (ESI ion source).

[0106] The synthesis methods for other novel spiro compounds C and D are exactly the same as those for C2, except that the raw materials added are slightly different. In Examples 55-83, only raw material 1 is replaced with C2-1 in Example 54, and raw material 2 is replaced with C2-2 in Example 54. The other excipients, operating methods, and molar ratios of raw materials and excipients are the same. For specific implementation schemes, please refer to Table 3.

[0107] Table 3

[0108]

[0109]

[0110]

[0111]

[0112] Application Example 1

[0113] Application Example 1 of the present invention provides a novel spiro compound as a material for the first hole transport layer, applied to the fabrication of a blue light-emitting device (top-emitting). The specific fabrication process is as follows:

[0114] A reflective anode ITO (150nm) / Ag (100nm) / ITO (50nm) film is formed on a glass substrate 101, serving as the first electrode 102 as the anode, followed by vapor deposition. With hole transport materials The mixed material was used as the hole injection layer 103, with a mixing ratio of 3:97 (mass ratio), and then a 100 nm thick layer of compound A1 prepared in Example 1 of this invention was deposited by vapor deposition. The first hole transport layer 104 was obtained, and then a 20 nm thick compound was deposited by evaporation. The second hole transport layer 105 was obtained, and then deposited at a deposition rate of 95:5. 30nm, fabricate blue light-emitting unit 106, then evaporate 10nm A hole-blocking layer 107 is formed, and then vapor-deposited. An electron transport layer 108 with a thickness of 30 nm is formed by mixing materials in a 4:6 mass ratio. Then, a ytterbium layer with a thickness of 3 nm and a magnesium-silver layer with a thickness of 10 nm (mass ratio 1:9) are formed sequentially as the second electrode 109. Finally, a 70 nm capping layer material is deposited on top of this. It forms 110 layers.

[0115] Application Examples 2-24 provide novel spiro compounds as materials for the first hole transport layer, applied to the fabrication of blue light devices (top-emitting). The specific preparation process is the same as in Application Example 1, except that compounds A4, A17, A23, A34, A52, A108, A114, A125, A138, A158, A170, B5, B12, B15, B22, B26, B38, B99, B114, B124, B134, B147, and B169 are used instead of compound A1 in Application Example 1 as the first hole transport layer 104.

[0116] Device testing was performed using a combination of a Keithley power supply and an MS-75 spectroradiometer. Voltage measurements were taken at 10 mA / cm². 2 The voltage at that time, with an efficiency of 10mA / cm 2 The current efficiency at that time is expressed as the color coordinate CIEy value divided by the value (unit: Cd / A / CIEy), and the lifetime is 10 mA / cm. 2 The time required for the brightness to decay to 95% of the initial brightness under current is shown in Table 4.

[0117] Table 4

[0118]

[0119] Application Example 25

[0120] Application Example 25 of the present invention provides a novel spiro compound as a material for the second hole transport layer, applied to the fabrication of a red light device (bottom-emitting), the specific fabrication process of which is as follows:

[0121] A transparent anodic ITO film with a thickness of 150 nm is formed on a glass substrate 101 to obtain the first electrode 102 as the anode, followed by vapor deposition. With the compounds of the present invention A mixed material was used as the hole injection layer 103, with a mixing ratio of 3:97 (mass ratio), followed by the deposition of a 100 nm thick compound layer. The first hole transport layer 104 is obtained, and then the Al1 prepared in this invention with a thickness of 100 nm is deposited by vapor deposition. The second hole transport layer 105 was obtained, and then deposited at a deposition rate of 95:5. 40nm, fabricate red light emitting unit 106, then evaporate 10nm A hole-blocking layer 107 is formed, and then vapor-deposited. An electron transport layer 108 with a thickness of 30 nm is formed by mixing in a ratio of 4:6 (mass ratio), followed by the formation of a magnesium-silver layer with a thickness of 100 nm (mass ratio of 1:9) as the second electrode 109.

[0122] Application Examples 26-44 provide novel spiro compounds as materials for the second hole transport layer, applied to the fabrication of red light devices (bottom-emitting). The specific preparation process is the same as in Application Example 25, except that compounds A18, A28, A65, A82, A97, A117, A132, A144, A172, B21, B25, B39, B62, B80, B90, B104, B132, B143, and B170 of the present invention are used to replace compound A11 in Application Example 25 as the second hole transport layer 105.

