A deuterated composition, organic electroluminescent device and display device

Abstract

The present application provides a kind of deuterated composition, organic electroluminescent device and display device.The deuterated composition includes deuterated mixture prepared by deuterium reaction of at least two compounds of formula I, wherein the molar mass of at least two compounds of formula I is the same.The deuterated mixture obtained by deuterium reaction of at least two compounds of formula I with specific structure in the present application, the deuterated composition comprising the deuterated mixture as the main material of light-emitting layer, and then an organic electroluminescent device with excellent comprehensive performance is obtained, and the organic electroluminescent device prepared thereby has lower driving voltage and higher current efficiency.

Description

Technical Field

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

[0002] Organic electroluminescence was discovered as early as 1963, but it did not attract much attention at the time. It was not until 1987, when Tang's research group at Kodak published a high-brightness, high-efficiency thin-film organic electroluminescent device (OLED) driven by low DC voltage using organic fluorescent materials and hole materials, that the technology regained attention and opened up a completely new research field.

[0003] OLED technology boasts significant advantages over other display technologies, such as low power consumption, fast response speed, flexibility, wide viewing angle, large-area display capability, and a full range of colors. Furthermore, it is compatible with various existing standards and technologies to create low-cost light-emitting devices, demonstrating broad application prospects in realizing color flat panel displays. Over the past few decades, OLED has made significant progress as a new display technology, finding widespread application in flat panel displays, flexible displays, solid-state lighting, and automotive displays.

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

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a deuterated composition, an organic electroluminescent device, and a display device. The present invention uses a deuterated mixture obtained by deuterating at least two compounds of Formula I with specific structures, and uses the deuterated composition including this deuterated mixture as the host material of the light-emitting layer, thereby obtaining an organic electroluminescent device with excellent overall performance. The organic electroluminescent device prepared in this way has a low driving voltage and high current efficiency.

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

[0007] In a first aspect, the present invention provides a deuterated composition comprising a deuterated mixture prepared by deuterating at least two compounds having structures as shown in Formula I, wherein the at least two compounds having structures as shown in Formula I have the same molar mass:

[0008]

[0009] Ar is selected from naphthyl groups;

[0010] Ar1 is selected from any one or a combination of at least two of the following: dibenzofuranyl, naphthobenzofuranyl, phenyl-substituted dibenzofuranyl, phenyl-substituted naphthobenzofuranyl, dibenzofuran-substituted phenyl, dibenzofuran-substituted naphthyl, phenyl-substituted naphthobenzofuranyl, and naphthyl-substituted naphthobenzofuranyl.

[0011] In this invention, at least two compounds with the same molar mass and conforming to the structure shown in Formula I are subjected to a deuteration reaction to obtain a deuterated mixture. The deuterated composition including the deuterated mixture is used as the host material of the light-emitting layer. The OLED light-emitting device prepared thereby has a lower driving voltage and a higher current efficiency.

[0012] It should be noted that in organic reactions, when there is no significant difference in the reactive sites on the reactant molecules, it is difficult to carry out substitution reactions at specific reactive sites. Therefore, in this invention, after deuterating compound A, 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 mass spectrometry is performed, its molecules are 1 more away from the main peak compared to the reactant. However, the mixture obtained at this time is a mixture of various isomers obtained by the substitution of each single deuterium atom.

[0013] Examples are given below:

[0014]

[0015] For BH1, which contains 24 hydrogen atoms, the isomers obtained by replacing one of the H atoms with a deuterium atom include, but are not limited to, the following:

[0016]

[0017] When the above compounds are present in deuterated compositions, the molecular ion peak m / z in the mass spectrometry is the same.

[0018] For BH1, which contains 24 hydrogen atoms, the isomers obtained by replacing 23 of the H atoms with deuterium atoms include, but are not limited to, the following:

[0019]

[0020]

[0021] When the above compounds are present in deuterated compositions, the molecular ion peak m / z in the mass spectrometry is the same.

[0022] Similarly, for BH1, which contains 24 hydrogen atoms, the isomers obtained by replacing 2-22 of the H atoms with deuterium atoms are numerous and complex. Those skilled in the art can draw the specific structures based on common knowledge.

[0023] As long as the deuteration reaction proceeds, and as long as the deuteration rate is not 0 or 100%, the resulting deuterated composition will inevitably contain multiple components.

[0024] As long as the deuteration reaction proceeds, the deuteration combination may contain any one or at least two of the following: products with 1 H atom replaced by deuterium, products with 2 H atom replaced by deuterium, products with 3 H atom replaced by deuterium, products with 4 H atom replaced by deuterium, products with 5 H atom replaced by deuterium, products with 6 H atom replaced by deuterium, products with 7 H atom replaced by deuterium, products with 8 H atom replaced by deuterium, products with 9 H atom replaced by deuterium, ..., products with 24 H atom replaced by deuterium.

