Deuterated composition, organic electroluminescent device and display device

Abstract

The invention provides a deuterated composition, an organic electroluminescent device and a display device. The deuterated composition comprises a deuterated mixture prepared from at least two compounds shown in the formula I through a deuterated reaction, and the molar masses of the at least two compounds shown in the formula I are the same; at least one of the at least two compounds shown in the formula I is a compound shown in a formula I-1. The invention provides a deuterated mixture obtained by a deuterated reaction of at least two compounds with specific structures shown in the formula I, and a deuterated composition comprising the deuterated mixture is used as a luminescent layer main body material, so that the organic electroluminescent device with excellent comprehensive performance is obtained. The organic light-emitting device has relatively low driving voltage and relatively high current efficiency.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescent materials, and in particular relates to a deuterated composition, an organic electroluminescent device and a display device. Background Art

[0002] The phenomenon of organic electroluminescence was discovered as early as 1963, but it did not attract much attention at the time. It was not until 1987 that the Tang research team at Eastman Kodak published a high-brightness, high-efficiency thin-film organic electroluminescent device (OLED) made of organic fluorescent materials and hole materials, which was driven by low DC voltage and high brightness. This technology then regained attention and opened up a new research field.

[0003] OLED technology offers significant advantages over other display technologies, including low power consumption, fast response time, flexibility, wide viewing angle, large display area, and a full range of luminous colors. Furthermore, it is compatible with various existing standards and technologies to create low-cost light-emitting devices, demonstrating broad application prospects in achieving color flat-panel displays. Over the past few decades, OLED, as a new display technology, has achieved significant development and has been widely adopted in flat-panel displays, flexible displays, solid-state lighting, and automotive displays.

[0004] Therefore, developing more types of light-emitting layer main materials with better performance to meet their use requirements in high-performance OLED devices is a research focus in this field. Summary of the Invention

[0005] In response to the shortcomings of the prior art, the present invention provides a deuterated composition, an organic electroluminescent device, and a display device. The present invention provides a deuterated mixture obtained by deuterating at least two compounds of Formula I having a specific structure. Using the deuterated composition comprising the deuterated mixture as the host material for the light-emitting layer, an organic electroluminescent device with excellent overall performance is obtained, including a low driving voltage and high current efficiency.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a deuterated composition, comprising a deuterated mixture prepared by a deuteration reaction of at least two compounds having structures represented by the following formula I, wherein the at least two compounds having structures represented by the following formula I have the same molar mass;

[0008]

[0009] wherein Ar2 is selected from a combination of at least one of phenyl, naphthyl, and biphenyl;

[0010] Ar3is selected from the group consisting of radicals having the structure of Formula I-M, and the dotted line indicates the site of attachment;

[0011] at least one of the at least two compounds having the structure of Formula I is a compound having the structure of Formula I-1:

[0012]

[0013] each of the hydrogen atoms in the compound of Formula I and the compound of Formula I-1 can be independently replaced by a deuterium atom.

[0014] In the present application, by carrying out a deuterium substitution reaction on at least two compounds having the structure of Formula I and having the same molar mass, and by controlling at least one of the compounds to have the structure of Formula I-1, a deuterium-substituted mixture is obtained. The components in the deuterium-substituted mixture are directly mixed more uniformly, and thus the film-forming property is better, the obtained film is more uniform, the charge transport ability is stronger, and the OLED light-emitting device prepared by using the deuterium-substituted mixture as the host material of the light-emitting layer has a lower driving voltage and a higher current efficiency.

[0015] If two compounds having the structure of Formula I and having the same molar mass are separately subjected to a deuterium substitution reaction to obtain two deuterium-substituted mixtures, and the two deuterium-substituted mixtures are used together as the host material of the light-emitting layer of an OLED device to prepare the OLED device, and if, according to the technical solution of the present application, at least two compounds having the structure of Formula I and having the same molar mass are selected, and at least one of the two compounds is controlled to have the structure of Formula I-1, and a deuterium-substituted mixture is prepared by carrying out a deuterium substitution reaction, and the deuterium-substituted mixture is used as the host material of the light-emitting layer of an OLED device to prepare the OLED device, compared with the former, the components in the deuterium-substituted mixture are directly mixed more uniformly, and thus the film-forming property is better, the obtained film is more uniform, the charge transport ability is stronger, and the OLED device prepared by using the deuterium-substituted composition containing the deuterium-substituted mixture as the host material of the light-emitting layer has improved driving voltage and current efficiency.

[0016] Furthermore, at least two compounds having the structure of Formula I and having the same molar mass, but neither of which has the structure of Formula I-1, are subjected to a deuterium substitution reaction to obtain a deuterium-substituted mixture, and the deuterium-substituted mixture is used as the host material of the light-emitting layer of an OLED device to prepare the OLED device, and the performance of the OLED device prepared is poor.

