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 the deuterated mixture prepared by deuterium reaction of compound A;The compound A has the structure shown as formula I.In the present application, the deuterated mixture obtained by deuterium reaction of the compound with a specific structure is used as the host material of light-emitting layer, and further an organic electroluminescent device with lower driving voltage, higher efficiency and longer service life is obtained.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic electroluminescent materials, and particularly relates to a deuterated composition, an organic electroluminescent device and a display device. BACKGROUND

[0002] The organic electroluminescent phenomenon has been discovered as early as 1963, but it did not attract people's attention at that time; until 1987, the Tang research group of Kodak Company in the United States published a high-brightness and high-efficiency thin film organic electroluminescent device (OLED) driven by direct current and low voltage made of organic fluorescent material and hole material, which attracted attention again and opened up a new research field.

[0003] Compared with other display technologies, OLED technology has outstanding advantages, such as low power consumption, fast response speed, easy bending, wide viewing angle, large-area display, full color light emission, and the like, and can be compatible with existing various standards and technologies to make low-cost light-emitting devices, which shows broad application prospects in realizing color flat panel display. In the past few decades, OLED has made great progress as a new display technology and has been widely used in flat panel display, flexible display, solid-state lighting and vehicle display fields.

[0004] Therefore, it is a research focus in the field to develop more kinds of luminescent layer host materials with more perfect performance to meet the use requirements of high-performance OLED devices. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a deuterated composition, an organic electroluminescent device and a display device. In the present application, a deuterated mixture obtained by deuterating a compound with a specific structure is used as a luminescent layer host material, and thus an organic electroluminescent device with excellent comprehensive performance is obtained.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a deuterated composition, which comprises a deuterated mixture prepared by deuterating at least one compound A;

[0008] The compound A has a structure as shown in Formula I;

[0009]

[0010] wherein Ar 301 , Ar 302 , Ar 401 , Ar 402 are each independently selected from one of phenyl, naphthyl and phenanthryl, and Ar 301Ar 302 Ar 401 Ar 402 are not phenanthryl at the same time; only one phenanthryl is contained in the structure shown in formula I;

[0011] The o, p are each independently selected from 0 or 1;

[0012] The deuterium substitution reaction condition is as follows:

[0013] The compound A is placed in D2O and C6D6 in the presence of a catalyst to carry out deuterium substitution reaction to obtain the deuterium substitution mixture, the reaction is carried out in the presence of one or more than one of the catalysts of palladium chloride, nickel chloride, Pd / C, Pt / C and PtO2; the reaction is carried out in a nitrogen atmosphere, the deuterium substitution reaction is carried out at a temperature of 60-100℃, and the volume ratio of D2O to C6D6 is 1:(1-3).

[0014] Preferably, the deuterium substitution rate of the deuterium substitution mixture is 34-70%;

[0015] Preferably, the deuterium substitution rate of the deuterium substitution mixture is 34-37%.

[0016] In the present application, the anthracene compound substituted by aromatic group is subjected to deuterium substitution reaction to obtain a deuterium substitution mixture, and the obtained deuterium substitution mixture is used as the main material of the light-emitting layer, so that the OLED light-emitting device prepared has high current efficiency and long service life.

[0017] In the present application, the anthracene compound (compound A) with a specific structure is subjected to deuterium substitution reaction, so that the cumbersome purification work is avoided, the preparation method is simple, the reaction condition is mild, the post-treatment is simple, and the deuterium substitution mixture can be obtained after the deuterium substitution reaction of the anthracene compound (compound A) with a specific structure, so that the comprehensive performance of the OLED light-emitting device prepared by using the obtained deuterium substitution mixture as the main material of the light-emitting layer is better, the driving voltage is lower, the current effect is higher, and the service life is longer.

[0018] It should be noted that in the process of organic reaction, when the reaction active sites on the reaction molecules have no significant difference, it is difficult to carry out substitution reaction at the characteristic reaction sites, therefore, in the present application, after the deuterium substitution reaction of the compound A, a mixture (deuterium substitution 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, at this time, the obtained mixture, if mass spectrometry is carried out, the molecular ion main peak is increased by 1 compared with the reactant, but at this time, the obtained mixture is a mixture of various isomers obtained by substitution of each deuterium atom.

