A composition, an organic electroluminescent device, and a display device

Abstract

This invention provides a composition, an organic electroluminescent device, and a display device. The composition comprises two compounds of Formula I; or the composition comprises one compound of Formula I and two compounds of Formula II; the compound of Formula I is obtained by fusion of a group of Formula I-A with any two adjacent carbon atoms on ring A of a group of Formula I-B; the compound of Formula II is obtained by fusion of a group of Formula I-C with any two adjacent carbon atoms on ring E of a group of Formula I-D. By designing the specific components of the composition, this invention uses this composition as the light-emitting layer material of the organic electroluminescent device, resulting in an organic electroluminescent device with excellent overall performance.

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to a composition, an organic electroluminescent device, and a display device. Background Technology

[0002] Organic electroluminescence (EL) refers to the phenomenon where organic materials directly convert electrical energy into light energy under the influence of an electric field. Organic electroluminescent devices are self-emissive light-emitting devices that utilize this principle. They possess characteristics such as self-illumination, vibrant and bright colors, thinness, light weight, fast response speed, wide viewing angle, low driving voltage, tolerance to harsh natural conditions, and the ability to be made into flexible panels. As a result, they have gradually become the most advantageous technology in the next generation of flat panel displays.

[0003] The structure of an organic light-emitting diode (OLED) device includes an anode, a cathode, and an organic layer between them. To improve the efficiency and stability of OLEDs, the organic material layers consist of multiple layers with different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer, a light-emitting layer, an electron transport layer (ETL), and an electron injection layer (EIL). The hole injection layer facilitates the injection of holes from the OLED anode into the hole transport layer. The hole injection layer is generally directly adjacent to the anode, and one or more hole transport layers are directly adjacent to the hole injection layer on the cathode side. The hole transport layer is the layer that transports holes. It is generally located between the cathode and the organic layer closest to the anode. The electron blocking layer blocks electrons from the cathode direction. Compared to the hole transport layer, the electron blocking layer has a shallower LUMO (Lower Luminous Moment of Motion), meaning the absolute value of the electron blocking layer's LUMO is smaller than the absolute value of the hole transport layer's LUMO.

[0004] To obtain high-performance organic electroluminescent devices, the research and development of organic materials has attracted widespread attention. Therefore, there is an urgent need in this field to develop more types and higher-performance materials to meet people's higher requirements for OLED devices. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a composition, an organic electroluminescent device, and a display device. In this invention, by designing the specific components of the composition, a composition with excellent performance is obtained. Using this composition as the material for the light-emitting layer of an organic electroluminescent device, a high-performance organic electroluminescent device can be prepared.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a composition comprising two compounds of Formula I;

[0008] Alternatively, the composition may comprise one compound of Formula I and two compounds of Formula II;

[0009] The compound shown in Formula I is obtained by fusion of a group shown in Formula IA with any two adjacent carbon atoms on ring A in the group shown in Formula IB.

[0010]

[0011] Where * represents a fusion site;

[0012] Ar 21 Ar 22 Each is independently selected from C6-C30 aryl or C6-C20 heteroaryl;

[0013] The hydrogen atom in the compound shown in Formula I can be substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl, and C1-C6 alkoxy.

[0014] The compound shown in Formula I meets at least one of the following conditions:

[0015] (1) The compound shown in Formula I does not contain deuterium atoms;

[0016] (2) In the compound shown in Formula I, all hydrogen atoms on at least one of the rings A, B, and C are replaced by deuterium atoms;

[0017] (3) Ar in the compound shown in formula I 21 At least one hydrogen atom is replaced by a deuterium atom;

[0018] (4) Ar in the compound shown in Formula I 22 At least one hydrogen atom is replaced by a deuterium atom;

[0019] (5) The hydrogen atoms in the compound shown in Formula I are replaced by C6-C20 aryl groups, and at least one hydrogen atom in the C6-C20 aryl groups is replaced by a deuterium atom.

[0020] (6) In the compound shown in Formula I, the hydrogen atoms are replaced by C1-C6 alkyl and / or C1-C6 alkoxy groups, and all hydrogen atoms in the C1-C6 alkyl and / or C1-C6 alkoxy groups are replaced by deuterium atoms.

[0021] The compound represented by Formula II is obtained by fusion of a group represented by Formula IC with any two adjacent carbon atoms on ring E of the group represented by Formula ID.

[0022]

[0023] Where * represents a fusion site;

[0024] Ar 11Selected from any one of single bonds, phenylene, naphthylene, and biphenylene;

[0025] R 101 R 102 Each is independently selected from H, C6-C30 aryl, or C6-C20 heteroaryl;

[0026] X, Y, and Z are each independently selected from N or CR. 304 R 304 It is selected from any one of H, phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, and dibenzothiopheneyl, and at least one of X, Y, and Z is N;

[0027] X1 is selected from O, S, Where R 301 R 302 Each is independently selected from C1-C5 alkyl or phenyl groups, R 303 Selected from phenyl or biphenyl, with dashed lines indicating connection sites;

[0028] The hydrogen atom in the compound shown in Formula II can be substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl, and C1-C6 alkoxy.