[0025] Furthermore, in the deuteration reaction conditions of this invention, assuming 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 with 2 H atoms, 1 H atom, 4 H atoms, and 5 H atoms 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% ​​will have at least 5 mass spectrum peaks 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, will appear, which are isotope peaks. Of course, it can be determined by common knowledge in the field that the two peaks of M+6 and M+7 are contributed by the individual isotopes of M+4 and M+5, or by the product in which 6 H atoms are replaced by deuterium atoms in the deuterated composition, or the product in which 7 H atoms are replaced by deuterium atoms.

[0026] In this invention, at least two compounds conforming to the structure shown in Formula I and having the same molar mass are selected for deuteration reaction to prepare a deuterated mixture. Direct mixing of the components in this deuterated mixture results in more uniform film formation, leading to a more uniform film with stronger charge transport capabilities. Using the deuterated composition containing this deuterated mixture as the main material for the light-emitting layer improves the driving voltage and current efficiency of the resulting OLED device.

[0027] As a preferred embodiment of the present invention, the compound of formula I is selected from any one of the following compounds:

[0028]

[0029]

[0030]

[0031]

[0032]

[0033] As a preferred embodiment of the present invention, the deuterated composition comprises a deuterated mixture prepared by a deuteration reaction of two compounds from any one of groups 1-4 below:

[0034] Group 1:

[0035] Group 2:

[0036] Group 3:

[0037] Group 4:

[0038] As a preferred embodiment of the present invention, the deuteration reaction includes the following steps:

[0039] In the presence of a catalyst, the starting materials for the deuteration reaction are placed in D2O and a solvent to carry out the deuteration reaction, thereby obtaining the deuterated mixture.

[0040] Preferably, the solvent is selected from any one or a combination of at least two of benzene, toluene, ethyl acetate or C6D6, and more preferably C6D6.

[0041] It should be noted that C6D6 is the product of benzene in which all hydrogen atoms are replaced by deuterium atoms.

[0042] 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.

[0043] Preferably, the reaction is carried out in the presence of a catalyst selected from any one or a combination of at least two of inorganic salts of metals, organic salts of metals, or metal complexes, wherein the metal in the inorganic salt, organic salt, or metal complex is independently selected from palladium, platinum, rhodium, ruthenium, iridium, iron, copper, cobalt, or nickel; the catalyst is further preferably PdCl2.

[0044] Preferably, the reaction is carried out in a hydrogen atmosphere.

[0045] Preferably, the temperature of the deuteration reaction is 60 to 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.

[0046] Preferably, the deuteration reaction time is 1 to 80 hours, for example, it can be 1 hour, 2 hours, 4 hours, 6 hours, 10 hours, 12 hours, 24 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, or 80 hours.

[0047] Preferably, the pressure of the deuteration reaction is 0.01 to 2 MPa, for example, it can be 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, etc.

[0048] Preferably, the deuteration 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%.

[0049] In this invention, the deuteration rate refers to the percentage of the number of deuterium atoms (D) in the composition or compound relative to the total number of deuterium atoms and hydrogen atoms (H), i.e., deuteration rate = y / (x+y)*100%, where 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 is entirely composed of H and has no D, its deuteration rate is 0%. If all H atoms in the composition or compound are replaced by D, its deuteration rate is 100%.

[0050] It should be noted that the deuteration reaction described in this invention is carried out in the presence of activated carbon. Furthermore, after the deuteration reaction is completed, a post-treatment step is also included, which includes cooling, filtration, separation, and drying.

[0051] In a second aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode and an organic layer disposed between the anode and the cathode;

[0052] The material of the organic layer includes the deuterated composition as described in the first aspect;

[0053] Preferably, the organic layer includes a light-emitting layer.

[0054] The material of the light-emitting layer includes a host material, which includes the deuterated composition as described in the first aspect.

[0055] 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).

[0056] As a preferred embodiment of the present invention, the material of the light-emitting layer further includes a doped material;

[0057] The doped material includes compounds having the structure shown by the formula BDI:

[0058]

[0059] Among them, Ar 101 Ar 102 Ar 201 Ar 202 Each is independently selected from any one of substituted or unsubstituted C6-C40 (e.g., C6, C10, C12, C15, C18, C24, C30, C36, or C40) aryl groups, or substituted or unsubstituted C12-C20 (e.g., C12, C13, C14, C15, C16, C17, C18, C19, or C20) heteroaryl groups;