[0019] The following is an example:

[0020] For BH1, which contains 24 hydrogen atoms, when one H atom is replaced by a deuterium atom, the isomers obtained include, but are not limited to, the following:

[0021]

[0022] The above compounds, when present in a deuterated composition, have the same mass spectrometry peak molecular ion peak m / z.

[0023] For BH1, which contains 24 hydrogen atoms, when 23 H atoms are replaced by deuterium atoms, the isomers obtained include, but are not limited to, the following:

[0024]

[0025] The above compounds, when present in a deuterated composition, have the same mass spectrometry peak molecular ion peak m / z.

[0026] Similarly, for BH1, which contains 24 hydrogen atoms, when 2-22 H atoms are replaced by deuterium atoms, the isomers obtained are numerous and complex, and a person skilled in the art can draw specific structures according to common knowledge.

[0027] As long as the deuterium substitution reaction proceeds, as long as the deuterium substitution rate is not 0 or 100%, the deuterated composition obtained must contain a plurality of components.

[0028] As long as the deuterium substitution reaction proceeds, the deuterated composition may contain any one of the following or a combination of at least two of the following: a product in which one H atom is replaced by deuterium, a product in which two H atoms are replaced by deuterium, a product in which three H atoms are replaced by deuterium, a product in which four H atoms are replaced by deuterium, a product in which five H atoms are replaced by deuterium, a product in which six H atoms are replaced by deuterium, a product in which seven H atoms are replaced by deuterium, a product in which eight H atoms are replaced by deuterium, a product in which nine H atoms are replaced by deuterium, …, a product in which 24 H atoms are replaced by deuterium.

[0029] And in the deuterium reaction condition of the present application, assuming that the deuterium substitution 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, and there must be 2 H, 1 H, 4 H, and 5 H atoms replaced by deuterium atoms. In this case, if the mass spectrum m / z of BH1 is represented by M, the deuterium composition with a deuterium substitution rate of 12.5% has at least 5 peaks on the right side of the mass spectrum on the mass spectrum, which are M+1, M+2, M+3, M+4, and M+5, and two peaks of M+6 and M+7 appear, which are isotope peaks. Of course, it can be judged by common knowledge in the art that the two peaks of M+6 and M+7 are the contribution of the isotope of M+4 and M+5 alone, or the product of 6 H atoms replaced by deuterium atoms in the deuterium composition and the product of 7 H atoms replaced by deuterium atoms.

[0030] The following is a preferred technical solution of the present application, but is not a limitation on the technical solutions provided by the present application. Through the following preferred technical solution, the purpose and beneficial effects of the present application can be better achieved and realized.

[0031] As a preferred technical solution of the present application, the deuterium composition includes a deuterium mixture prepared from two compounds A by deuterium reaction.

[0032] Preferably, the deuterium mixture includes at least 7 types of compounds, for example, 7 types, 8 types, 9 types, 10 types, 11 types, 12 types, 13 types, 14 types, 15 types, 16 types, 17 types, 18 types, etc.

[0033] Preferably, the deuterium mixture includes at least 8 types of compounds, for example, 8 types, 9 types, 10 types, 11 types, 12 types, 13 types, 14 types, 15 types, 16 types, 17 types, 18 types, etc.

[0034] More preferably, preferably, the deuterium mixture includes at least 11 types of compounds, for example, 11 types, 12 types, 13 types, 14 types, 15 types, 16 types, 17 types, 18 types, etc.

[0035] It should be noted that each type of compound in the present application refers to a compound with the same number of deuterium atoms obtained after deuterium reaction of compound A. The right side mass spectrum peak m / z on the mass spectrum of the same type of compound after mass spectrometry is the same peak.

[0036] For example, in the above-mentioned compound BH1, only 1 hydrogen atom is replaced by a deuterium atom, and the compound with 1 deuterium atom is referred to as 1 type of compound. Since the position of deuterium substitution is uncertain, any one of the 24 hydrogen atoms in the BH1 compound can be replaced by a deuterium atom. Therefore, this type of compound with 1 deuterium atom includes 24 compounds.