[0029] The compound shown in Formula II meets at least one of the following conditions:

[0030] (a) The compound shown in Formula II does not contain deuterium atoms;

[0031] (b) In the compound shown in Formula II, all hydrogen atoms on at least one of the rings F, D, and E are replaced by deuterium atoms;

[0032] (c) R in the compound shown in Formula II 101 At least one hydrogen atom is replaced by a deuterium atom;

[0033] (d) R in the compound shown in Formula II 102 At least one hydrogen atom is replaced by a deuterium atom;

[0034] Ar in the compound shown in formula (e) II 11 At least one hydrogen atom is replaced by a deuterium atom;

[0035] (f) R in the compound shown in formula II 301 and R 302 All hydrogen atoms in it are replaced by deuterium atoms;

[0036] (g) R in the compound shown in Formula II 303 At least one hydrogen atom in the group is replaced by a deuterium atom;

[0037] (h) R in the compound shown in formula II304 It is a deuterium atom;

[0038] (i) R in the compound shown in Formula II 304 When selected from phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, and dibenzothiopheneyl, at least one hydrogen atom in phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, and dibenzothiopheneyl is replaced by a deuterium atom;

[0039] (j) In the compound shown in Formula II, the hydrogen atoms are replaced by C6-C20 aryl groups, and at least one hydrogen atom in the C6-C20 aryl groups is replaced by a deuterium atom;

[0040] (k) In the compound shown in formula II, the hydrogen atoms are replaced by C1-C6 alkyl and / or C1-C6 alkoxy groups, and all hydrogen atoms in the C1-C6 alkyl and / or C1-C6 alkoxy groups are replaced by deuterium atoms.

[0041] In this invention, by designing the specific composition of the composition and further using at least two specific compounds in combination, a composition with a specific composition is obtained. Using this composition as the material of the light-emitting layer of an organic electroluminescent device, an organic electroluminescent device with excellent performance can be prepared.

[0042] In this invention, C6 to C30 are selected from C6, C10, C12, C18, C24 or C30, etc.

[0043] The C6 to C20 are selected from C6, C10, C12, C18, or C20, etc.

[0044] C1 to C6 are selected from C1, C2, C3, C4, C5 or C6.

[0045] C1 to C5 are selected from C1, C2, C3, C4 or C5.

[0046] It should be noted that the two compounds shown in Formula I in this invention refer to compounds that both conform to the general formula of Formula I, but the specific structural formulas of the two compounds shown in Formula I are different; similarly, the two compounds shown in Formula II refer to compounds that both conform to the general formula of Formula II, but the specific structural formulas of the two compounds shown in Formula II are different.

[0047] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0048] As a preferred embodiment of the present invention, the composition comprises two compounds of Formula I, and the composition further comprises at least one compound of Formula II.

[0049] Preferably, the composition comprises two compounds of Formula I and one compound of Formula II.

[0050] Preferably, the composition comprises two compounds of Formula I and two compounds of Formula II.

[0051] In this invention, the composition comprises two compounds of Formula I (denoted as compound 1-1 and compound 1-2), and the volume ratio of compound 1-1 to compound 1-2 is (2:8)-(8:2), for example, it can be 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 or 8:2, etc.

[0052] Alternatively, the composition may comprise two compounds of Formula I (denoted as Compound 1-1 and Compound 1-2) and one compound of Formula II (denoted as Compound 2-1), wherein the volume ratio of Compound 1-1, Compound 1-2, and Compound 2-1 is 1:(1-2):(1-6), for example, it may be 1:1:1, 1:1:2, 1:1:3, 1:1:4, 1:2:1, 1:2:2, 1:2:3, 1:2:4, 1:2:5, or 1:2:6, etc.

[0053] Alternatively, the composition may comprise one compound of Formula I (denoted as compound 1-1) and two compounds of Formula II (denoted as compound 2-1 and compound 2-2), wherein the volume ratio of compound 1-1, compound 2-1, and compound 2-2 is (1-6):(1-2):1, for example, it may be 1:1:1, 2:1:1, 3:1:1, 4:1:1, 1:2:1, 2:2:1, 3:2:1, 4:2:1, 5:2:1, or 6:2:1, etc.

[0054] Alternatively, the composition comprises two compounds of Formula I (denoted as compound 1-1 and compound 1-2) and two compounds of Formula II (denoted as compound 2-1 and compound 2-2), wherein the volume ratio of compound 1-1 to compound 1-2 is (2:8) to (8:2), for example, it can be 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 or 8:2, etc., and the volume ratio of compound 2-1 to compound 2-2 is (2:8) to (8:2), for example, it can be 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 or 8:2, etc., and the ratio of the sum of the volumes of compound 1-1 and compound 1-2 to the sum of the volumes of compound 2-1 and compound 2-2 is (2:8) to (8:2), for example, it can be 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 or 8:2, etc.

[0055] Preferably, in the composition, at least one compound of formula I meets at least one of conditions (2) to (6).

[0056] Preferably, in the composition, at least one compound of formula I meets at least one of conditions (2) to (6), and the compound of formula II meets condition (a).

[0057] Preferably, the composition comprises a compound of formula I containing deuterium atoms and a compound of formula I that does not contain deuterium atoms.

[0058] The compound containing deuterium atoms shown in Formula I is selected from any one of compounds I-1-D, I-2-D, and I-3-D.

[0059] As a preferred technical solution of the present invention, the Ar 21 Ar 22 Each is independently selected from any one or a combination of at least two of phenyl, naphthyl, fluorenyl, anthracene, phenanthryl, diphenyl, dibenzofuranyl, dibenzothiophene, triphenyl or tetraphenyl.