[0017] It should be noted that in an organic reaction process, when the reactive sites on the reacting molecules are not significantly different, it is difficult to carry out a substitution reaction at a specific reactive site. Therefore, in the present invention, after subjecting at least two compounds of Formula I to a deuteration reaction, a mixture (deuterated mixture) is obtained. Even if only one H atom on the reactant molecule is replaced by a deuterium atom, because the activity of each H atom on the reactant is not significantly different, the mixture obtained at this time, if subjected to mass spectrometry, has a molecular weight increase of 1 compared to the main peak of the reactants. However, the mixture obtained at this time is a mixture of various isomers obtained by substitution of single deuterium atoms.

[0018] The following are examples:

[0019]

[0020] For BH1, it contains 24 hydrogen atoms. When one of the H atoms is replaced by a deuterium atom, the resulting isomers include but are not limited to the following:

[0021]

[0022] When the above compounds are present in a deuterated composition, the mass spectrum peaks and molecular ion peaks m / z are the same.

[0023] For BH1, it contains 24 hydrogen atoms, 23 of which are replaced by deuterium atoms, resulting in isomers including but not limited to the following:

[0024]

[0025]

[0026] When the above compounds are present in a deuterated composition, the mass spectrum peaks and molecular ion peaks m / z are the same.

[0027] Similarly, for BH1, which contains 24 hydrogen atoms, 2-22 of which are replaced by deuterium atoms, the resulting isomers are numerous and complex. Those skilled in the art can draw the specific structure based on common knowledge.

[0028] As long as the deuteration reaction proceeds and the deuteration rate is not 0 or 100%, the obtained deuterated composition will inevitably contain multiple components.

[0029] As long as the deuteration reaction proceeds, the deuterated combination may contain any one of the products in which 1 H atom is replaced by deuterium, products in which 2 H atoms are replaced by deuterium, products in which 3 H atoms are replaced by deuterium, products in which 4 H atoms are replaced by deuterium, products in which 5 H atoms are replaced by deuterium, products in which 6 H atoms are replaced by deuterium, products in which 7 H atoms are replaced by deuterium, products in which 8 H atoms are replaced by deuterium, products in which 9 H atoms are replaced by deuterium, ..., products in which 24 H atoms are replaced by deuterium, or a combination of at least two of them.

[0030] Moreover, in the deuteration reaction conditions of the present invention, assuming that the deuteration rate of BH1 is 12.5%, theoretically, 3 H atoms are replaced by deuterium atoms. According to the reaction principle and common knowledge, not all BH1 molecules have 3 H atoms replaced by deuterium atoms. There must be products in which 2 H, 1 H, 4 H, and 5 H are replaced by deuterium atoms. In this case, if the mass spectrum m / z of BH1 is represented by M, the deuterated composition with a deuteration rate of 12.5% ​​has at least 5 mass peaks at m / z on the far right of the mass spectrum, namely M+1, M+2, M+3, M+4, and M+5, and two peaks M+6 and M+7 appear, which are isotope peaks. Of course, it can be judged based on common knowledge in this field whether the two peaks of M+6 and M+7 are the contributions of the separate isotopes of M+4 and M+5, or the products of 6 H replaced by deuterium atoms or 7 H replaced by deuterium atoms in the deuterated composition.

[0031] It should be noted that the present invention does not have any special restrictions on the mass ratio between the at least two compounds undergoing the deuteration reaction, and can be adjusted according to actual use requirements and performance.

[0032] As a preferred technical aspect of the present invention, Ar2 in the at least two compounds of formula I are both selected from biphenyl groups.

[0033] As a preferred technical aspect of the present invention, Ar2 in the at least two compounds of formula I are both selected from phenyl.

[0034] As a preferred technical aspect of the present invention, Ar2 in the at least two compounds of formula I are both selected from naphthyl.

[0035] As a preferred technical solution of the present invention, the compound of formula I is selected from any one of the following compounds:

[0036]

[0037] As a preferred technical solution of the present invention, the deuterated composition includes a deuterated mixture prepared by a deuterated reaction of two compounds in any one of the following groups 1 to 4:

[0038] Group 1:

[0039] Group 2:

[0040] Group 3:

[0041] Group 4:

[0042] As a preferred technical solution of the present invention, the deuteration reaction comprises the following steps:

[0043] In the presence of a catalyst, the raw materials for the deuteration reaction are placed in D2O and a solvent to carry out a deuteration reaction to obtain the deuterated mixture.

[0044] Preferably, the solvent is selected from any one of benzene, toluene, ethyl acetate or C6D6 or a combination of at least two thereof, more preferably C6D6.

[0045] It should be noted that C6D6 is the product after all hydrogen atoms on benzene are replaced by deuterium atoms.