[0123] Device testing was performed using a combination of Keithley power supply and MS-75 spectroradiometer. Voltage and efficiency are expressed as voltage (V) and current efficiency at 10 mA / cm² (unit: Cd / A), and lifetime is the time required for brightness to decay to 95% of initial brightness at a current of 10 mA / cm². The results are shown in Table 5.

[0124] Table 5

[0125]

[0126]

[0127] Application Example 45

[0128] Application Example 45 of the present invention provides a novel spiro compound as a material for the electron transport layer, applied to the fabrication of blue light devices (bottom-emitting), the specific fabrication process of which is as follows:

[0129] A transparent anodic ITO film with a thickness of 150 nm is formed on a glass substrate 101 to obtain the first electrode 102 as the anode, followed by vapor deposition. With hole transport materials A mixed material was used as the hole injection layer 103, with a mixing ratio of 3:97 (mass ratio), followed by the deposition of a 100 nm thick compound. The first hole transport layer 104 was obtained, and then a 20 nm thick compound was deposited by evaporation. The second hole transport layer 105 was obtained, and then deposited at a deposition rate of 95:5. 30nm, fabricate blue light-emitting unit 106, then evaporate 10nm A hole-blocking layer 107 is formed, and then vapor-deposited with... An electron transport layer 108 with a thickness of 30 nm was formed by mixing in a 4:6 mass ratio, followed by the deposition of a 10 nm thick layer. A hole-blocking layer 107 is formed, and then the compound C2 of the present invention is deposited by vapor deposition. An electron transport layer 108 with a thickness of 30 nm is formed by mixing in a ratio of 4:6 (mass ratio), followed by the formation of a magnesium-silver layer with a thickness of 100 nm (mass ratio of 1:9) as the second electrode 109.

[0130] Application Examples 46-68 provide novel spiro compounds as electron transport layer materials for the fabrication of blue light devices (bottom-emitting). The specific preparation process is the same as in Application Example 45, except that compounds C7, C22, C35, C41, C49, C51, C59, C108, C117, C119, C123, C137, C151, D10, D24, D44, D59, D71, D84, D95, D106, D117, and D139 of the present invention are used to replace compound C2 in Application Example 45 as electron transport layer 108.

[0131] Device testing was performed using a combination of Keithley power supply and MS-75 spectroradiometer. Voltage and efficiency were measured at 10 mA / cm². 2 Voltage (V) and current efficiency are expressed (in Cd / A), with a lifetime of 10 mA / cm. 2 The time required for the brightness to decay to 95% of the initial brightness under current is shown in Table 6.

[0132] Table 6

[0133]

[0134]

[0135] Application Example 69

[0136] Application Example 69 of the present invention provides a novel spiro compound as a material for the light-emitting host layer, applied to the fabrication of green light devices (bottom-emitting), the specific preparation process of which is as follows:

[0137] A transparent anodic ITO film with a thickness of 150 nm is formed on a glass substrate 101 to obtain the first electrode 102 as the anode, followed by vapor deposition. With hole transport materials A mixed material was used as the hole injection layer 103, with a mixing ratio of 3:97 (mass ratio), followed by the deposition of a 100 nm thick compound layer. The first hole transport layer 104 was obtained, and then a 400nm thick layer was deposited by vapor deposition. A second hole transport layer 105 was obtained, and then compound A43 of the present invention was deposited by vapor deposition at a deposition rate of 5:4:1. 40nm, fabricate red light emitting unit 106, then evaporate 10nm A hole-blocking layer 107 is formed, and then vapor-deposited. An electron transport layer 108 with a thickness of 30 nm is formed by mixing in a ratio of 4:6 (mass ratio), followed by the formation of a magnesium-silver layer with a thickness of 100 nm (mass ratio of 1:9) as the second electrode 109.

[0138] Application Examples 70-83 provide novel spiro compounds as materials for the light-emitting host layer, applied to the fabrication of green light devices (bottom-emitting). The specific preparation process is the same as in Application Example 69, except that compounds A69, A72, A100, A162, B43, B71, B161, C25, C27, C31, C132, D29, and D130 of the present invention are used to replace compound A43 in Application Example 69 as the light-emitting host layer 106.