[0060] Preferably, the Ar 21 Selected from phenyl, diphenyl, or triphenyl.

[0061] Preferably, the Ar 22 Selected from diphenyl, triphenyl, or tetraphenyl.

[0062] Preferably, the Ar 21 The Ar is phenyl. 22 Selected from diphenyl, triphenyl, or tetraphenyl.

[0063] Preferably, the Ar 21 It is a diphenyl group, and the Ar is... 22 Selected from diphenyl or triphenyl.

[0064] Preferably, the R 101 R 102 Each is independently selected from any one of H, phenyl, naphthyl, triphenylene, fluoranyl, fluorenyl, anthracene, phenanthryl, biphenyl, naphthyl, dibenzofuranyl, and dibenzothiophene.

[0065] Preferably, the R 101 R 102 Each is independently selected from any one of phenyl, biphenyl, or triphenylene.

[0066] Preferably, the R 303 Selected from phenyl.

[0067] Preferably, the Ar 11 It is selected from any one of single bonds, phenylene, or naphthylene.

[0068] As a preferred embodiment of the present invention, the compound represented by Formula I has a structure as shown in Formula I-1, Formula I-2, or Formula I-3:

[0069]

[0070] Among them, Ar 21 Ar 22 It has the same scope of protection as described above;

[0071] Preferably, the compound represented by Formula I meets condition (3) and / or condition (4).

[0072] Preferably, the compound represented by Formula I is selected from any one of compounds I-1-D, I-2-D, and I-3-D:

[0073]

[0074] Among them, Ar 21 Ar 22 It has the same protection scope as the above, and Ar 21 Ar 22 The hydrogen atom was not replaced by a deuterium atom.

[0075] As a preferred embodiment of the present invention, the compound represented by Formula I is selected from any one of the following compounds:

[0076]

[0077]

[0078]

[0079]

[0080] In the above compounds, hydrogen atoms can be replaced by deuterium atoms.

[0081] Preferably, the compound represented by Formula I is selected from any one of compounds H-1 to H-44:

[0082]

[0083]

[0084]

[0085] The hydrogen atoms in compounds H-1 to H-44 can be replaced by deuterium atoms.

[0086] As a preferred embodiment of the present invention, the compound represented by Formula II is selected from any one of the following compounds:

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] In the above compounds, hydrogen atoms can be replaced by deuterium atoms.

[0102] In a second aspect, the present invention provides a compound, said compound comprising the following compounds:

[0103]

[0104]

[0105] The compound is used to prepare the composition as described in the first aspect.

[0106] Thirdly, the present invention provides an intermediate comprising the following compounds:

[0107]

[0108] The intermediate is used to prepare the compound of formula I in the composition as described in the first aspect.

[0109] It should be noted that in this invention, no special restrictions are placed on the preparation methods of the compounds shown in Formula I and Formula II. They can be prepared by methods commonly used in the art. For example, the preparation methods described in CN112996793A, CN112805277A, and CN102212066A can be referred to.

[0110] Fourthly, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;

[0111] The material of the organic thin film layer includes the composition described in the first aspect;

[0112] Preferably, the organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes the composition described in the first aspect;

[0113] Preferably, the organic thin film layer includes a hole layer;

[0114] Preferably, the hole layer includes an electron blocking layer; the material of the electron blocking layer includes spirofluorene compounds;

[0115] The spirofluorene compound has the specific structure shown in Formula III below:

[0116]

[0117] Where X is selected from O or S;

[0118] R 11 R 21 Each is independently selected from hydrogen, deuterium, fluorine, CN, substituted or unsubstituted C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18 or C20, etc.) straight-chain or branched alkyl, substituted or unsubstituted C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18 or C20, etc.) alkoxy, substituted or unsubstituted C6-C40 (e.g., C6, C8, C10, C12, C15, C18, C24, C30, C36 or C40, etc.) aryl;

[0119] Ar is selected from substituted or unsubstituted C6 to C40 (e.g., C6, C8, C10, C12, C15, C18, C24, C30, C36, or C40, etc.) arylene groups;

[0120] Ar1 and Ar2 are each independently selected from substituted or unsubstituted C6-C40 (e.g., C6, C8, C10, C12, C15, C18, C24, C30, C36, or C40, etc.) aryl, substituted or unsubstituted C12-C40 (C12, C14, C16, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, or C40, etc.) oxaaryl, substituted or unsubstituted C12-C40 (C12, C14, C16, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, or C40, etc.) thioaryl, and at least one of Ar1 or Ar2 is selected from any one of phenyl, naphthyl, triphenylene, or fluoranthracene; p is selected from 0 or 1;

[0121] m and n are each independently selected from integers from 0 to 4, for example, they can be 0, 1, 2, 3, 4.

[0122] It should be noted that the oxaaryl group refers to a structure with an oxygen-containing five-membered heterocycle formed by two aromatic rings connected by a single bond and bridged by an O atom. For example, two benzene rings are connected by a single bond to form biphenyl. The carbon atoms on the two benzene rings that make up the biphenyl are simultaneously connected to an O atom to form dibenzofuran.

[0123] The thioheroaryl group refers to a structure with a sulfur-containing five-membered heterocycle formed by two aromatic rings connected by a single bond and bridged by an S atom. For example, two benzene rings are connected by a single bond to form biphenyl. The carbon atoms on the two benzene rings that make up the biphenyl are simultaneously connected to an S atom to form dibenzothiophene.