[0046] Preferably, the solvent is C6D6, and the volume ratio of D2O to C6D6 is 1:(4-6), for example, it can be 1:4, 1:4.2, 1:4.4, 1:4.6, 1:4.8, 1:5, 1:5.2, 1:5.4, 1:5.6, 1:5.8 or 1:6, etc.

[0047] Preferably, the reaction is carried out in the presence of a catalyst, and the catalyst is selected from any one or a combination of at least two of an inorganic salt of a metal, an organic salt of a metal, or a metal complex, wherein the metal in the inorganic salt of the metal, the organic salt of the metal, or the metal complex is independently selected from palladium, platinum, rhodium, ruthenium, iridium, iron, copper, cobalt, or nickel; the catalyst is further preferably PdCl2.

[0048] Preferably, the reaction is carried out in a hydrogen atmosphere.

[0049] Preferably, the temperature of the deuteration reaction is 60-200°C, for example, it can be 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C.

[0050] Preferably, the deuteration reaction time is 1 to 80 h, for example, 1 h, 2 h, 4 h, 6 h, 10 h, 12 h, 24 h, 30 h, 40 h, 50 h, 60 h, 70 h or 80 h.

[0051] Preferably, the pressure of the deuteration reaction is 0.01 to 2 MPa, for example, 0.01 MPa, 0.05 MPa, 0.1 MPa, 0.2 MPa, 0.4 MPa, 0.6 MPa, 0.8 MPa, 1 MPa, 1.2 MPa, 1.4 MPa, 1.6 MPa, 1.8 MPa or 2 MPa.

[0052] Preferably, the deuterium substitution rate of the deuterated mixture is 15% to 99%, for example, it can be 15.0%, 20.5%, 28.4%, 38.0%, 46.1%, 53.4%, 60.7%, 69.8%, 70.2%, 80.6%, 88.2%, 90.3% or 99.0%.

[0053] In the present invention, the deuterium substitution rate refers to the percentage of the number of deuterium atoms (D) in the composition or compound to the total number of deuterium atoms and hydrogen atoms (H), that is, deuterium substitution rate = y / (x+y)*100%, wherein y is the number of deuterium atoms in the composition or compound, and x is the number of hydrogen atoms in the composition or compound. Assuming that the composition or compound contains all H and no D, the deuterium substitution rate is 0%. If all H in the composition or compound is replaced by D, the deuterium substitution rate is 100%.

[0054] It should be noted that the deuteration reaction of the present invention is also carried out in the presence of activated carbon. At the same time, after the deuteration reaction of the present invention is completed, a post-treatment step is also included. The post-treatment method includes cooling, filtering, liquid separation, and drying.

[0055] In a second aspect, the present invention provides an organic electroluminescent device, comprising an anode, a cathode, and an organic layer between the anode and the cathode;

[0056] The material of the organic layer includes the deuterated composition as described in the first aspect;

[0057] Preferably, the organic layer includes a light-emitting layer;

[0058] The material of the light-emitting layer includes a host material, and the host material includes the deuterated composition as described in the first aspect.

[0059] Preferably, the organic layer further includes a hole transport layer (including at least one of a hole injection layer, a hole transport layer, and an electron blocking layer) and an electron layer (including at least one of a hole blocking layer, an electron transport layer, and an electron injection layer).

[0060] As a preferred technical solution of the present invention, the material of the light-emitting layer further includes a doping material;

[0061] The doping material includes a compound having a structure shown in the following formula BDI:

[0062]

[0063] Among them, Ar 101 、Ar 102 、Ar 201 、Ar 202 Each is independently selected from any one of a substituted or unsubstituted C6-C40 (for example, C6, C10, C12, C15, C18, C24, C30, C36 or C40) aryl group, and a substituted or unsubstituted C12-C20 (for example, C12, C13, C14, C15, C16, C17, C18, C19 or C20) heteroaryl group;

[0064] R 101 and R 102 Each is independently selected from any one of substituted or unsubstituted C1-C12 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12) alkyl, substituted or unsubstituted C6-C40 (for example, C6, C10, C12, C15, C18, C24, C30, C36 or C40, etc.) aryl, and substituted or unsubstituted C12-C20 (for example, C12, C13, C14, C15, C16, C17, C18, C19 or C20) heteroaryl;

[0065] R 101 and R 102 Can be connected into rings by single bonds;

[0066] m and n are each independently selected from 0 or 1, and m and n are not 0 at the same time;

[0067] Ar 101 、Ar 102 、Ar 201 、Ar 202 、R 101 and R 102 The substituted substituents are each independently selected from any one or a combination of at least two of -D, -F, -CN, C1-C12 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12) alkyl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkoxy, C2-C8 (for example, C2, C3, C4, C5, C6, C7 or C8) alkenyl, C6-C15 (for example, C6, C7, C8, C10, C12 or C15, etc.) aryl, and C12-C20 (for example, C12, C15, C18 or C20, etc.) heteroaryl.

