A deuterated composition, organic electroluminescent device and display device

Abstract

The application provides a deuterated composition, an organic electroluminescent device and a display device. The deuterated composition comprises a deuterated mixture prepared by deuterating a compound A; the compound A has a structure as shown in formula I. The OLED device prepared by using the deuterated composition provided by the application as a hole layer material has a lower driving voltage, a higher current efficiency and a longer service life.

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] Displays integrate electronics, communication, and information processing technologies, and are considered another major development opportunity for the electronics industry after electronics and computers. Display technology and displays occupy a very important position in the development of information technology. Displays on televisions, computers, telephones, and various instruments provide a wealth of information for people's daily lives and work. In recent years, new display technologies have become a research focus, among which flat panel displays, with their advantages of small weight, low power consumption, and portability, have become a research hotspot.

[0003] Among the various flat panel displays currently available, liquid crystal displays (LCDs) hold a significant position. However, LCDs have many drawbacks: they do not emit their own light and require a light source or ambient light; they suffer from viewing angle limitations; their response time is slow; and their resolution is low. Therefore, researchers have been constantly searching for new flat panel display technologies. Organic electroluminescence (OLED) was discovered as early as 1963, but it did not attract much attention at the time. It wasn't until 1987, when Tang's research group at Kodak published their work on a high-brightness, high-efficiency thin-film organic light-emitting diode (OLED) driven by low DC voltage using organic fluorescent and hole materials, that this technology regained attention and opened up a completely new research field.

[0004] OLEDs possess significant advantages, such as low power consumption, fast response speed, flexibility, wide viewing angle, large-area display capability, and a full range of colors. They are also 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, OLEDs have made significant progress as a new display technology, finding widespread application in flat panel displays, flexible displays, solid-state lighting, and automotive displays.

[0005] Currently, organic electroluminescence has become the mainstream display technology, and correspondingly, various novel OLED materials have been developed. As hole layer materials, including hole injection materials, hole transport materials, and electron blocking materials, they are currently mainly triarylamine compounds containing one or more nitrogen atoms. However, their various properties still need improvement, especially in terms of efficiency, lifetime, and voltage.

[0006] Therefore, developing more types of hole-like 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

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a deuterated composition, an organic electroluminescent device, and a display device. In this invention, a deuterated mixture is obtained by deuterating a triarylamine compound, and this deuterated mixture is used as the hole layer material. The resulting OLED device exhibits lower driving voltage, higher current efficiency, and longer lifetime.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a deuterated composition comprising a deuterated mixture prepared from compound A by a deuteration reaction;

[0010] The compound A has the structure shown in Formula I:

[0011]

[0012] Among them, Ar 11 Ar 12 Ar 21 Ar 22 Ar is independently selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C12-C20 heteroaryl groups;

[0013] Ar 11 Ar 12 They can be connected via a single key, Ar 21 Ar 22 They can be connected via a single key; Ar, Ar 12 They can be connected via a single key, Ar, Ar 11 They can be connected via a single key, Ar, Ar 21 They can be connected via a single key, Ar, Ar 22 They can be connected via a single button;

[0014] n is selected from 0 or 1;

[0015] Ar 11 Ar 12 Ar 21 Ar 22 The substituents described in Ar are each independently selected from at least one of C1-C12 alkyl, C1-C12 alkoxy, and C6-C12 aryl.

[0016] In this invention, a deuterated mixture is obtained by deuterating a triarylamine compound, and the resulting deuterated mixture is used as the hole layer material. The OLED device prepared in this way has a lower driving voltage, higher current efficiency, and longer lifetime.