[0124] Preferably, the spirofluorene compound is selected from the compounds shown in III-1 or III-2:

[0125]

[0126] Among them, X and X1 are each independently selected from O or S;

[0127] R 11 R 21 Ar has the same protection scope as the above;

[0128] Ar1 is selected from any one of phenyl, naphthyl, triphenylene, or fluoranthyl;

[0129] R 31Selected from C1 to C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, or C20, etc.) straight-chain or branched alkyl groups, C1 to C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, or C20, etc.) alkoxy groups, and C6 to C40 (e.g., C6, C8, C10, C12, C15, C18, C24, C30, C36, or C40, etc.) aryl groups;

[0130] R 41 R 42 Each is independently selected from C1 to C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, or C20, etc.) straight-chain or branched alkyl groups, and C6 to C40 (e.g., C6, C8, C10, C12, C15, C18, C24, C30, C36, or C40, etc.) aryl groups, and R 41 and R 42 They can be independent of each other or connected in a ring by a single bond.

[0131] Preferably, the spirofluorene compound is selected from any one of the following compounds 1-140 and compounds 1S-140S:

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140] The compound 1S-140S is a mixture of compound 1-140... Replace with The dashed lines represent connection points.

[0141] For example, the structure of compound 2 is The structure of compound 2S is then:

[0142] Fifthly, the present invention provides a display device comprising the organic electroluminescent device as described in the fourth aspect.

[0143] Compared with the prior art, the present invention has the following beneficial effects:

[0144] By designing the specific components of the composition and further using at least two specific compounds in combination, a composition with a specific composition is obtained. Using this composition as the material of the light-emitting layer of an organic electroluminescent device, an organic electroluminescent device with low driving voltage, high current efficiency, and long lifespan can be prepared. Detailed Implementation

[0145] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0146] Synthesis Example 1

[0147] This synthetic example provides compound H-28-D1 and its synthetic method, which is as follows:

[0148]

[0149] (1) Synthesis of intermediate H-28-D1-1

[0150] Under nitrogen protection, 80 mL of dry toluene, 2.56 g of the compound shown in IBC-1, 2.5 g of brominated deuterated biphenyl, 0.0575 g of Pd(dba)2 (bis(dibenzylacetone)palladium, 0.4 g of a 10% (w / w) toluene solution of tri-tert-butylphosphine, and 1.44 g of sodium tert-butoxide were added to a 250 mL three-necked flask. The mixture was slowly heated to reflux and reacted for 8 hours. After cooling to room temperature, water was added to dissolve the mixture. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and separated by silica gel column chromatography with petroleum ether:dichloromethane = 10:1 (v / v) to give 3.1 g of intermediate H-28-D1-1.

[0151] Mass spectrometry analysis of intermediate H-28-D1-1 showed a mass-to-charge ratio (m / z) of 417.22.

[0152] (2) Synthesis of compound H-28-D1

[0153] The synthesis of intermediate H-28-D1-1 is similar to that of intermediate H-28-D1-1, except that the compound shown in IBC-1 is replaced with an equal amount of intermediate H-28-D1-1, and the brominated deuterated biphenyl is replaced with an equal amount of 3-bromodibenzo[b,d]furan, to obtain compound H-28-D1.

[0154] Mass spectrometry analysis of compound H-28-D1 revealed a mass-to-charge ratio (m / z) of 583.26.

[0155] Synthesis Examples 2-8

[0156] Synthesis Examples 2-8 provide a compound and its synthesis method, respectively. An intermediate is synthesized by reactant 1 and reactant 2, and then the intermediate is reacted with the corresponding bromide to obtain the corresponding compound (see Table 1 below). The specific synthesis method is the same as that in Synthesis Example 1.

[0157] The intermediates and compounds provided in Synthesis Examples 2-8 were subjected to mass spectrometry analysis, and the measured mass-to-charge ratios (m / z) are detailed in Tables 1 and 2 below.

[0158] Table 1

[0159]

[0160]

[0161] Table 2

[0162]

[0163]

[0164] Other compounds for which specific synthesis steps are not listed can be prepared using common knowledge in the art, in conjunction with the above examples.

[0165] The specific structures of the compounds used in the following device embodiments and device comparative examples are as follows:

[0166] The specific structures of the compounds used in the following examples are shown below:

[0167]

[0168]

[0169]

[0170] Device Example 1

[0171] This embodiment of the device provides an organic electroluminescent device, in which the composition provided by the present invention is selected as the red light host material in the organic electroluminescent device.

[0172] The structure of the organic electroluminescent device is as follows: ITO / HT-1 (20nm) / red light host material (35nm): Ir(piq)3 [10%] / TPBI (10nm) / Alq3 (15nm) / LiF (0.5nm) / Al (150nm). Here, "Ir(piq)3 [10%]" refers to the doping ratio of the red light dye, i.e., the volume ratio of the red light host material to Ir(piq)3 is 90:10.

[0173] The fabrication process of organic electroluminescent devices is as follows:

[0174] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a acetone:ethanol mixed solvent, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0175] The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁶. -5 ~9×10 -4 Pa, a hole transport layer HT-1 is vacuum-deposited on the above-mentioned anodic layer film at a deposition rate of 0.1 nm / s and a film thickness of 20 nm.