[0068] As a preferred technical solution of the present invention, the C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, benzofluorenyl, 9,10-diphenylanthracenyl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzoanthracenyl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthofluorenyl or benzonaphthofluorenyl, preferably any one of phenyl, naphthyl, biphenyl, terphenyl, fluoranthenyl, fluorenyl, 9,10-diphenylanthracenyl or benzofluorenyl.

[0069] Preferably, the C12-C20 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl and dinaphthothiophenyl.

[0070] Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, cyclopentyl or cyclohexyl.

[0071] Preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, propoxy, butoxy or The dotted line indicates the connection site.

[0072] Preferably, the C6-C15 aryl group is selected from any one of phenyl, naphthyl or biphenyl.

[0073] As a preferred technical solution of the present invention, the Ar 101 and Ar 102 Each independently selected from any one of the following substituted or unsubstituted groups: phenyl, naphthyl, biphenyl, terphenyl, fluoranthenyl, fluorenyl, 9,10-diphenylanthryl, benzofluorenyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl or naphthobenzothiophenyl;

[0074] The substituted substituent is selected from -D (deuterium atom), -F, -CN, phenyl, biphenyl, dibenzofuranyl, methyl, deuterated methyl, adamantyl, tert-butyl, 1-methylcyclopentyl, cyclohexyl, cyclopentyl, methoxy, Any one of naphthyl, dibenzothienyl, naphthobenzothienyl or a combination of at least two thereof; the dotted line indicates the connection site.

[0075] Preferably, the Ar 201 and Ar 202 Each independently selected from any one of the following substituted or unsubstituted groups: phenyl, naphthyl, dibenzofuranyl or biphenyl;

[0076] The substituted substituent is selected from any one or a combination of at least two of methyl, methoxy, phenyl or dibenzofuranyl.

[0077] Preferably, R 101 and R 102 Each is independently selected from any one of methyl, ethyl, propyl or phenyl.

[0078] Preferably, R 101 and R 102 same.

[0079] As a preferred technical solution of the present invention, the compound of formula BDI is selected from any one of the following compounds:

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088] Preferably, the compound of formula BDI is selected from any one of the following compounds:

[0089]

[0090]

[0091] As a preferred technical solution of the present invention, the doping material includes a compound having a structure shown in the following formula II:

[0092]

[0093] Among them, the R 21 、R 22 and R 23 Each is independently selected from hydrogen, C1-C12 (for example, C1, C2, C4, C6, C8, C10 or C12) linear or branched alkyl, C6-C12 (for example, C6, C7, C8, C9, C10, C11 or C12) cycloalkyl, -NAr 23 Ar 24 Any of the following;

[0094] The Ar 21 、Ar 22 、Ar 23 、Ar 24 Each is independently selected from any one of a substituted or unsubstituted C6-C20 (for example, C6, C8, C10, C12, C14, C16, C18 or C20, etc.) aryl group, and a substituted or unsubstituted C3-C20 (for example, C3, C6, C8, C10, C12, C14, C16, C18 or C20, etc.) heteroaryl group;

[0095] Ar 21 、Ar 22 、Ar 23 、Ar 24 The substituted substituents are each independently selected from C1-C5 (e.g., C1, C2, C3, C4, or C5) linear or branched alkyl groups or C6-C12 (e.g., C6, C7, C8, C9, C10, C11, or C12) aryl groups.

[0096] Preferably, the Ar 21 、Ar 22 、Ar 23 、Ar 24 Each independently selected from

[0097]

[0098] Any of the above, with the short key indicating the attachment site.

[0099] Preferably, the R 21 、R 22 and R 23 Each is independently selected from any one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group or an adamantyl group.

[0100] As a preferred technical solution of the present invention, the compound of formula II is selected from any one of the following compounds:

[0101]

[0102]

[0103] As a preferred technical solution of the present invention, the doping material includes a compound having a structure shown in the following formula III:

[0104]

[0105] Wherein, the Ar 31 、Ar 32 、Ar 33 and Ar 34 Each is independently selected from any one of a substituted or unsubstituted C6-C22 (for example, C6, C8, C10, C12, C15, C18 or C22) aryl group, and a substituted or unsubstituted C12-C40 (for example, C12, C15, C18, C24, C30, C36 or C40) heteroaryl group;

[0106] R 31 Any one selected from phenyl, naphthyl or biphenyl;

[0107] Said a is selected from 0 or 1;

[0108] Ar 31 、Ar 32 、Ar 33 、Ar 34 The substituted substituents are each independently selected from C1-C5 (e.g., C1, C2, C3, C4, or C5) linear or branched alkyl groups or C6-C12 (e.g., C6, C7, C8, C9, C10, C11, or C12) aryl groups.