[0017] In the field of display technology, triarylamine compounds are often used as hole layer materials to prepare organic electroluminescent devices (OLEDs). However, the performance of these OLEDs needs improvement, particularly in efficiency, lifetime, and voltage. Therefore, deuterated triarylamine compounds can be used as hole layer materials to improve the performance of OLEDs. However, the preparation process of deuterated triarylamine compounds in existing technologies is complex and costly. For example, the preparation process of the deuterated triarylamine compound D8-HTSP2 is as follows:

[0018]

[0019] The above preparation process requires the use of 2-bromodeuterated biphenyl. In order to obtain 2-bromodeuterated biphenyl with high purity, a complicated reaction and purification process is required. Therefore, the preparation of deuterated triarylamine compound D8-HTSP2 is complicated and costly. Furthermore, when D8-HTSP2 is used as the hole layer material, the overall performance of the prepared OLED device is poor.

[0020] In this invention, a deuterated mixture is obtained by deuterating a compound (compound A) with a specific structure and then performing a simple post-processing. The OLED light-emitting device prepared using this deuterated mixture has good overall performance, low driving voltage, high current efficiency, and long service life.

[0021] The preparation of this deuterated mixture avoids tedious purification work, the preparation method is simple, the reaction conditions are mild, and the post-processing is simple.

[0022] It should be noted that in organic reactions, when there is no significant difference in the reactive sites on the reacting molecules, it is difficult to carry out substitution reactions at the specific reactive sites. Therefore, in this invention, after deuterating compound A, a mixture (deuterated mixture) is obtained.

[0023] In this invention, Ar 11 Ar 12 Ar 21 Ar 22 Ar is independently selected from substituted or unsubstituted C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl groups, and substituted or unsubstituted C12-C20 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) heteroaryl groups.

[0024] Ar 11 Ar 12Ar 21 Ar 22 The substituents described in Ar are each independently selected from at least one of C1-C12 (e.g., C1, C2, C5, C6, C8, C10 or C12), C1-C12 (e.g., C1, C2, C5, C6, C8, C10 or C12), and C6-C12 (e.g., C6, C7, C8, C9, C10, C11 or C12) aryl groups.

[0025] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0026] As a preferred technical solution of the present invention, the Ar 11 Ar 12 Ar 21 Ar 22 Ar is independently selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, tetraphenyl, naphthyl, phenanthryl, anthracene, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, triphenylene, fluoranyl, pyrene, perylene, spirofluorenyl, ind[a]fluorenyl, hydrogenated benzo[a]anthryl, dibenzofuran, dibenzo[a]thiophene, naphtho[a]benzofuran, naphtho[a]thiophene, dinaphtho[a]thiophene, dinaphtho[a]furan, dibenzo[a]furan, benzo[a]furan;

[0027] The substituents are each independently selected from at least one of C1-C12 (e.g., C1, C2, C5, C6, C8, C10, or C12), C1-C12 (e.g., C1, C2, C5, C6, C8, C10, or C12), and C6-C12 (e.g., C6, C7, C8, C9, C10, C11, or C12) aryl groups.

[0028] Preferably, the Ar 11 Ar 12 Ar 21 Ar 22 The substituents described in Ar are each independently selected from at least one of methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophene, or naphthyl.

[0029] As a preferred embodiment of the present invention, the Ar is selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, phenanthryl, anthracene, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiopheneyl, triphenylene, fluorenyl, benzofluorenyl;

[0030] The substituent is selected from at least one of methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophene, or naphthyl.

[0031] In this invention, the Ar is selected from any one of the following groups:

[0032]

[0033]

[0034] Preferably, the Ar 11 Ar 12 Ar 21 Ar 22 Each group is independently selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, triphenylene, fluoranyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiopheneyl, dibenzofuranobenzofuranyl, dibenzothiophenebenzothiopheneyl;

[0035] The substituents are each independently selected from at least one of methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiopheneyl or naphthyl.

[0036] In this invention, the Ar 11 Ar 12 Ar 21 Ar 22 Each group is independently selected from any one of the following groups:

[0037]

[0038]

[0039] As a preferred embodiment of the present invention, compound A is selected from any one of the following compounds:

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053] As a preferred embodiment of the present invention, the deuteration reaction includes the following steps:

[0054] In the presence of a catalyst, compound A is placed in D2O and a solvent to undergo a deuteration reaction, yielding the deuterated mixture.