[0176] A red light host material and dye Ir(piq)3 are vacuum-deposited on the hole transport layer as the light-emitting layer of the organic electroluminescent device. The deposition rate is 0.1 nm / s and the total film thickness is 35 nm. In this embodiment of the device, if the red light host is compound H-2 and compound H-2D, compound H-2 and compound H-2D are placed in different evaporation sources for heating. The heating rate is controlled so that the volume ratio of each material deposited on the substrate is 1:1, which serves as the red light host material.

[0177] Electron transport layers TPBI and Alq3 were sequentially vacuum-deposited on top of the light-emitting layer at a deposition rate of 0.1 nm / s, with film thicknesses of 10 nm and 15 nm, respectively.

[0178] 0.5 nm of LiF was vacuum-deposited on the electron transport layer, and 150 nm of Al was used as the electron injection layer and cathode.

[0179] Device Comparison Example 1-2

[0180] Comparative Examples 1 and 2 provide an organic electroluminescent device, which differs from Device Example 1 only in that the red light host material is different (see Table 3 below). The other preparation steps and conditions are the same as those in Device Example 1.

[0181] Performance testing:

[0182] The brightness, driving voltage, current efficiency, and lifetime (LT90) of the fabricated organic electroluminescent device were measured using an OLED-1000 multi-channel accelerated aging lifetime and photochromic performance analysis system manufactured by Hangzhou Yuanfang. The lifetime test (LT90) refers to maintaining a constant current density (1000 cd / m²) at room temperature (25–27°C) while retaining the initial brightness. 2 The time required for the brightness to decrease to 90% of the initial brightness. In the table below, the driving voltage, current efficiency, and LT90 lifetime are all relative values. See Table 3 below for detailed test results.

[0183] Table 3

[0184]

[0185] Note: In the table, " / " indicates that the red light host material of this device embodiment does not contain this compound, and the same applies below.

[0186] As can be seen from Table 3, in this invention, using the two compounds shown in Formula I as the light-emitting layer materials, and further controlling one of the two compounds shown in Formula I to contain deuterium atoms, can further reduce the driving voltage of the organic electroluminescent device and improve the current efficiency and lifespan of the organic electroluminescent device.

[0187] Device Examples 2-10

[0188] Device Examples 2-10 each provide an organic electroluminescent device. The only difference between them and Device Example 1 is that the red light host material is different. If the red light host is two or more compounds, each compound is placed in a different evaporation source for heating. The heating rate is controlled so that the volume ratio of each compound deposited on the substrate is the same, which serves as the red light host material (see Tables 4 and 5 below). Other preparation steps and conditions are the same as those in Device Example 1.

[0189] Device Comparison Example 3-4

[0190] Comparative Examples 3-4 provide an organic electroluminescent device, which differs from Device Example 1 only in that the red light host material is different. If the red light host is two or more compounds, each compound is placed in a different evaporation source for heating, and the heating rate is controlled so that the volume ratio of each vaporized onto the substrate is the same, which serves as the red light host material (see Table 4 below). Other preparation steps and conditions are the same as those in Device Example 1.

[0191] The performance of the organic electroluminescent devices provided in Device Examples 2-10 and Device Comparative Examples was tested using the same methods as above. The test results are detailed in Tables 4 and 5 below.

[0192] Table 4

[0193]

[0194] As can be seen from Table 4, in this invention, the composition designed with at least one compound of Formula I containing deuterium atoms can further reduce the driving voltage of organic electroluminescent devices and improve the current efficiency and lifespan of organic electroluminescent devices.

[0195] As can be seen from Device Comparison Example 3 and Device Comparison Example 4, using the compound shown in Formula I containing deuterium atoms can significantly improve the lifetime of organic electroluminescent devices.

[0196] Compared to Device Example 3, using compound H-3-DE (with deuterium atoms attached to the indole-3-carbazole ring group) and compound H-3, along with optional compound H-3-D, as the host materials for red light (Device Examples 2 and 4) can further reduce the driving voltage of the organic electroluminescent device and improve its current efficiency and lifetime. In particular, using compound H-3-DE (with deuterium atoms attached to the indole-3-carbazole ring group) and compound H-3 as the host materials for red light results in organic electroluminescent devices with superior performance. This is because, when used as the host material, HOMO is mainly distributed on the middle indole-3-carbazole ring. When HOMO loses electrons, the D atoms attached to the middle indole-3-carbazole ring are more stable and the material is less prone to decomposition.

[0197] In addition, the present invention uses a multi-component compound as the main material for red light, which improves its film-forming properties and increases charge mobility, thereby further improving the driving voltage and current efficiency of the organic electroluminescent device. At the same time, since the film formed by the multi-component compound has higher stability, the lifespan of the organic electroluminescent device is improved.

[0198] Table 5

[0199]

[0200] As can be seen from Device Examples 9 and 10, if the compound of Formula I selected has a high content of deuterium atoms (compound H-28DF used in Device Example 10), the overall performance of the prepared organic electroluminescent device is poor.

[0201] As can be seen from Device Example 7 and Device Example 8, the overall performance of the organic electroluminescent devices prepared by the two is quite similar. However, Device Example 7 uses H-28, a low-cost compound that does not contain deuterium atoms, which meets the requirements of industrial production.