[0060] R 101 and R 102 Each is independently selected from any one of the following: substituted or unsubstituted C1-C12 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, or C12) alkyl, substituted or unsubstituted C6-C40 (e.g., C6, C10, C12, C15, C18, C24, C30, C36, or C40, etc.) aryl, and substituted or unsubstituted C12-C20 (e.g., C12, C13, C14, C15, C16, C17, C18, C19, or C20) heteroaryl;

[0061] R 101 and R 102 They can be connected in a ring using a single key;

[0062] m and n are each independently selected from 0 or 1, and m and n are not both 0 at the same time;

[0063] Ar 101 Ar 102 Ar 201 Ar 202 R 101 and R 102The substituents described herein are each independently selected from any one or a combination of at least two of the following: -D, -F, -CN, C1-C12 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, or C12) alkyl, C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkoxy, C2-C8 (e.g., C2, C3, C4, C5, C6, C7, or C8) alkenyl, C6-C15 (e.g., C6, C7, C8, C10, C12, or C15), and C12-C20 (e.g., C12, C15, C18, or C20) heteroaryl.

[0064] As a preferred embodiment of the present invention, the C6-C40 aryl group is selected from any one of phenyl, diphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, benzo[a]fluorenyl, 9,10-diphenylanthryl, dibenzo[a]fluorenyl, naphthene, pyrene, perylene, spirofluorenyl, triphenylene, fluoranthyl, hydrogenated benzo[a]anthryl, ind[a]fluorenyl, benzo[a]ind[a]fluorenyl, dibenzo[a]ind[a]fluorenyl, naphthene, or benzo[a]naphthenefluorenyl, preferably any one of phenyl, naphthyl, diphenyl, terphenyl, fluoranthyl, fluorenyl, 9,10-diphenylanthryl, or benzo[a]fluorenyl.

[0065] Preferably, the C12-C20 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, and dinaphthothiophenyl.

[0066] Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, cyclopentyl, or cyclohexyl.

[0067] Preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, propoxy, butoxy, or... Any of the following, with dashed lines representing connection points.

[0068] Preferably, the C6-C15 aryl group is selected from any one of phenyl, naphthyl, or diphenyl.

[0069] As a preferred technical solution of the present invention, the Ar 101 and Ar 102 Each group is independently selected from any one of the following groups, whether substituted or unsubstituted: phenyl, naphthyl, diphenyl, triphenyl, fluoranyl, fluorenyl, 9,10-diphenylanthryl, benzofluorenyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl or naphthobenzothiophenyl;

[0070] The substituents are selected from -D (deuterium atom), -F, -CN, phenyl, biphenyl, dibenzofuranyl, methyl, deuterated methyl, adamantyl, tert-butyl, 1-methylcyclopentyl, cyclohexyl, cyclopentyl, methoxy, Any one or a combination of at least two of naphthyl, dibenzothiophene, and naphthobenzothiophene, with dashed lines indicating connection sites.

[0071] Preferably, the Ar 201 and Ar 202 Each group is independently selected from any one of the following groups, whether substituted or unsubstituted: phenyl, naphthyl, dibenzofuranyl or diphenyl;

[0072] The substituents are selected from any one or a combination of at least two of methyl, methoxy, phenyl, or dibenzofuranyl.

[0073] Preferably, R 101 and R 102 Each is independently selected from any one of methyl, ethyl, propyl, or phenyl.

[0074] Preferably, R 101 and R 102 same.

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

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] Preferably, the BDI compound is selected from any one of the following compounds:

[0085]

[0086]

[0087] As a preferred embodiment of the present invention, the doped material comprises a compound having the structure shown in Formula II:

[0088]

[0089] Wherein, the R 21 R 22 and R 23 Each is independently selected from hydrogen, C1-C12 (e.g., C1, C2, C4, C6, C8, C10, or C12) straight-chain or branched alkyl groups, C6-C12 (e.g., C6, C7, C8, C9, C10, C11, or C12) cycloalkyl groups, -NAr 23 Ar 24 Any one of them;

[0090] The Ar 21 Ar 22 Ar 23 Ar 24 Each is independently selected from any one of substituted or unsubstituted C6-C20 (e.g., C6, C8, C10, C12, C14, C16, C18, or C20) aryl groups, or substituted or unsubstituted C3-C20 (e.g., C3, C6, C8, C10, C12, C14, C16, C18, or C20) heteroaryl groups;

[0091] Ar 21 Ar 22 Ar 23 Ar 24 The substituents described herein are each independently selected from C1-C5 (e.g., C1, C2, C3, C4, or C5, etc.) straight-chain or branched alkyl groups or C6-C12 (e.g., C6, C7, C8, C9, C10, C11, or C12, etc.) aryl groups.