[0055] As a preferred embodiment of the present invention, the catalyst is selected from any one or a combination of at least two of PdCl2, NiCl2, triphenylphosphine or tri-o-tolylphosphine; more preferably, it is any one or a combination of at least two of PdCl2 and NiCl2, PdCl2, NiCl2 and triphenylphosphine, or PdCl2, NiCl2 and tri-o-tolylphosphine.

[0056] Preferably, the molar ratio of PdCl2 to NiCl2 in the combination of PdCl2 and NiCl2 is (1-2):1 (for example, it can be 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1 or 2:1, etc.), and more preferably 1:1.

[0057] Preferably, in the combination of PdCl2, NiCl2 and triphenylphosphine, the ratio of the amount of triphenylphosphine to the sum of the amounts of PdCl2 and NiCl2 is (1-3):1 (for example, it can be 1:1, 1.5:1, 2:1, 2.2:1, 2.5:1 or 3:1, etc.), and more preferably (2-2.5):1.

[0058] Preferably, in the combination of PdCl2, NiCl2 and tri-o-tolylphosphine, the ratio of the amount of tri-o-tolylphosphine to the sum of the amounts of PdCl2 and NiCl2 is (1-3):1 (for example, it can be 1:1, 1.5:1, 2:1, 2.2:1, 2.5:1 or 3:1, etc.), and more preferably (2-2.2):1.

[0059] It should be noted that in this invention, the deuteration reaction is carried out in the presence of activated carbon, which allows the catalyst to be adsorbed on the surface of the activated carbon, thereby increasing the contact area between the catalyst and the reactants and promoting the reaction.

[0060] As a preferred embodiment of the present invention, 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.

[0061] It should be noted that C6D6 is the product of benzene in which all hydrogen atoms are replaced by deuterium atoms.

[0062] 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.

[0063] Preferably, the deuteration reaction is carried out in a hydrogen atmosphere.

[0064] 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.

[0065] Preferably, the deuteration rate of the deuterated mixture is 15% to 99% (e.g., it can be 15%, 20%, 28%, 38%, 50%, 53%, 60%, 69%, 70%, 80%, 90%, or 99%), and more preferably 28% to 90%.

[0066] 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%.

[0067] 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.

[0068] As a preferred embodiment of the present invention, the deuterated composition further includes compound B;

[0069] Compound B is selected from any one of the following HI-1 to HI-9 compounds:

[0070]

[0071]

[0072] Preferably, the volume percentage of compound B in the deuterated composition is 3-5%, for example, it can be 3%, 3.3%, 3.6%, 4%, 4.2%, 4.6% or 5%, etc.

[0073] In a second aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;

[0074] The material of the organic thin film layer includes the deuterated composition as described in the first aspect.

[0075] Preferably, the organic thin film layer includes a hole layer, which includes a hole injection layer, a hole transport layer, and an electron blocking layer;

[0076] The material of the cavity layer includes the deuterated composition as described in the first aspect.

[0077] Thirdly, the present invention provides a display device comprising the organic electroluminescent device as described in the second aspect.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] In this invention, compound A is deuterated to obtain a deuterated mixture, which is then used as the hole layer material. The resulting OLED device exhibits a low driving voltage, high current efficiency, and long lifetime. Furthermore, the deuteration reaction process for preparing the deuterated mixture in this invention is simple, the reaction conditions are mild, no complicated purification process is required, and the post-processing is simple, making it suitable for preparing organic electroluminescent devices. Detailed Implementation

[0080] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0081] Example 1

[0082] This embodiment provides a deuterated mixture of the HTSP1-D series, and its reaction equation is as follows:

[0083]

[0084] Where a1, b1, and c1 are selected from integers from 0 to 4; d1 is selected from integers from 0 to 3; e1 and h1 are selected from integers from 0 to 5; f1 and g1 are selected from integers from 0 to 4; and a1+b1+c1+d1+e1+g1+h1≥1.