[0109] Preferably, the Ar 31 、Ar 32 、Ar 33 and Ar 34 Each independently selected from Any one or a combination of at least two of the following, the short bond represents the connection site.

[0110] Preferably, the compound of formula III is selected from any one of the following compounds:

[0111]

[0112]

[0113] In a third aspect, the present invention provides a display device, comprising the organic electroluminescent device according to the second aspect.

[0114] Compared with the prior art, the present invention has the following beneficial effects:

[0115] The present invention designs the composition of the deuterated mixture, performs a deuteration reaction on at least two compounds having the same molar mass and conforming to the structure shown in Formula I, and at least one compound conforming to the structure shown in Formula I-1, to obtain a deuterated mixture, and uses the deuterated mixture as the main material of the light-emitting layer. The OLED light-emitting device prepared in this way has a lower driving voltage and higher current efficiency. DETAILED DESCRIPTION

[0116] The technical solution of the present invention is further described with reference to specific embodiments. It should be understood by those skilled in the art that the embodiments are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0117] Preparation Example 1 Synthesis of Compound BH364-6

[0118] This preparation example provides compound BH364-6 and its synthesis method, which is as follows:

[0119]

[0120] Under nitrogen, 60 mL of toluene, 60 mL of ethanol, and 16 mL of water were added to a three-necked flask, followed by addition of 3.0 g of the raw material 9-phenylanthracene-10-boric acid, 3.0 g of the raw material 5-bromonaphtho[1,2-b]benzofuran, 2.12 g of sodium carbonate, and 0.23 g of tetrakistriphenylphosphine palladium. The temperature was slowly raised to reflux for 6 h, then cooled to room temperature, and water was added to separate the layers. The organic layer was washed with water, dried over magnesium sulfate, and after removing the desiccant, the mixture was concentrated to dryness and crystallized from a mixed solvent of chloroform and ethanol to obtain compound BH364D (4.1 g).

[0121] The obtained compound BH364-6 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 470.17.

[0122] Example 1

[0123] This embodiment provides a BHAD series deuterated composition, which is prepared by a deuterated reaction of a mixture of compounds BH364 and BH446. The preparation method is as follows:

[0124]

[0125] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0126] The specific preparation method of the above-mentioned BHAD series deuterated compositions is as follows:

[0127] At room temperature, compound BH364 (2.3 g), compound BH446 (2.3 g), palladium chloride (0.0177 g, 0.0001 mol), activated carbon (0.2 g), D2O (12 mL) and C6D6 (100 mL) were added to a 500 mL autoclave, and hydrogen was introduced therein to a pressure of 0.02 MPa. The mixture was then heated to 90° C. and reacted for a certain period of time. The mixture was then cooled to room temperature, filtered, and separated. The organic layer after separation was dried over magnesium sulfate, decolorized using a short silica gel column, concentrated to dryness, and vacuum dried for 24 hours to obtain a BHAD series deuterated composition.

[0128] After the products prepared at different reaction times were sublimed, the deuteration rate was detected. The deuteration rate was tested using the internal standard method. For example, the test can be performed by referring to the method described in the document "Wu Yurong, Chen Minzhu, Determination of the content of deuterated bromobenzene by 1HNMR method [J], Journal of Sichuan University: Natural Science Edition, 1997, 34(6):2". The values ​​of the reaction time and the deuteration rate of the product are shown in Table 1 below:

[0129] Table 1

[0130] No. Deuterated composition Reaction time / (h) Deuteration rate 1 BHAD01 1 19.15％ 2 BHAD02 10 52.67％ 3 BHAD03 40 83.12％ 4 BHAD04 80 99.06％

[0131] Example 2

[0132] This example provides a BHBD series deuterated composition, which is prepared by a deuterated reaction of a mixture of compound BH364-3 and compound BH446-3, wherein the mass ratio of compound BH364-3 to compound BH446-3 is 1:1. The preparation method is as follows:

[0133]

[0134] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0135] Referring to the preparation of the deuterated composition in Example 1, the products prepared at different reaction times were sublimed and the deuteration rate was tested. The test method for the deuteration rate was the same as above. The values ​​of the reaction time and the deuteration rate of the product are shown in Table 2 below:

[0136] Table 2

[0137] No. Deuterated composition Reaction time / (h) Deuteration rate 1 BHBD01 1 21.19％ 2 BHBD02 10 55.12％ 3 BHBD03 40 84.11％ 4 BHBD04 80 99.18％