[0092] Preferably, the Ar 21 Ar 22 Ar 23 Ar 24 Each group is independently selected from any of the following groups, with short bonds indicating linkage sites:

[0093]

[0094]

[0095] Preferably, the R 21 R 22 and R 23Each is independently selected from any one of hydrogen atom, methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl or adamantyl.

[0096] As a preferred embodiment of the present invention, the compound of formula II is selected from any one of the following compounds:

[0097]

[0098]

[0099] As a preferred technical solution of the present invention, the doped material includes a compound having the structure shown in Formula III:

[0100]

[0101] Wherein, the Ar 31 Ar 32 Ar 33 and Ar 34 Each is independently selected from any one of substituted or unsubstituted C6-C22 (e.g., C6, C8, C10, C12, C15, C18, or C22, etc.) aryl, substituted or unsubstituted C12-C40 (e.g., C12, C15, C18, C24, C30, C36, or C40, etc.) heteroaryl;

[0102] R 31 Selected from any one of phenyl, naphthyl, or biphenyl;

[0103] The a is selected from 0 or 1;

[0104] Ar 31 Ar 32 Ar 33 Ar 34 The substituents described herein are each independently selected from C1-C5 (e.g., C1, C2, C3, C4, or C5, etc.) straight-chain or branched alkyl groups or C6-C12 (e.g., C6, C7, C8, C9, C10, C11, or C12, etc.) aryl groups.

[0105] Preferably, the Ar 31 Ar 32 Ar 33 and Ar 34 Each independently selected Any one or at least two of them, short bonds represent connection sites.

[0106] Preferably, the compound of formula III is selected from any one of the following compounds:

[0107]

[0108] Thirdly, the present invention provides a display device comprising the organic electroluminescent device as described in the second aspect.

[0109] Compared with the prior art, the present invention has the following beneficial effects:

[0110] This invention designs the composition of a deuterated mixture and further deuterates at least two compounds with the same molar mass and conforming to the structure shown in Formula I to obtain a deuterated mixture. The deuterated mixture is then used as the main material of the light-emitting layer. The resulting OLED light-emitting device has a lower driving voltage and higher current efficiency.

[0111] If two compounds conforming to Formula I of this application and having the same molar mass are deuterated separately to obtain two deuterated mixtures, and these two deuterated mixtures are used together as the main material for the light-emitting layer of an OLED device to prepare an OLED device; compared with the method of the present invention, at least two compounds conforming to the structure shown in Formula I and having the same molar mass are selected and deuterated to prepare a deuterated mixture, and this deuterated mixture is used as the main material for the light-emitting layer of an OLED device to prepare an OLED device, the latter deuterated mixture has more uniform direct mixing of each component, resulting in better film formation, a more uniform film, and stronger charge transport capability. When the deuterated composition containing this deuterated mixture is used as the main material for the light-emitting layer, the driving voltage and current efficiency of the obtained OLED device are improved. Detailed Implementation

[0112] Specific embodiments will be provided to further illustrate the technical solution of the present invention. Those skilled in the art should understand that the embodiments described are merely illustrative of the invention and should not be construed as limiting the invention.

[0113] Example 1

[0114] This embodiment provides a BHAD series of deuterated compositions, which are prepared by a deuteration reaction of a mixture of compounds BHA1 and BHA2. The preparation method is as follows:

[0115]

[0116] The right side of the reaction equation represents the product obtained by replacing H atoms at unspecified positions in the starting material with D atoms.

[0117] The specific preparation methods for the above-mentioned BHAD series deuterated compositions are as follows:

[0118] At room temperature, compounds BH1 (2.3 g), BH11 (2.3 g), palladium chloride (0.0177 g, 0.0001 mol), activated carbon (0.2 g), D2O (12 mL), and C6D6 (110 mL) were added to a 500 mL autoclave, and hydrogen gas was introduced into the autoclave until the pressure reached 0.02 MPa. The autoclave was then heated to 90 °C and reacted for a certain period of time. After cooling to room temperature, the autoclave was filtered and separated. The organic layer after separation was dried with magnesium sulfate, decolorized with a short silica gel column, concentrated to dryness, and then vacuum dried for 24 h to obtain the BHAD series of deuterated compositions.

[0119] After sublimation, the deuteration rate of the products prepared at different reaction times was detected. The deuteration rate was tested using the internal standard method. For example, the method described in the literature "Wu Yurong, Chen Minzhu, Determination of deuterated bromobenzene content by 1H NMR [J], Journal of Sichuan University: Natural Science Edition, 1997, 34(6):2" can be used for testing. The values ​​of reaction time and deuteration rate of the product are shown in Table 1 below.