[0037] As a preferred technical solution of the present application, the compound A is selected from any one of the following compounds:

[0038]

[0039]

[0040] As a preferred technical solution of the present application, the deuterium exchange reaction comprises the following steps:

[0041] In the presence of a catalyst, compound A is placed in D2O and a solvent to perform a deuterium exchange reaction to obtain the deuterium exchange mixture;

[0042] Preferably, the solvent is selected from C6D6.

[0043] It should be noted that C6D6 is the product obtained by replacing all hydrogen atoms on benzene with deuterium atoms.

[0044] Preferably, the solvent is C6D6, and the volume ratio of D2O to C6D6 is 1:(1-3), for example, it can be 1:1, 1:1.2, 1:3.

[0045] Preferably, the reaction is carried out in the presence of a catalyst selected from one or more combinations of palladium chloride, nickel chloride, Pd / C, Pt / C, and PtO2.

[0046] Preferably, the reaction is carried out in a nitrogen atmosphere.

[0047] Preferably, the temperature of the deuterium exchange reaction is 60-100℃, for example, it can be 60℃, 70℃, 80℃, 90℃, or 100℃.

[0048] Preferably, the deuterium exchange reaction time is 1-80h, for example, it can be 1h, 2h, 4h, 6h, 10h, 12h, 24h, 30h, 40h, 50h, 60h, 70h, or 80h, etc.

[0049] Preferably, the nitrogen pressure of the deuterium exchange reaction is 0.01-2MPa, for example, it can be 0.01MPa, 0.05MPa, 0.1MPa, 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, or 2MPa, etc.

[0050] Preferably, the deuterium substitution rate of the deuterium-substituted 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%, etc.

[0051] More preferably, the deuterium substitution rate of the deuterium-substituted mixture is 34% to 70%, for example, it can be 34.0%, 38.5%, 42.4%, 58.0%, 66.1%, 70%, etc.

[0052] More preferably, the deuterium substitution rate of the deuterium-substituted mixture is 34% to 70%, for example, it can be 34.0%, 38.5%, 42.4%, 58.0%, 66.1%, 70%, etc.

[0053] In the present application, 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, the deuterium substitution 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 all H in the composition or compound is replaced by D, the deuterium substitution rate is 0%, and 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 deuterium substitution reaction according to the present application can also be carried out in the presence of activated carbon, and the deuterium substitution reaction according to the present application also includes a post-treatment step after the reaction is completed. The post-treatment method includes cooling, filtering, separating, and drying.

[0055] In a second aspect, the present application provides an organic electroluminescent device, which comprises an anode, a cathode, and an organic layer between the anode and the cathode.

[0056] The material of the organic layer comprises the deuterium-substituted composition according to the first aspect.

[0057] Preferably, the organic layer comprises a light-emitting layer.

[0058] The material of the light-emitting layer comprises a host material, and the host material comprises the deuterium-substituted composition according to the first aspect.

[0059] Preferably, the organic layer further comprises a hole transport layer (including at least one of a hole injection layer, a hole transport layer, and an electron blocking layer), 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 application, the material of the light-emitting layer further comprises a dopant material.

[0061] The dopant material includes a compound having a structure as shown in Formula BDI:

[0062]

[0063] wherein Ar 101 , Ar 102 , Ar 201 , Ar 202 each independently is selected from any one of or a combination of at least two of a substituted or unsubstituted C6-C40 (e.g., can be C6, C10, C12, C15, C18, C24, C30, C36, or C40, etc.) aryl, a substituted or unsubstituted C12-C20 (e.g., can be C12, C13, C14, C15, C16, C17, C18, C19, or C20) heteroaryl;