[0138] Example 3

[0139] This example provides a series of deuterated BHCD compositions, which are prepared by deuterating a mixture of compound BH364-6 and compound BH446-5. The mass ratio of compound BH364-6 to compound BH446-5 is 1:1. The preparation method is as follows:

[0140]

[0141] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0142] Referring to the preparation of the deuterated composition in Example 1, the products prepared at different reaction times were sublimed and then subjected to deuteration rate detection. The deuteration rate test method was the same as above. The values ​​of the reaction time and the deuteration rate of the product are shown in Table 3 below:

[0143] Table 3

[0144] No. Deuterated composition Reaction time / (h) Deuteration rate 1 BHCD01 1 19.99％ 2 BHCD02 10 54.21％ 3 BHCD03 40 83.01％ 4 BHCD04 80 98.19％

[0145] Example 4

[0146] This example provides a BHDD series deuterated composition, which is prepared by a deuterated reaction of a mixture of compound BH364-3 and compound BH446-4, wherein the mass ratio of compound BH364-3 to compound BH446-4 is 1:1. The preparation method is as follows:

[0147]

[0148] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0149] Referring to the preparation of the deuterated composition in Example 1, the products prepared at different reaction times were sublimed and the deuteration rate was tested. The test method for the deuteration rate was the same as above. The values ​​of the reaction time and the deuteration rate of the product are shown in Table 4 below:

[0150] Table 4

[0151] No. Deuterated composition Reaction time / (h) Deuteration rate 1 BHDD01 1 22.09％ 2 BHDD02 10 51.89％ 3 BHDD03 40 83.97％ 4 BHDD04 80 99.26％

[0152] Comparative Example 1

[0153] This comparative example provides a BH364D series deuterated composition, which is prepared by deuterating compound BH364. The preparation method is as follows:

[0154]

[0155] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0156] The preparation method of Example 1 was used to prepare the BH364D series deuterated compositions. After sublimation, the products prepared at different reaction times were tested for deuteration rate. The test method for deuteration rate was the same as above. The values ​​of reaction time and product deuteration rate are shown in Table 5 below:

[0157] Table 5

[0158] No. Deuterated composition Reaction time / (h) Deuteration rate 1 BH364D01 1 20.99％ 2 BH364D02 10 51.58％ 3 BH364D03 40 82.66％ 4 BH364D04 80 99.01％

[0159] Comparative Example 2

[0160] This comparative example provides a BH446D series deuterated composition, which is prepared by deuterating compound BH446. The preparation method is as follows:

[0161]

[0162] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0163] The preparation method of Example 1 was used to prepare the BH446D series deuterated compositions. After sublimation, the products prepared at different reaction times were tested for deuteration rate. The test method for deuteration rate was the same as above. The values ​​of reaction time and product deuteration rate are shown in Table 6 below:

[0164] Table 6

[0165] No. Deuterated composition Reaction time / (h) Deuteration rate 1 BH446D01 1 20.10％ 2 BH446D02 10 51.02％ 3 BH446D03 40 80.11％ 4 BH446D04 80 97.61％

[0166] Comparative Example 3

[0167] This comparative example provides a D1D series deuterated composition, which is prepared by a deuterated reaction of a mixture of compound BH446-3 and compound BH446-4, wherein the mass ratio of compound BH446-3 to compound BH446-4 is 1:1. The preparation method is as follows:

[0168]

[0169] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0170] Referring to the preparation of the deuterated composition in Example 1, the products prepared at different reaction times were sublimed and the deuteration rate was tested. The test method for the deuteration rate was the same as above. The values ​​of the reaction time and the deuteration rate of the product are shown in Table 7 below:

[0171] Table 7

[0172] No. Deuterated composition Reaction time / (h) Deuteration rate 1 D1D01 1 23.10％ 2 D1D02 10 50.37％ 3 D1D03 40 78.26％ 4 D1D04 80 98.18％

[0173] Comparative Example 4

[0174] This comparative example provides a D2D series deuterated composition, which is prepared by a deuterated reaction of a mixture of compound BH446 and compound BH446-5, wherein the mass ratio of compound BH446 to compound BH446-5 is 1:1. The preparation method is as follows:

[0175]

[0176] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0177] Referring to the preparation of the deuterated composition in Example 1, the products prepared at different reaction times were sublimed and then subjected to deuteration rate detection. The deuteration rate test method was the same as above. The values ​​of the reaction time and the deuteration rate of the product are shown in Table 8 below:

[0178] Table 8

[0179] No. Deuterated composition Reaction time / (h) Deuteration rate 1 D2D01 1 22.10％ 2 D2D02 10 51.09％ 3 D2D03 40 83.86％ 4 D2D04 80 98.23％

[0180] Comparative Example 5

[0181] This comparative example provides a 2024-125BHCD series deuterated composition, which is prepared by a deuterated reaction of a mixture of compound BHC1 and compound BHC2, wherein the mass ratio of compound BHC1 to compound BHC2 is 1:1. The preparation method is as follows:

[0182]

[0183] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0184] Referring to the preparation of the deuterated composition in Example 1, the products prepared at different reaction times were sublimed and then subjected to deuteration rate detection. The deuteration rate test method was the same as above. The values ​​of the reaction time and the deuteration rate of the product are shown in Table 9 below:

[0185] Table 9

[0186] No. Deuterated composition Reaction time / (h) Deuteration rate 1 2024-125BHCD01 1 19.06％ 2 2024-125BHCD02 10 54.18％ 3 2024-125BHCD03 40 82.09％ 4 2024-125BHCD04 80 98.91％

[0187] Comparative Example 6

[0188] This comparative example provides a 2024-126BHCD series deuterated composition, which is prepared by a deuterated reaction of a mixture of compound BHC1 and compound BHC2, wherein the mass ratio of compound BHC1 to compound BHC2 is 1:1. The preparation method is as follows:

[0189]

[0190] The right side of the reaction equation represents the product obtained by replacing the H atom at an unspecified position of the raw material with a D atom.

[0191] Referring to the preparation of the deuterated composition in Example 1, the products prepared at different reaction times were sublimed and the deuteration rate was tested. The test method for the deuteration rate was the same as above. The values ​​of the reaction time and the deuteration rate of the product are shown in Table 10 below:

[0192] Table 10

[0193] No. Deuterated composition Reaction time / (h) Deuteration rate 1 2024-126BHCD01 1 21.19％ 2 2024-126BHCD02 10 53.10％ 3 2024-126BHCD03 40 81.86％ 4 2024-126BHCD04 80 98.21％

[0194] Other compounds for which specific synthesis steps are not listed can be prepared by common knowledge in the art in combination with the above examples.

[0195] Other specific structures used in the following application examples are as follows:

[0196]

[0197] Application Example 1

[0198] This application example provides an organic electroluminescent device, the structure of which is: ITO / HT (40nm) light-emitting layer (30nm): BD-1 (3%) / TPBI (30nm) / LiF (0.5nm) / Al (150nm).

[0199] The preparation method of the organic electroluminescent device is as follows:

[0200] (1) A glass substrate coated with an ITO transparent conductive layer (as an anode) is ultrasonically treated in a cleaning agent, rinsed in deionized water, and then ultrasonically degreased in a mixed solvent of acetone and ethanol. After drying, it is cleaned with ultraviolet light and ozone, and the surface is bombarded with a low-energy cation beam to improve the energy level properties of the ITO surface and enhance its binding ability with the hole injection layer;

[0201] (2) Place the glass substrate in a vacuum chamber and evacuate to 1×10 -6 ~1×10 -5 Pa, HT was vacuum evaporated on the anode as a hole transport layer with an evaporation rate of 0.01 nm / s and a film thickness of 40 nm;

[0202] (3) Vacuum evaporation of a light-emitting layer on the hole transport layer at a deposition rate of 0.01 nm / s and a total deposition thickness of 30 nm. The main material of the light-emitting layer is BHAD03, the dopant material is BD-1, and the volume ratio of the main material to the dopant material of the light-emitting layer is 97:3.

[0203] (4) Vacuum evaporating TPBI on the organic light-emitting layer as the electron transport layer of the organic electroluminescent device; the evaporation rate is 0.01 nm / s, and the total evaporation film thickness is 30 nm;

[0204] (5) Vacuum evaporation of 0.5 nm of LiF and 150 nm of Al on the electron transport layer as an electron injection layer and a cathode to obtain the organic electroluminescent device.

[0205] Application Example 2

[0206] This application example provides an organic electroluminescent device, which differs from Application Example 1 only in that the luminescent host material BHBA03 in Application Example 1 is replaced (see Table 11 below for details). Other structures, materials and preparation methods are the same as those in Application Example 1.

[0207] Comparative Application Examples 1-5

[0208] Comparative Application Examples 1-5 each provide an organic electroluminescent device, which differs from Application Example 1 only in that the luminescent host material BHAD03 in Application Example 1 is replaced (see Table 11 below for details), and the other structures, materials and preparation methods are the same as those in Application Example 1.

[0209] Performance testing:

[0210] The driving voltage and current efficiency of the organic electroluminescent device provided above were tested; the specific test results are shown in Table 11 below, where the voltage and current efficiency are relative values.

[0211] Table 11

[0212]

[0213] In Comparative Application Example 5, BH364D03 and BH446D03 were placed in separate evaporation sources and heated at a volume ratio of 1:1, serving as the host materials for the light-emitting layer. It should be noted that since the two materials have similar structures and identical molar masses, their volume ratios and masses are similar in this usage scenario and can be considered equivalent.