[0120] Table 1

[0121] Serial Number Deuterated composition Reaction time (h) Deuteration rate 1 BHAD01 1 19.16％ 2 BHAD02 10 51.31％ 3 BHAD03 40 81.18％ 4 BHAD04 80 98.38％

[0122] Example 2

[0123] This embodiment provides a BHBD series deuterated composition, which is prepared by a deuteration reaction of a mixture of compounds BHB1 and BHB2, wherein the mass ratio of compounds BHB1 to BHB2 is 1:1. The preparation method is as follows:

[0124]

[0125] The right side of the reaction equation represents the product obtained by replacing H atoms at unspecified positions in the starting material with D atoms.

[0126] The BHBD series deuterated compositions were prepared according to the preparation method of BHAD. After sublimation, the deuteration rate of the products prepared at different reaction times was detected. The test method for deuteration rate is the same as above. The reaction time and the deuteration rate of the products are shown in Table 2 below:

[0127] Table 2

[0128] Serial Number Deuterated composition Reaction time (h) Deuteration rate 1 BHBD01 1 21.72％ 2 BHBD02 10 52.23％ 3 BHBD03 40 84.47％ 4 BHBD04 80 98.74％

[0129] Example 3

[0130] This embodiment provides a BHCD series deuterated composition, which is prepared by a deuteration reaction of a mixture of compounds BHC1 and BHC2, wherein the mass ratio of compounds BHC1 to BHC2 is 1:1. The preparation method is as follows:

[0131]

[0132] The right side of the reaction equation represents the product obtained by replacing H atoms at unspecified positions in the starting material with D atoms.

[0133] The BHCD series deuterated compositions were prepared according to the preparation method of BHAD. After sublimation, the deuteration rate of the products prepared at different reaction times was detected. The test method for deuteration rate is the same as above. The reaction time and the deuteration rate of the products are shown in Table 3 below:

[0134] Table 3

[0135] Serial Number Deuterated composition Reaction time (h) Deuteration rate 1 BHCD01 1 21.19％ 2 BHCD02 10 53.10％ 3 BHCD03 40 81.86％ 4 BHCD04 80 98.21％

[0136] Example 4

[0137] This embodiment provides a BHDD series deuterated composition, which is prepared by a deuteration reaction of a mixture of compounds BHD1 and BHD2, wherein the mass ratio of compounds BHD1 to BHD2 is 1:1. The preparation method is as follows:

[0138]

[0139] The right side of the reaction equation represents the product obtained by replacing H atoms at unspecified positions in the starting material with D atoms.

[0140] The BHDD series of deuterated compositions were prepared according to the preparation method of BHAD. After sublimation, the deuteration rate of the products prepared at different reaction times was detected. The test method for deuteration rate is the same as above. The reaction time and the deuteration rate of the products are shown in Table 4 below:

[0141] Table 4

[0142] Serial Number Deuterated composition Reaction time (h) Deuteration rate 1 BHDD01 1 19.28％ 2 BHDD02 10 50.39％ 3 BHDD03 40 83.29％ 4 BHDD04 80 99.11％

[0143] Comparative Example 1

[0144] This comparative example provides a series of deuterated compositions of the BHA1D series, which are prepared by deuteration reaction of compound BHA1, and the preparation method is as follows:

[0145]

[0146] The right side of the reaction equation represents the product obtained by replacing H atoms at unspecified positions in the starting material with D atoms.

[0147] The BHA1D series deuterated compositions were prepared according to the preparation method of BHAD. After sublimation, the deuteration rate of the products prepared at different reaction times was detected. The test method for deuteration rate was the same as above. The reaction time and the deuteration rate of the products are shown in Table 5 below:

[0148] Table 5

[0149] Serial Number Deuterated composition Reaction time (h) Deuteration rate 1 BHA1D01 1 22.06％ 2 BHA1D02 10 52.16％ 3 BHA1D03 40 81.78％ 4 BHA1D04 80 98.88％

[0150] Comparative Example 2

[0151] This comparative example provides a series of deuterated compositions of BHA2D, which are prepared by deuteration reaction of compound BHA2, and the preparation method is as follows:

[0152]

[0153] The right side of the reaction equation represents the product obtained by replacing H atoms at unspecified positions in the starting material with D atoms.

[0154] The BHA2D series of deuterated compositions were prepared according to the preparation method of BHAD. After sublimation, the deuteration rate of the products prepared at different reaction times was detected. The test method for deuteration rate is the same as above. The reaction time and the deuteration rate of the products are shown in Table 6 below:

[0155] Table 6

[0156] Serial Number Deuterated composition Reaction time (h) Deuteration rate 1 BHA2D01 1 21.76％ 2 BHA2D02 10 54.03％ 3 BHA2D03 40 83.67％ 4 BHA2D04 80 99.71％

[0157] Comparative Example 3

[0158] This comparative example provides a BHABD series of deuterated compositions, which are prepared by a deuteration reaction of a mixture of compounds BHA1 and BHB1, with a mass ratio of BHA1 to BHB1 of 1:1. The preparation method is as follows:

[0159]

[0160] The right side of the reaction equation represents the product obtained by replacing H atoms at unspecified positions in the starting material with D atoms.