[0064] R 101 and R 102 each independently is selected from any one of or a combination of at least two of a substituted or unsubstituted C1-C12 (e.g., can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, or C12) alkyl, a substituted or unsubstituted C6-C40 (e.g., can be C6, C10, C12, C15, C18, C24, C30, C36, or C40, etc.) aryl, a substituted or unsubstituted C12-C20 (e.g., can be C12, C13, C14, C15, C16, C17, C18, C19, or C20) heteroaryl;

[0065] R 101 and R 102 may be connected into a ring by a single bond;

[0066] m, n each independently is selected from 0 or 1, and m, n are not simultaneously 0;

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

[0068] As a preferred technical solution of the present application, the C6-C40 aryl is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, benzofluorenyl, 9,10-diphenylanthryl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, perylenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, hydrobenzanthryl, indenofluorenyl, benzindenofluorenyl, dibenzindenofluorenyl, naphthofluorenyl, or benzonaphthofluorenyl, preferably any one of phenyl, naphthyl, biphenyl, terphenyl, fluoranthenyl, fluorenyl, 9,10-diphenylanthryl, or benzofluorenyl.

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

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

[0071] Preferably, the C1-C6 alkoxy is selected from any one of methoxy, ethoxy, propoxy, butoxy, or , and the dotted line represents a connection site.

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

[0073] As a preferred technical solution of the present application, the Ar 101 and Ar 102 are 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, naphthyl, dibenzothiophenyl, naphthobenzothiophenyl, or a combination of at least two thereof, and the dotted line represents a connection site.

[0075] Preferably, the Ar 201 and Ar 202 are 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.

[0076] The 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 are each independently selected from any one of methyl, ethyl, propyl, or phenyl.

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

[0079] As a preferred technical solution of the present application, the compound having the structure as shown in formula BDI is selected from any one of the following compounds:

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087] Preferably, the compound having the structure as shown in formula BDI is selected from any one of the following compounds:

[0088]

[0089] As a preferred technical solution of the present application, the composition further comprises a compound having the structure as shown in formula II:

[0090]

[0091] wherein, the R 21 , R 22 and R 23 are each independently selected from any one of hydrogen, C1-C12 (e.g., can be C1, C2, C4, C6, C8, C10, or C12, etc.) straight chain or branched alkyl, C6-C12 (e.g., can be C6, C7, C8, C9, C10, C11, or C12) cycloalkyl, -NAr 23 Ar 24 .

[0092] the Ar 21 , Ar 22 , Ar 23 , Ar 24 each independently is selected from any one of substituted or unsubstituted C6-C20 (e.g., can be C6, C8, C10, C12, C14, C16, C18, or C20, etc.) aryl, substituted or unsubstituted C3-C20 (e.g., can be C3, C6, C8, C10, C12, C14, C16, C18, or C20, etc.) heteroaryl;

[0093] the Ar 21 , Ar 22 , Ar 23 , Ar 24 each independently is selected from any one of C1-C5 (e.g., can be C1, C2, C3, C4, or C5, etc.) straight chain or branched alkyl or C6-C12 (e.g., can be C6, C7, C8, C9, C10, C11, or C12, etc.) aryl.

[0094] Preferably, the Ar 21 , Ar 22 , Ar 23 , Ar 24 each independently is selected from any one of

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

[0096] As a preferred technical solution of the present application, the compound having the structure as shown in formula II is selected from any one of the following compounds:

[0097]

[0098]

[0099] As a preferred technical solution of the present application, the composition further comprises a compound having the structure as shown in formula III:

[0100]

[0101] wherein, the Ar 31 , Ar 32 , Ar 33 , and Ar​34 each independently selected from any one or a combination of at least two of substituted or unsubstituted C6-C22 (e.g., can be C6, C8, C10, C12, C15, C18, or C22, etc.) aryl, substituted or unsubstituted C12-C40 (e.g., can be C12, C15, C18, C24, C30, C36, or C40, etc.) heteroaryl;

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

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

[0104] Ar 31 , Ar 32 , Ar 33 , Ar 34 each of the substituents in said substituted is independently selected from C1-C5 (e.g., can be C1, C2, C3, C4, or C5, etc.) straight chain or branched alkyl, or C6-C12 (e.g., can be C6, C7, C8, C9, C10, C11, or C12, etc.) aryl.