[0214] As can be seen from the contents of Table 11, the present invention designs the composition of the deuterated mixture to obtain a deuterated mixture, and uses the deuterated mixture as the main material of the light-emitting layer, thereby improving the driving voltage, current efficiency and life of the OLED device, so that the prepared OLED light-emitting device has a lower driving voltage, higher current efficiency and longer life.

[0215] Application Examples 3-7, Comparative Application Example 6

[0216] Application Examples 3-6 and Comparative Application Example 6 each provide an organic electroluminescent device, the only difference between which and Application Example 1 is that the luminescent host material BHBD03 in Application Example 1 is replaced (see Table 12 below for details), and the other structures, materials and preparation methods are the same as those in Application Example 1.

[0217] Performance testing:

[0218] The driving voltage and current efficiency of the organic electroluminescent device provided above were tested. The specific test results are shown in Table 12 below, where the voltage and current efficiency are relative values.

[0219] Table 12

[0220]

[0221] As can be seen from the above content, the present invention designs the composition of the deuterated mixture to obtain a deuterated mixture, and uses the deuterated mixture as the main material of the light-emitting layer, thereby improving the driving voltage, current efficiency and life of the OLED device, so that the prepared OLED light-emitting device has a lower driving voltage, higher current efficiency and longer life.

[0222] The applicant declares that the present invention uses the above-described embodiments to illustrate the detailed process flow of the present invention, but the present invention is not limited to the above-described detailed process flow, that is, it does not mean that the present invention must rely on the above-described detailed process flow to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for various raw materials in the products of the present invention, addition of auxiliary ingredients, and selection of specific methods, etc., are all within the scope of protection and disclosure of the present invention.

Claims

1. A deuterated composition, characterized in that The deuterated composition includes a deuterated mixture prepared by a deuterated reaction of at least two compounds having the structure shown in Formula I below, wherein the molar masses of at least two compounds having the structure shown in Formula I are the same; wherein Ar2 is selected from a combination of at least one of phenyl, naphthyl, and biphenyl; Ar3 is selected from a group having a structure shown in formula IM, and the dotted line represents the attachment site; At least one of the at least two compounds having the structure shown in Formula I below has the structure shown in Formula I-1 below: The hydrogen atoms in the compound of formula I and the compound of formula I-1 may each independently be replaced by a deuterium atom.

2. The deuterated composition according to claim 1, characterized in that Ar2 in the at least two compounds of formula I are both selected from biphenyl; Preferably, Ar2 in the at least two compounds of formula I are both selected from phenyl; Preferably, Ar2 in the at least two compounds of formula I are both selected from naphthyl.

3. The deuterated composition according to claim 1 or 2, characterized in that The compound of formula I is selected from any one of the following compounds:

4. The deuterated composition according to any one of claims 1 to 3, characterized in that The deuterated composition includes a deuterated mixture prepared by a deuterated reaction of two compounds in any one of the following groups 1 to 4: Group 1: Group 2: Group 3: Group 4:

5. The deuterated composition according to any one of claims 1 to 4, characterized in that The deuteration reaction comprises the following steps: In the presence of a catalyst, the raw materials for the deuteration reaction are placed in D2O and a solvent to carry out a deuteration reaction to obtain the deuterated mixture.

6. The deuterated composition according to claim 5, characterized in that The solvent is selected from any one or a combination of at least two of benzene, toluene, ethyl acetate or C6D6, and is more preferably C6D6; Preferably, the solvent is C6D6, and the volume ratio of D2O to C6D6 is 1:(4-6); Preferably, the catalyst is selected from any one or a combination of at least two of an inorganic salt of a metal, an organic salt of a metal, or a metal complex, wherein the metal in the inorganic salt of a metal, the organic salt of a metal, or the metal complex is independently selected from palladium, platinum, rhodium, ruthenium, iridium, iron, copper, cobalt, or nickel; the catalyst is further preferably PdCl2; Preferably, the reaction is carried out in a hydrogen atmosphere; Preferably, the temperature of the deuteration reaction is 60 to 200°C; Preferably, the deuteration reaction time is 1 to 80 hours; Preferably, the pressure of the deuteration reaction is 0.01-2 MPa.

7. The deuterated composition according to any one of claims 4 to 6, characterized in that The deuterium substitution rate of the deuterated mixture is 15% to 99%.

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic layer between the anode and the cathode; The material of the organic layer includes the deuterated composition according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic layer includes a light-emitting layer; The material of the light-emitting layer includes a host material, and the host material includes the deuterated composition according to any one of claims 1 to 7; Preferably, the organic layer further includes a hole transport layer and an electron layer.

10. A display device, characterized in that: The display device comprises the organic electroluminescent device according to claim 8 or 9.

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