[0161] The BHABD series of deuterated compositions were prepared according to the preparation method of BHAD. After sublimation, the deuteration rate of the products prepared at different reaction times was detected. The test method for deuteration rate is the same as above. The reaction time and the deuteration rate of the products are shown in Table 7 below:

[0162] Table 7

[0163] Serial Number Deuterated composition Reaction time (h) Deuteration rate 1 BHABD01 1 22.79％ 2 BHABD02 10 50.67％ 3 BHABD03 40 83.98％ 4 BHABD04 80 99.01％

[0164] Comparative Example 4

[0165] This comparative example provides a BH612D series of deuterated compositions, which are prepared by a deuteration reaction of a mixture of compounds BH61 and BH62, wherein the mass ratio of compounds BH61 to BH62 is 1:1. The preparation method is as follows:

[0166]

[0167] The right side of the reaction equation represents the product obtained by replacing H atoms at unspecified positions in the starting material with D atoms.

[0168] The BH612D series deuterated compositions were prepared according to the preparation method of BHAD. After sublimation, the deuteration rate of the products obtained at different reaction times was determined using the same method as above. The reaction time and the deuteration rate values ​​of the products are shown in Table 8 below.

[0169] Table 8

[0170] Serial Number Deuterated composition Reaction time (h) Deuteration rate 1 BH612D01 1 21.90％ 2 BH612D02 10 55.13％ 3 BH612D03 40 82.36％ 4 BH612D04 80 98.74％

[0171] 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.

[0172] Other specific structures used in the following application examples are shown below:

[0173]

[0174] Application Example 1

[0175] This application example provides an organic electroluminescent device with the following structure: ITO / HT (40nm) emitting layer (30nm): BD-3 (3%) / TPBI (30nm) / LiF (0.5nm) / Al (150nm).

[0176] The fabrication method of the above-mentioned organic electroluminescent device is as follows:

[0177] (1) The glass substrate coated with ITO transparent conductive layer (as anode) is ultrasonically treated in cleaning agent, rinsed in deionized water, then ultrasonically degreased in a mixed solvent of acetone and ethanol, dried, cleaned with ultraviolet light and ozone, and bombarded with low-energy cation beam to improve the energy level properties of ITO surface and enhance its binding ability with hole injection layer.

[0178] (2) Place the glass substrate in a vacuum chamber and evacuate it to 1×10⁻⁶. -6 ~1×10 -5Pa, HT is vacuum-deposited on the anode as a hole transport layer at a deposition rate of 0.01 nm / s and a film thickness of 40 nm.

[0179] (3) A light-emitting layer is vacuum-deposited on the hole transport layer at a deposition rate of 0.01 nm / s and a total film thickness of 30 nm. The main material of the light-emitting layer is BHAD03, the doping material is BD-3, and the volume ratio of the main material to the doping material is 97:3.

[0180] (4) TPBI was vacuum-deposited on the organic light-emitting layer as the electron transport layer of the organic electroluminescent device; the deposition rate was 0.01 nm / s and the total film thickness was 30 nm.

[0181] (5) Vacuum evaporation of 0.5 nm LiF and 150 nm Al on the electron transport layer as electron injection layer and cathode to obtain the organic electroluminescent device.

[0182] Application Example 2-3

[0183] Application Example 2-3 provides an organic electroluminescent device, which differs from Application Example 1 only in that the light-emitting host material BHADO3 in Application Example 1 is replaced (see Table 9 below). The other structures, materials and preparation methods are the same as those in Application Example 1.

[0184] Compare and contrast examples 1-4

[0185] Comparative Application Examples 1-4 provide an organic electroluminescent device, which differs from Application Example 1 only in that the main light-emitting material BHADO3 in Application Example 1 is replaced (see Table 9 below). The other structures, materials and preparation methods are the same as those in Application Example 1.

[0186] Performance testing:

[0187] The driving voltage and current efficiency of the organic electroluminescent devices provided above were tested, and the specific test results are shown in Table 9 below. The voltage and current efficiencies are relative values.

[0188] Table 9

[0189]

[0190] In Comparative Application Example 3, BHA1D03 and BHA2D03 were placed in different evaporation sources and heated, with their volume ratio controlled at 1:1, serving as the main material for the luminescent layer. It should be noted that since the two materials have similar structures and the same molar mass, their volume ratio and mass ratio are very close under this application condition and can be considered identical.