[0202] Comparing Device Examples 5-7 with Device Example 8, if both compounds of Formula I in the composition contain deuterium atoms (Device Example 8), the performance of the organic electroluminescent device will actually deteriorate. Furthermore, as shown in Tables 3-5, if the composition of the present invention consists of two compounds of Formula I, it is preferable to have one compound of Formula I containing deuterium atoms and one compound of Formula I without deuterium atoms. More preferably, it is preferable to have one compound of Formula I with deuterium atoms attached to the indole-carbazole ring group and one compound of Formula I without deuterium atoms, thereby preparing an organic electroluminescent device with excellent overall performance.

[0203] Device Example 11

[0204] This embodiment of the device provides an organic electroluminescent device, in which the composition provided by the present invention is selected as the red light host material in the organic electroluminescent device.

[0205] The structure of the organic electroluminescent device is as follows: ITO / HT-1 (20nm) / red light host material (35nm): Ir(piq)3 [10%] / TPBI (10nm) / Alq3 (15nm) / LiF (0.5nm) / Al (150nm). Here, "Ir(piq)3 [10%]" refers to the doping ratio of the red light dye, i.e., the volume ratio of the red light host material to Ir(piq)3 is 90:10.

[0206] The fabrication process of organic electroluminescent devices is as follows:

[0207] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a acetone:ethanol mixed solvent, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0208] The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁶. -5 ~9×10 -4 Pa, a hole transport layer HT-1 is vacuum-deposited on the above-mentioned anodic layer film at a deposition rate of 0.1 nm / s and a film thickness of 20 nm.

[0209] A red light host material and dye Ir(piq)3 are vacuum-deposited on the hole transport layer as the light-emitting layer of the organic electroluminescent device. The deposition rate is 0.1 nm / s and the total film thickness is 35 nm. In this embodiment, if the red light host is two or more compounds, each compound is placed in a different evaporation source for heating. The heating rate is controlled so that the volume ratio of each compound deposited on the substrate is the same, which serves as the red light host material (the specific composition of the red light host material is detailed in Table 6).

[0210] Electron transport layers TPBI and Alq3 were sequentially vacuum-deposited on top of the light-emitting layer at a deposition rate of 0.1 nm / s, with film thicknesses of 10 nm and 15 nm, respectively.

[0211] 0.5 nm of LiF was vacuum-deposited on the electron transport layer, and 150 nm of Al was used as the electron injection layer and cathode.

[0212] Device Examples 12-25

[0213] Device Examples 12-25 each provide an organic electroluminescent device. The only difference between them and Device Example 11 is that the red light host material is different. If the red light host is two or more compounds, each compound is placed in a different evaporation source for heating. The heating rate is controlled so that the volume ratio of each compound deposited on the substrate is the same, which serves as the red light host material (see Table 6 below). Other preparation steps and conditions are the same as those in Device Example 11.

[0214] Device Comparison Examples 5-10

[0215] Comparative Examples 5-10 each provide an organic electroluminescent device. The only difference between them and Example 11 is that the red light host material is different. If the red light host is two or more compounds, each compound is placed in a different evaporation source for heating. The heating rate is controlled so that the volume ratio of each compound deposited on the substrate is the same, which serves as the red light host material (see Table 6 below). Other preparation steps and conditions are the same as in Example 11.

[0216] The performance of the organic electroluminescent devices provided in Device Examples 12-25 and Device Comparative Examples 5-10 was tested using the same methods as above. The test results are detailed in Table 6 below.

[0217] Table 6

[0218]

[0219]

[0220] As can be seen from device examples 11-13, the organic electroluminescent device prepared by using a composition containing four compounds in this invention has better performance than the organic electroluminescent device prepared by using a combination of three compounds.

[0221] As can be seen from Device Examples 11-13 and Device Comparative Examples 5-6, if the composition includes a compound of Formula I (Device Comparative Examples 5-6), the overall performance of the prepared organic electroluminescent device is poor.

[0222] As can be seen from device examples 20, 21, and 23, if R in the compound shown in Formula II... 101 Ar is a triphenylene oxide or one of the compounds shown in Formula II. 11 It is a naphthyl group, which can further improve the lifetime of organic electroluminescent devices.

[0223] As can be seen from the comparison between device example 16 and device example 11, if the composition contains compound E-8, the driving voltage of the organic electroluminescent device can be further reduced and its current efficiency improved.

[0224] As can be seen from device examples 18-19, if Ar in the compound shown in formula II 11 It is a single bond, which can improve the current efficiency of organic electroluminescent devices.

[0225] As can be seen from Comparative Examples 5 and 10, the device containing one compound of Formula I and two compounds of Formula II exhibits better performance than the device containing one compound of Formula I and one compound of Formula II.

[0226] Device Example 26

[0227] This embodiment of the device provides an organic electroluminescent device, in which the composition provided by the present invention is selected as the red light host material in the organic electroluminescent device.

[0228] The structure of the organic electroluminescent device is as follows: ITO / HT-1 (20nm) / electron blocking layer (5nm) / red light host material (35nm): Ir(piq)3 [10%] / TPBI (10nm) / Alq3 (15nm) / LiF (0.5nm) / Al (150nm). Here, "Ir(piq)3 [10%]" refers to the doping ratio of the red light dye, i.e., the volume ratio of the red light host material to Ir(piq)3 is 90:10.