[0139] Device testing was performed using a combination of Keithley power supply and MS-75 spectroradiometer. Voltage and efficiency are expressed as voltage (V) and current efficiency at 10 mA / cm² (unit: Cd / A). The time required for brightness to decay to 95% of initial brightness at a lifetime of 10 mA / cm² current is shown in Table 7.

[0140] Table 7

[0141]

[0142] Comparative Example 1

[0143] The specific embodiment of Comparative Example 1 of the present invention is the same as that of Application Example 1, except that Comparative Compound 1 is used instead of Compound A1 in Application Example 1 as the first hole transport layer 104. The structure of Comparative Compound 1 is as follows:

[0144]

[0145] Comparative Example 2

[0146] The specific embodiment of Comparative Example 1 of the present invention is the same as that of Application Example 1, except that comparative compound 2 is used instead of compound A1 in Application Example 1 as the first hole transport layer 104. The structure of comparative compound 2 is as follows:

[0147]

[0148] Comparative Example 3

[0149] The specific embodiment of Comparative Example 3 of the present invention is the same as that of Application Example 25, except that comparative compound 3 is used instead of compound A11 in Application Example 25 as the second hole transport layer 105. The structure of comparative compound 3 is as follows:

[0150]

[0151] Comparative Example 4

[0152] The specific embodiment of Comparative Example 4 of the present invention is the same as that of Application Example 25, except that comparative compound 4 is used instead of compound A11 in Application Example 25 as the second hole transport layer 105. The structure of comparative compound 4 is as follows:

[0153]

[0154] Comparative Example 5

[0155] The specific embodiment of Comparative Example 5 of the present invention is the same as that of Application Example 45, except that Comparative Compound 5 is used instead of Compound C2 in Application Example 45 as the electron transport layer 108. The structure of Comparative Compound 5 is as follows:

[0156]

[0157] Comparative Example 6

[0158] The specific embodiment of Comparative Example 6 of the present invention is the same as that of Application Example 45, except that comparative compound 6 is used instead of compound C2 in Application Example 45 as the electron transport layer 108. The structure of comparative compound 6 is as follows:

[0159]

[0160] Comparative Example 7

[0161] The specific embodiment of Comparative Example 7 of the present invention is the same as that of Application Example 69, except that comparative compound 7 is used instead of compound A43 in Application Example 69 as the light-emitting host layer 106. The structure of comparative compound 7 is as follows:

[0162]

[0163] Comparative Example 8

[0164] The specific embodiment of Comparative Example 8 of the present invention is the same as that of Application Example 69, except that comparative compound 8 is used instead of compound A43 in Application Example 69 as the light-emitting host layer 106. The structure of comparative compound 8 is as follows:

[0165]

Claims

1. A spiro compound, characterized in that, The spiro compound has a general structural formula of any one of the following: A, B, C, or D. A、 B、 C、 D、 , Where: X is O or S; X1 and X2 are each independently selected from O or CR. e R f , where R e R f Each group is independently selected from hydrogen, straight-chain or branched alkyl groups having 1-10 carbon atoms; R1-R8 are selected from H, straight-chain or branched alkyl groups having 6-60 carbon atoms, or two adjacent groups connected to each other to form a ring; L1 is a single bond, L2 and L3 are selected from arylene groups having 6-30 carbon atoms and heteroarylene groups having 5-30 carbon atoms; Y1, Y2 and Y3 are each independently selected from aromatic hydrocarbon groups having 6-60 carbon atoms and heteroaromatic hydrocarbon groups having 5-60 carbon atoms.

2. The application of the spiro compound according to claim 1 in an organic electroluminescent device, characterized in that, It is used in the fabrication of organic electroluminescent devices.

3. The application of the spiro compound according to claim 2 in organic electroluminescent devices, characterized in that, The organic electroluminescent device includes at least a substrate, a first electrode, a hole transport layer, a light-emitting layer, an electron transport layer, and a second electrode.

4. The application of the spiro compound according to claim 3 in organic electroluminescent devices, characterized in that, In the organic electroluminescent device, any one of the hole transport layer, electron transport layer, and light-emitting layer includes one or more of the spiro compounds.

5. A display or lighting device, characterized in that, Including the organic electroluminescent device as described in any one of claims 2-4.

6. An electronic device, characterized in that, Including the organic electroluminescent device as described in any one of claims 2-4.

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