[0191] As can be seen from the above, the present invention designs the composition of the deuterated mixture, and further conducts a deuteration reaction on at least two compounds with the same molar mass and conforming to the structure shown in Formula I to obtain a deuterated mixture, and uses the deuterated mixture as the main material of the light-emitting layer, thereby improving the driving voltage and current efficiency of the OLED device, so that the prepared OLED light-emitting device has a lower driving voltage and a higher current efficiency.

[0192] As can be seen from the comparison between Application Examples 1-2 and Application Example 1, the present invention uses two compounds with the same molar mass and conforming to the structure shown in Formula I as raw materials to carry out a deuteration reaction to obtain a deuterated mixture. Using this deuterated mixture as the main material of the light-emitting layer, the performance of the OLED device prepared is better than that of the OLED device prepared by using the deuterated mixture prepared from a single compound as the main material of the light-emitting layer.

[0193] As can be seen from the comparison between Application Example 3 and Application Example 1, the present invention selects two compounds with the same molar mass and conforming to the structure shown in Formula I as raw materials to carry out a deuteration reaction to obtain a deuterated mixture. Using this deuterated mixture as the main material of the light-emitting layer, the performance of the OLED device prepared is better than that of the OLED device prepared by carrying out deuteration reactions of two compounds with the same molar mass separately and then mixing the deuterated mixture as the main material of the light-emitting layer.

[0194] As can be seen from the comparison between Comparative Application Example 5 and Application Example 1, the present invention uses two compounds with the same molar mass and conforming to the structure shown in Formula I as raw materials to carry out a deuteration reaction to obtain a deuterated mixture. Using this deuterated mixture as the main material of the light-emitting layer, the prepared OLED light-emitting device has a lower driving voltage and a higher current efficiency. However, although the two compounds in Comparative Application Example 5 have the same molar mass, their structures are different from the structures of the compounds of Formula I claimed in this application. The OLED device prepared by using the deuterated mixture obtained therefrom as the main material of the light-emitting layer has poor performance.

[0195] Application Examples 4-5, Comparative Application Example 6

[0196] Application Examples 4-5 and Comparative Application Example 6 each provide an organic electroluminescent device. The only difference between them and Application Example 1 is that the light-emitting host material BHADO3 in Application Example 1 is replaced (see Table 10 below). The other structures, materials and preparation methods are the same as in Application Example 1.

[0197] Performance testing:

[0198] The driving voltage and current efficiency of the organic electroluminescent devices provided above were tested. The specific test results are shown in Table 10 below, where the voltage and current efficiencies are relative values:

[0199] Table 10

[0200]

[0201] As can be seen from the above, the present invention designs the composition of the deuterated mixture, and further conducts a deuteration reaction on at least two compounds with the same molar mass and conforming to the structure shown in Formula I to obtain a deuterated mixture, and uses the deuterated mixture as the main material of the light-emitting layer, thereby improving the driving voltage and current efficiency of the OLED device, so that the prepared OLED light-emitting device has a lower driving voltage and a higher current efficiency.

[0202] 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 deuterated composition, characterized in that, The deuterated composition comprises a deuterated mixture prepared by deuterating at least two compounds having the structure shown in Formula I, wherein the at least two compounds having the structure shown in Formula I have the same molar mass. Ar is selected from naphthyl groups; Ar1 is selected from any one or a combination of at least two of the following: dibenzofuranyl, naphthobenzofuranyl, phenyl-substituted dibenzofuranyl, phenyl-substituted naphthobenzofuranyl, dibenzofuran-substituted phenyl, dibenzofuran-substituted naphthyl, phenyl-substituted naphthobenzofuranyl, and naphthyl-substituted naphthobenzofuranyl.

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

3. The deuterated composition according to claim 1 or 2, characterized in that, The deuterated composition comprises a deuterated mixture prepared by deuteration of two compounds from any one of groups 1-4 below: Group 1: Group 2: Group 3: Group 4:

4. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic layer between the anode and the cathode; The material of the organic layer includes the deuterated composition as described in any one of claims 1-3; Preferably, the organic layer includes a light-emitting layer; The material of the light-emitting layer includes a host material, which includes the deuterated composition as described in any one of claims 1-3.

5. The organic electroluminescent device according to claim 4, characterized in that, The material of the light-emitting layer also includes doped materials; The doped material includes compounds having the structure shown by the formula BDI: Among them, Ar 101 Ar 102 Ar 201 Ar 202 Each is independently selected from any one of substituted or unsubstituted C6-C40 aryl groups or substituted or unsubstituted C12-C20 heteroaryl groups; R 101 and R 102 Each is independently selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted C12-C20 heteroaryl; R 101 and R 102 They can be connected in a ring using a single key; m and n are each independently selected from 0 or 1, and m and n are not both 0 at the same time; Ar 101 Ar 102 Ar 201 Ar 202 R 101 and R 102 The substituents described herein are each independently selected from any one or a combination of at least two of -D, -F, -CN, C1-C12 alkyl, C1-C6 alkoxy, C2-C8 alkenyl, C6-C15 aryl, and C12-C20 heteroaryl.