[0229] The fabrication process of organic electroluminescent devices is as follows:

[0230] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a acetone:ethanol mixed solvent, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0231] The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁶. -5 ~9×10 -4 Pa, a hole transport layer HT-1 is vacuum-deposited on the above-mentioned anodic layer film at a deposition rate of 0.1 nm / s and a film thickness of 20 nm.

[0232] EB was vacuum-deposited on top of the hole transport layer as an electron blocking layer at a deposition rate of 0.1 nm / s and a film thickness of 5 nm.

[0233] A red light host material and dye Ir(piq)3 are vacuum-deposited on an electron blocking layer to serve as the light-emitting layer of an organic electroluminescent device. The deposition rate is 0.1 nm / s, and the total film thickness is 35 nm. In this embodiment of the device, if the red light host is H-3, H-3-DE, E-1, or E-1D, each compound is placed in a different evaporation source and heated. The heating rate is controlled so that the volume ratio of each material deposited on the substrate is the same, thus serving as the red light host material.

[0234] Electron transport layers TPBI and Alq3 were sequentially vacuum-deposited on top of the light-emitting layer at a deposition rate of 0.1 nm / s, with film thicknesses of 10 nm and 15 nm, respectively.

[0235] 0.5 nm of LiF was vacuum-deposited on the electron transport layer, and 150 nm of Al was used as the electron injection layer and cathode.

[0236] Device Example 27

[0237] Device Example 27 provides an organic electroluminescent device, which differs from Device Example 26 only in that the electron blocking layer material is different (see Table 7 below). The other preparation steps and conditions are the same as those of Device Example 26.

[0238] The performance of the organic electroluminescent devices provided in Device Examples 26-27 was tested using the same methods as above. The test results are detailed in Table 7 below.

[0239] Table 7

[0240]

[0241] As shown in Table 7, by selecting spirofluorene compounds with specific structures as electron blocking layer materials and combining them with the composition provided by this invention as light-emitting layer materials, the organic electroluminescent devices prepared in this invention have higher current efficiency and longer service life.

[0242] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A composition, characterized in that, The composition comprises two compounds of Formula I; Alternatively, the composition may comprise one compound of Formula I and two compounds of Formula II; The compound shown in Formula I is obtained by fusion of a group shown in Formula IA with any two adjacent carbon atoms on ring A in the group shown in Formula IB. ； Where * represents a fusion site; Ar 21 Ar 22 Each is independently selected from any one or a combination of at least two of phenyl, naphthyl, fluorenyl, anthracene, phenanthryl, diphenyl, dibenzofuranyl, dibenzothiophene, triphenyl or tetraphenyl; The hydrogen atom in the compound shown in Formula I can be substituted by at least one of -F, -CN, C6~C20 aryl, C1~C6 alkyl, and C1~C6 alkoxy. The compound shown in Formula I meets at least one of the following conditions: (1) The compound shown in Formula I does not contain deuterium atoms; (2) In the compound shown in Formula I, all hydrogen atoms on at least one of the rings A, B, and C are replaced by deuterium atoms; (3) Ar in the compound shown in Formula I 21 At least one hydrogen atom is replaced by a deuterium atom; (4) Ar in the compound shown in Formula I 22 At least one hydrogen atom is replaced by a deuterium atom; (5) The hydrogen atoms in the compound shown in Formula I are replaced by C6~C20 aryl groups, and at least one hydrogen atom in the C6~C20 aryl groups is replaced by a deuterium atom; (6) The hydrogen atoms in the compound shown in Formula I are replaced by C1~C6 alkyl and / or C1~C6 alkoxy groups, and all hydrogen atoms in the C1~C6 alkyl and / or C1~C6 alkoxy groups are replaced by deuterium atoms; The compound represented by Formula II is obtained by fusion of a group represented by Formula IC with any two adjacent carbon atoms on ring E of the group represented by Formula ID. ； Where * represents a fusion site; Ar 11 Selected from any one of single bonds, phenylene, naphthylene, and biphenylene; R 101 R 102 Each is independently selected from any one of H, phenyl, naphthyl, triphenylene, fluoranyl, fluorenyl, anthracene, phenanthryl, biphenyl, naphthyl, dibenzofuranyl, and dibenzothiopheneyl; X, Y, and Z are each independently selected from N or CR. 304 R 304 It is selected from any one of H, phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, and dibenzothiopheneyl, and at least one of X, Y, and Z is N; X1 is selected from O, S, , , where R 301 R 302 Each is independently selected from C1-C5 alkyl or phenyl groups, R 303 Selected from phenyl or biphenyl, with dashed lines indicating connection sites; The hydrogen atom in the compound shown in Formula II can be substituted by at least one of -F, -CN, C6~C20 aryl, C1~C6 alkyl, and C1~C6 alkoxy. The compound shown in Formula II meets at least one of the following conditions: (a) The compound shown in Formula II does not contain deuterium atoms; (b) In the compound shown in Formula II, all hydrogen atoms on at least one of the rings F, D, and E are replaced by deuterium atoms; (c) R in the compound shown in Formula II 101 At least one hydrogen atom is replaced by a deuterium atom; (d) R in the compound shown in Formula II 102 At least one hydrogen atom is replaced by a deuterium atom; (e) Ar in the compound shown in formula II 11 At least one hydrogen atom is replaced by a deuterium atom; (f) R in the compound shown in Formula II 301 and R 302 All hydrogen atoms in it are replaced by deuterium atoms; (g) R in the compound shown in Formula II 303 At least one hydrogen atom in the group is replaced by a deuterium atom; (h) R in the compound shown in Formula II 304 It is a deuterium atom; (i) R in the compound shown in Formula II 304 When selected from phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, and dibenzothiopheneyl, at least one hydrogen atom in phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, and dibenzothiopheneyl is replaced by a deuterium atom; (j) In the compound shown in Formula II, the hydrogen atoms are replaced by C6~C20 aryl groups, and at least one hydrogen atom in the C6~C20 aryl groups is replaced by a deuterium atom; (k) In the compound shown in Formula II, the hydrogen atoms are replaced by C1~C6 alkyl and / or C1~C6 alkoxy groups, and all hydrogen atoms in the C1~C6 alkyl and / or C1~C6 alkoxy groups are replaced by deuterium atoms.