[0105] Preferably, said Ar 31 , Ar 32 , Ar 33 , and Ar 34 are each independently selected from or a combination of at least two thereof.

[0106] Preferably, said compound having a structure as shown in Formula III is selected from any one of the following compounds:

[0107]

[0108] In a third aspect, the present application provides a display device, which comprises the organic electroluminescent device according to the second aspect.

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

[0110] In the present application, a specific aromatic group-substituted anthracene compound is subjected to a deuterium substitution reaction to obtain a deuterium-substituted mixture, and the obtained deuterium-substituted mixture is used as a host material of a light-emitting layer, so that the OLED light-emitting device prepared therefrom has a lower driving voltage and a longer service life. Meanwhile, the deuterium substitution reaction process for preparing the deuterium-substituted mixture is simple, the reaction conditions are mild, no complicated purification process is required, the post-treatment is simple, and the present application is suitable for preparing an organic electroluminescent device, and especially when the compound shown as BDI is used as a doping material, the device performance is more excellent. DETAILED DESCRIPTION

[0111] The technical solutions of the present application are further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations on the present application.

[0112] Synthesis Example 1

[0113] This embodiment provides BH1-D series deuterated compositions prepared from compound BH1 through deuterium substitution reaction, and the preparation method is as follows:

[0114]

[0115] wherein a is selected from an integer from 0 to 7; b is selected from an integer from 0 to 4; c is selected from an integer from 0 to 8; d is selected from an integer from 0 to 5; and a+b+c+d≥1.

[0116] The specific preparation method of the above BH1-D series deuterated compositions is as follows:

[0117] At room temperature, 500 mL autoclave is added with compound BH1 (4.56 g, 0.01 mol), palladium chloride (0.0177 g, 0.0001 mol), activated carbon (0.2 g), D2O (20 mL) and C6D6 (20 mL), and nitrogen is introduced into the autoclave to a pressure of 0.2 MPa, then the temperature is raised to 90°C for a certain period of time, then the temperature is lowered to room temperature, filtered, separated, and the organic layer after separation is dried with magnesium sulfate, then short silica gel column is used for decolorization, concentrated to dryness, and vacuum dried for 24 h to obtain BH1-D;

[0118] The products prepared at different reaction times are weighed, sublimed, and then deuterium substitution rate detection is performed (the deuterium substitution rate is tested by using the internal standard method, and the method is tested according to the method described in the literature “Wu Yurong, Chen Minzhu, Determination of Deuterated Bromobenzene Content by 1H NMR Method [J], Journal of Sichuan University: Natural Science Edition, 1997, 34(6): 2”), and the reaction time and the value of the deuterium substitution rate of the product are shown in Table 1 as follows:

[0119] Table 1

[0120]

[0121]

[0122] Synthesis Example 2

[0123] This embodiment provides BH3-D series deuterated compositions prepared from compound BH3 through deuterium substitution reaction, and the preparation method is as follows:

[0124]

[0125] Where a is an integer from 0 to 7; b is an integer from 0 to 8; c is an integer from 0 to 7; and a + b + c ≥ 1.

[0126] The preparation method of the above-mentioned BH3-D series deuterated compositions can refer to the preparation method of the BH1-D series deuterated compositions, except that compound BH1 is replaced with an equal amount of compound BH3.

[0127] The products prepared at different reaction times were weighed, sublimated, and then subjected to deuteration rate testing (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" was used for testing). The values ​​of reaction time and deuteration rate of the products are shown in Table 2 below:

[0128] Table 2

[0129] No. Deuterated composition Reaction time / (h) Product weight / (g) Deuterium enrichment 1 BH3-D01 1 4.10 9.56％ 2 BH3-D02 10 4.11 36.26％ 3 BH3-D03 20 4.17 55.09％ 4 BH3-D04 40 4.36 69.16％ 5 BH3-D05 100 4.31 98.32％

[0130] Take BH3-D01 and test its deuteration rate according to the methods disclosed in CN115280531A

[0098] -

[0106] :

[0131] Table 2-1

[0132]

[0133]

[0134] Take BH3-D03 and test its deuteration rate according to the methods disclosed in CN115280531A

[0098] -

[0106] :

[0135] Table 2-2

[0136]

[0137] Synthesis Example 3

[0138] This embodiment provides a BH3-D series of deuterated compositions, which are prepared from compound BH3 via a deuteration reaction. The preparation method is as follows:

[0139]

[0140] Where a is an integer from 0 to 7; b is an integer from 0 to 8; c is an integer from 0 to 7; and a + b + c ≥ 1.