6. The organic electroluminescent device according to claim 5, characterized in that, The C6-C40 aryl group is selected from any one of phenyl, diphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, benzo[a]fluorenyl, 9,10-diphenylanthryl, dibenzo[a]fluorenyl, naphthene, pyrene, perylene, spirofluorenyl, triphenylene, fluoranyl, hydrogenated benzo[a]anthryl, ind[a]fluorenyl, benzo[a]ind[a]fluorenyl, dibenzo[a]ind[a]fluorenyl, naphthene, or benzo[a]naphthene, preferably any one of phenyl, naphthyl, diphenyl, terphenyl, fluoranyl, fluorenyl, 9,10-diphenylanthryl, or benzo[a]fluorenyl. Preferably, the C12-C20 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, and dinaphthothiophenyl; Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, cyclopentyl, or cyclohexyl; Preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, propoxy, butoxy, or... Any of the following, with dashed lines representing connection points; Preferably, the C6-C15 aryl group is selected from any one of phenyl, naphthyl, or diphenyl; Preferably, the Ar 101 and Ar 102 Each group is independently selected from any one of the following groups, whether substituted or unsubstituted: phenyl, naphthyl, diphenyl, triphenyl, fluoranyl, fluorenyl, 9,10-diphenylanthryl, benzofluorenyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl or naphthobenzothiophenyl; The substituents are selected from -D, -F, -CN, phenyl, biphenyl, dibenzofuranyl, methyl, deuterated methyl, adamantyl, tert-butyl, 1-methylcyclopentyl, cyclohexyl, cyclopentyl, methoxy, etc. Any one or a combination of at least two of naphthyl, dibenzothiophene, and naphthobenzothiophene; the dashed line indicates the linking site. Preferably, the Ar 201 and Ar 202 Each group is independently selected from any one of the following groups, whether substituted or unsubstituted: phenyl, naphthyl, dibenzofuranyl or diphenyl; The substituents are selected from any one or a combination of at least two of methyl, methoxy, phenyl or dibenzofuranyl; Preferably, R 101 and R 102 Each is independently selected from any one of methyl, ethyl, propyl, or phenyl; Preferably, R 101 and R 102 same; Preferably, the BDI compound is selected from any one of the following compounds:

7. The organic electroluminescent device according to claim 4, characterized in that, The material of the light-emitting layer also includes doped materials; The doped material includes a compound having the structure shown in Formula II: Among them, R 21 R 22 and R 23 Each is independently selected from hydrogen, C1-C12 straight-chain or branched alkyl, C6-C12 cycloalkyl, -NAr 23 Ar 24 Any one of them; Ar 21 Ar 22 Ar 23 Ar 24 Each is independently selected from any one of substituted or unsubstituted C6-C20 aryl groups or substituted or unsubstituted C3-C20 heteroaryl groups; Ar 21 Ar 22 Ar 23 Ar 24 The substituents described herein are each independently selected from C1-C5 straight-chain or branched alkyl groups or C6-C12 aryl groups; Preferably, the Ar 21 Ar 22 Ar 23 Ar 24 Each group is independently selected from any of the following groups, with short bonds indicating linkage sites: Preferably, the R 21 R 22 and R 23 Each is independently selected from any one of hydrogen atom, methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl or adamantyl.

8. The organic electroluminescent device according to claim 7, characterized in that, The compound of formula II is selected from any one of the following compounds:

9. The organic electroluminescent device according to claim 4, characterized in that, The material of the light-emitting layer also includes doped materials; The doped material includes compounds having the structure shown in Formula III: Among them, Ar 31 Ar 32 Ar 33 and Ar 34 Each is independently selected from any one of substituted or unsubstituted C6-C22 aryl groups or substituted or unsubstituted C12-C40 heteroaryl groups; R 31 Selected from any one of phenyl, naphthyl, or biphenyl; a is selected from 0 or 1; Ar 31 Ar 32 Ar 33 Ar 34 The substituents described herein are each independently selected from C1-C5 straight-chain or branched alkyl groups or C6-C12 aryl groups; Preferably, the Ar 31 Ar 32 Ar 33 and Ar 34 Each independently selected Any one or at least two of the following, short bonds represent connection sites; Preferably, the compound of formula III is selected from any one of the following compounds:

10. A display device, characterized in that, The display device includes an organic electroluminescent device as described in any one of claims 4-9.

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