2. The composition according to claim 1, characterized in that, The composition comprises two compounds of Formula I, and the composition further comprises at least one compound of Formula II.

3. The composition according to claim 2, characterized in that, The composition comprises two compounds of Formula I and one compound of Formula II.

4. The composition according to claim 2, characterized in that, The composition comprises two compounds of Formula I and two compounds of Formula II.

5. The composition according to claim 1, characterized in that, In the composition, at least one compound of formula I meets at least one of conditions (2) to (6).

6. The composition according to claim 5, characterized in that, In the composition, at least one compound of formula I meets at least one of conditions (2) to (6), and the compound of formula II meets condition (a).

7. The composition according to claim 1, characterized in that, The composition includes a compound of formula I containing deuterium atoms and a compound of formula I that does not contain deuterium atoms. The compound of formula I containing deuterium atoms is selected from any one of compounds I-1-D, I-2-D, and I-3-D: ； Among them, Ar 21 Ar 22 It has the same scope of protection as claim 1, and Ar 21 Ar 22 The hydrogen atom was not replaced by a deuterium atom.

8. The composition according to claim 1, characterized in that, The Ar 21 Selected from phenyl, diphenyl, or triphenyl.

9. The composition according to claim 1, characterized in that, The Ar 22 Selected from diphenyl, triphenyl, or tetraphenyl.

10. The composition according to claim 1, characterized in that, The Ar 21 The Ar is phenyl. 22 Selected from diphenyl, triphenyl, or tetraphenyl.

11. The composition according to claim 1, characterized in that, The Ar 21 It is a diphenyl group, and the Ar is... 22 Selected from diphenyl or triphenyl.

12. The composition according to claim 1, characterized in that, The R 101 R 102 Each is independently selected from any one of phenyl, biphenyl, or triphenylene.

13. The composition according to claim 1, characterized in that, The R 303 Selected from phenyl.

14. The composition according to claim 1, characterized in that, The Ar 11 It is selected from any one of single bonds, phenylene, or naphthylene.

15. The composition according to claim 1, characterized in that, The compound represented by Formula I has a structure as shown in Formula I-1, Formula I-2, or Formula I-3: ； Among them, Ar 21 Ar 22 It has the same scope of protection as claim 1.

16. The composition according to claim 1, characterized in that, The compound shown in Formula I meets conditions (3) and / or condition (4).

17. The composition according to claim 1, characterized in that, The compound represented by Formula I is selected from any one of compounds I-1-D, I-2-D, and I-3-D: ； Among them, Ar 21 Ar 22 It has the same scope of protection as claim 1, and Ar 21 Ar 22 The hydrogen atom was not replaced by a deuterium atom.

18. The composition according to claim 1, characterized in that, The compound represented by Formula I is selected from any one of the following compounds: ； In the above compounds, hydrogen atoms can be replaced by deuterium atoms.

19. The composition according to claim 1, characterized in that, The compound represented by Formula I is selected from any one of compounds H-1 to H-44: ； The hydrogen atoms in compounds H-1 to H-44 can be replaced by deuterium atoms.

20. The composition according to claim 1, characterized in that, The compound represented by Formula II is selected from any one of the following compounds: ； In the above compounds, hydrogen atoms can be replaced by deuterium atoms.

21. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode; The material of the organic thin film layer includes the composition as described in any one of claims 1-20.

22. The organic electroluminescent device according to claim 21, characterized in that, The organic thin film layer includes a light-emitting layer, and the material of the light-emitting layer includes the composition according to any one of claims 1-20.

23. The organic electroluminescent device according to claim 21, characterized in that, The organic thin film layer includes a void layer.

24. The organic electroluminescent device according to claim 23, characterized in that, The hole layer includes an electron blocking layer; the material of the electron blocking layer includes spirofluorene compounds; The spirofluorene compound has the specific structure shown in Formula III below: Formula III; Where X is selected from O or S; R 11 R 21 Each is independently selected from hydrogen, deuterium, fluorine, CN, C1~C20 straight-chain or branched alkyl, C1~C20 alkoxy, and C6~C40 aryl; Ar is selected from C6~C40 arylene groups; Ar1 and Ar2 are each independently selected from C6~C40 aryl, C12~C40 oxaaryl, and C12~C40 thiaaryl, and at least one of Ar1 or Ar2 is selected from any one of phenyl, naphthyl, triphenylene or fluoranthyl. p is selected from 0 or 1; m and n are each independently selected from integers between 0 and 4.

25. A display device, characterized in that, The display device includes an organic electroluminescent device as described in any one of claims 21-24.

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