[0141] The preparation method of the above-mentioned BH3-D series deuterated compositions can refer to the preparation method of the BH1-D series deuterated compositions in Synthesis Example 1, except that compound BH1 is replaced with an equal amount of compound BH3, and PdCl2 is replaced with an equal amount of PtO2.

[0142] The products prepared at different reaction times were weighed, sublimated, and then subjected to deuteration rate testing (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" was used for testing). The values ​​of reaction time and deuteration rate of the product are shown in Table 3 below:

[0143] Table 3

[0144]

[0145]

[0146] Comparative Synthesis Example 1

[0147] This embodiment provides a BH3-D series of deuterated compositions, which are prepared from compound BH3 via a deuteration reaction. The preparation method is as follows:

[0148]

[0149] Where a is an integer from 0 to 7; b is an integer from 0 to 8; c is an integer from 0 to 7; and a + b + c ≥ 1.

[0150] At room temperature, compound BH3 (4.3 g, 0.01 mol), palladium chloride (0.0177 g, 0.0001 mol), activated carbon (0.2 g), D2O (10 mL), and C6D6 (50 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 mixture was filtered and separated. The organic layer after separation was dried with magnesium sulfate, decolorized by a short silica gel column, concentrated to dryness, and then vacuum dried for 24 h to obtain BH3-D.

[0151] The products prepared at different reaction times were weighed, sublimated, and then subjected to deuteration rate detection (the deuteration rate was tested using the internal standard method, referring to 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"). The values ​​of reaction time and deuteration rate of the products are shown in Table 4 below.

[0152] Table 4

[0153] No. Deuterated composition Reaction time / (h) Product weight / (g) Deuterium enrichment 1 BH3-DD01 1 4.16 16.38％ 2 BH3-DD02 10 4.22 57.62％ 3 BH3-DD03 40 4.28 89.11％ 4 BH3-DD04 80 4.21 98.92％

[0154] Take BH3-DD02 and test its deuteration rate according to the methods disclosed in CN115280531A

[0098] -

[0106] :

[0155] Table 4-1

[0156]

[0157] Compared with synthesis example 2, the reaction was carried out under a hydrogen atmosphere, and the ratio of deuterium water to deuterium benzene was changed from 1:1 to 1:5. After the proportion of deuterium benzene increased, the reaction selectivity became worse.

[0158] Comparative Synthesis Example 2

[0159] This embodiment provides a BH3-D series deuterated composition, which is prepared by deuteration reaction of compound BH3. The preparation method is based on the method disclosed in CN115280531A

[0131] -

[0133] , with the reaction time controlled at 40-50 minutes and the reaction temperature at 70°C. The resulting deuterated composition is BH3-DC.

[0160]

[0161] Where a is an integer from 0 to 7; b is an integer from 0 to 8; c is an integer from 0 to 7; and a + b + c ≥ 1.

[0162] After sublimation of BH3-DC, the deuteration rate was determined (the deuteration rate was determined by the internal standard method, referring to 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"), and the deuteration rate was found to be 58.26%.

[0163] Referring to the methods disclosed in CN115280531A

[0098] -

[0106] , its deuteration rate was tested:

[0164] Table 5

[0165]

[0166]

[0167] Other specific structures used in the following application examples are shown below:

[0168]

[0169] Application Example 1

[0170] 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).

[0171] The fabrication method of the above-mentioned organic electroluminescent device is as follows:

[0172] (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.

[0173] (2) Place the glass substrate in a vacuum chamber and evacuate it to 1×10⁻⁶. -5 ~1×10 -4 Pa, 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.

[0174] (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 BH3-D01, the doping material is BD-3, and the volume ratio of the main material to the doping material is 97:3.

[0175] (4) TPBI is vacuum-deposited on the organic light-emitting layer as the electron transport layer of the organic electroluminescent device; the deposition rate is 0.01 nm / s and the total film thickness is 30 nm.

[0176] (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.

[0177] Application Example 2-11

[0178] Application Examples 2-11 provide an organic electroluminescent device, which differs from Application Example 1 only in that the light-emitting host material BH3-D01 in Application Example 1 is replaced (see Table 6 for details). The other structures, materials and preparation methods are the same as those in Application Example 1.

[0179] Comparative Application Examples 1-2

[0180] Comparative Application Examples 1-2 provide an organic electroluminescent device, which differs from Application Example 1 only in that the light-emitting host material BH3-D01 in Application Example 1 is replaced (see Table 6 for details). The other structures, materials and preparation methods are the same as those in Application Example 1.

[0181] Performance testing:

[0182] The driving voltage, current efficiency, and lifetime LT90 of the organic electroluminescent devices provided above were tested using the OLED-1000 multi-channel accelerated aging lifetime and photochromic performance analysis system manufactured by Hangzhou Yuanfang. LT90 refers to the time required for the brightness to decrease to 90% of its original brightness while maintaining an initial brightness of 2000 nits with a constant current density. Specific test results are shown in Table 10, where voltage, current efficiency, and LT90 are all relative values.

[0183] Table 6

[0184]

[0185] As shown in Table 6, in this invention, a deuterated mixture is obtained by subjecting specific aromatic-substituted anthracene compounds to a deuteration reaction under specific conditions. The resulting deuterated mixture is then used as the main material for the light-emitting layer. The OLED light-emitting device prepared in this way has a lower driving voltage, higher efficiency, and longer lifespan.

[0186] As can be seen from Application Examples 1-5 and Application Examples 6-10, as the deuteration rate of the deuterated composition increases, the driving voltage of the organic electroluminescent device prepared by using this deuterated compound as the main material of the light-emitting layer first decreases and then increases, while the efficiency and lifespan first increase and then decrease.

[0187] The device exhibits superior overall performance when the deuteration rate is between 34% and 70%. The device voltage is lowest when the deuteration rate is between 34% and 37%.

[0188] Comparing Application Examples 1-2 and 3, the deuteration rates are roughly the same, but the device performance differs significantly. The reasons are as follows:

[0189] One of the important factors affecting the deterioration of device life is the decomposition of materials. Specifically, in BH3, this is reflected in the breakage of CH bonds. When CH bonds are replaced by CD bonds, the device life can be improved because CD bonds are less prone to breakage.

[0190] In the BH3 structure, the highly reactive CH bonds are easily broken in the device. Therefore, preferential replacement of the more reactive CH bonds has a positive impact on the device lifetime.

[0191] In the BH3-DC used in Example 2, a large amount of deuterated benzene was used as the deuterating agent and trifluoromethanesulfonic acid was used as the catalyst. The reaction was completed in 40-50 minutes, and the reaction rate was relatively fast.

[0192] The BH3-DO3 used in Example 3 was used with a small amount of a mixed solvent of deuterium benzene and deuterium water as the deuterating agent, palladium chloride as the catalyst, the reaction conditions were mild, the reaction rate was slow, and the reaction time was 20 hours.

[0193] The faster the reaction rate, the worse the reaction selectivity. A comparison of Tables 5 and 2-2 shows that in BH3-DC, compounds substituted with 12 deuterium atoms account for 27.2%, with a large number of compounds substituted with 11, 13, and 14 deuterium atoms. In contrast, in BH3-DO3, compounds substituted with 12 deuterium atoms account for a high proportion of 69.2%, while compounds substituted with 11, 13, and 14 deuterium atoms are relatively fewer.

[0194] For BH3, the activity of each H atom is different. When deuteration is carried out at a lower reaction rate, most of the highly active H atoms in the product are replaced by D atoms. When the reaction rate is faster, the reaction selectivity becomes worse, and more of the less active H atoms are replaced by D atoms. This can also be seen from the comparison between Table 5 and Table 2-2.

[0195] Furthermore, BH3-DC contains 7 types of components, while BH3-DO3 contains 11 types of components.

[0196] The film formed by multiple components during device fabrication is more amorphous and has a denser structure, resulting in better and more stable charge transport performance, which in turn leads to lower voltage, higher efficiency, and reduced lifetime.

[0197] Based on the above explanation, it can be seen that devices fabricated using BH3-DD02 have better performance than devices fabricated using BH3-DC, but are inferior to devices fabricated using BH3-DO3.

[0198] Application Example 12

[0199] This application example provides an organic electroluminescent device, which differs from Application Example 1 only in that the host material BH3-D01 of the light-emitting layer in Application Example 1 is replaced with BH1-D02, and the doping material is BD-3 (see Table 7 for details). The other structures, materials and preparation methods are the same as in Application Example 1.

[0200] Application Examples 13-14

[0201] Application Examples 13-14 provide an organic electroluminescent device, which differs from Application Example 12 only in that the doping material is different (see Table 7 for details). The other structures, materials and preparation methods are the same as those in Application Example 12.

[0202] The performance of the organic electroluminescent device provided in test case 12-14 was tested using the same method as above, and the test results are shown in Table 7.

[0203] Table 7

[0204] Doping material cd / m 2 )]]> Driving voltage LT90 Application Example 12 BD-3 1000 1 1 Application Example 13 BD-1 1000 1.32 0.79 Application Example 14 BD-2 1000 1.09 0.62

[0205] As shown in Table 7, using the deuterated composition provided by this invention as the main material of the light-emitting layer and the compound (BD-3) having the structure shown in formula BDI as the dopant material of the light-emitting layer can further reduce the driving voltage of the organic electroluminescent device and improve the service life of the organic electroluminescent device.

[0206] In summary, this invention involves deuterating specific aromatic-substituted anthracene compounds to obtain a deuterated mixture, which is then used as the host material for the light-emitting layer. The resulting OLED light-emitting device exhibits a lower driving voltage and a longer lifetime. Furthermore, by using a compound (BD-3) with the structure shown in formula BDI as a dopant material for the light-emitting layer, the driving voltage of the organic light-emitting device can be further reduced, and its lifetime can be improved. The applicant declares that while the above embodiments illustrate the detailed process flow of this invention, this invention is not limited to the above detailed process flow, and 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 the raw materials in the product of this invention, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. A deuterated composition, characterized in that, The deuterated composition comprises a deuterated mixture prepared by deuteration of at least one compound A; Compound A is selected from any one of the following compounds: ； The deuteration reaction conditions are as follows: Compound A is placed in D2O and C6D6 in the presence of a catalyst to carry out a deuteration reaction, thereby obtaining the deuterated mixture. The catalyst is one or more of palladium chloride and PtO2. The reaction is carried out in a nitrogen atmosphere, the temperature of the deuteration reaction is 60-100°C, the volume ratio of D2O to C6D6 is 1:(1-3), and the time of the deuteration reaction is 1-80 h. The deuteration rate of the deuterated mixture is 34-70%.

2. The deuterated composition according to claim 1, characterized in that, The deuterated mixture includes at least 7 classes of compounds, each class of compounds being compounds with the same number of deuterium atoms obtained by deuterating compound A.

3. The deuterated composition according to claim 1, characterized in that, The deuterated mixture includes at least 8 classes of compounds, each class of compounds being compounds with the same number of deuterium atoms obtained by deuterating compound A.

4. The deuterated composition according to claim 1, characterized in that, The deuterated mixture includes at least 11 classes of compounds, each class of compounds being compounds with the same number of deuterium atoms obtained by deuterating compound A.

5. The deuterated composition according to claim 1, characterized in that, The deuteration rate of the deuterated mixture is 34-37%.

6. 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 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 1-5.

7. A display device, characterized in that, The display device includes the organic electroluminescent device as described in claim 6.

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