[0085] The preparation method of the above-mentioned HTSP1-D series deuterated mixtures is as follows:

[0086] At room temperature, HTSP1 (6.36 g, 0.01 mol), palladium chloride (0.0177 g, 0.0001 mol), activated carbon (0.2 g), D2O (30 mL), and C6D6 (100 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. The mixture was weighed to obtain a deuterated mixture of HTSP1-D series.

[0087] The products prepared at different reaction times were weighed, sublimated, and then subjected to deuteration rate testing (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"). The reaction time and the deuteration rate of the products are shown in Table 1 below:

[0088] Table 1

[0089] Serial Number Deuterated mixture Reaction time (h) Product weight (g) Deuteration rate 1 HTSP1-D01 1 6.28 12.3％ 2 HTSP1-D02 2 6.31 22.1％ 3 HTSP1-D03 4 6.32 31.2％ 4 HTSP1-D04 10 6.38 55.6％ 5 HTSP1-D05 30 6.45 75.1％ 6 HTSP1-D06 60 6.55 88.6％ 7 HTSP1-D07 120 6.56 98.1％

[0090] Example 2

[0091] This embodiment provides a deuterated mixture of the HTSP2-D series, and its reaction equation is as follows:

[0092]

[0093] Where a1, b1, c1 are selected from integers from 0 to 4; d1, g2 are selected from integers from 0 to 3; e1 is selected from integers from 0 to 5; f1, h2 are selected from integers from 0 to 4; m is selected from integers from 0 to 3; n is selected from integers from 0 to 3, and a1+b1+c1+d1+e1+g2+h2+3-m+3-n≥1.

[0094] The preparation method of the above-mentioned HTSP2-D series deuterated mixtures is the same as that of the HTSP1-D series deuterated mixtures, except that HTSP1 is replaced with an equal amount of HTSP2, and all other conditions are the same.

[0095] The products obtained from different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same testing method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 2 below:

[0096] Table 2

[0097] Serial Number Deuterated mixture Reaction time (h) Product weight (g) Deuteration rate 1 HTSP2-D01 1 6.55 8.9％ 2 HTSP2-D02 2 6.57 16.2％ 3 HTSP2-D03 4 6.59 23.8％ 4 HTSP2-D04 10 6.71 45.1％ 5 HTSP2-D05 30 6.66 60.1％ 6 HTSP2-D06 55 6.77 77.3％ 7 HTSP2-D07 120 6.88 82.2％ 8 HTSP2-D08 180 6.79 81.9％

[0098] Hydrogen NMR spectroscopy was performed on HTSP2-D07. 1 H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3) showed only a single peak at δ 1.70, with no other peaks. This confirms that the hydrogen atom on the methyl group in the HTSP2 molecule was not replaced by a deuterium atom.

[0099] Example 2-1

[0100] This embodiment provides a deuterated mixture of the HTSP2-D series, and its reaction equation is as follows:

[0101]

[0102] Where a1, b1, c1 are selected from integers from 0 to 4; d1, g2 are selected from integers from 0 to 3; e1 is selected from integers from 0 to 5; f1, h2 are selected from integers from 0 to 4; m is selected from integers from 0 to 3; n is selected from integers from 0 to 3, and a1+b1+c1+d1+e1+g2+h2+3-m+3-n≥1.

[0103] Preparation method of the above-mentioned HTSP2-D series deuterated mixtures:

[0104] At room temperature, HTSP2 (6.76 g, 0.01 mol), palladium chloride (0.0177 g, 0.0001 mol), anhydrous nickel chloride (0.013 g, 0.0001 mol), activated carbon (0.2 g), D2O (30 mL), and C6D6 (100 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. The mixture was weighed to obtain a HTSP2-D series deuterated mixture.

[0105] The products obtained at different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 2-1 below:

[0106] Table 2-1

[0107] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTSP2-D21 1 6.66 15.6％ 2 HTSP2-D22 2 6.70 28.8％ 3 HTSP2-D23 4 6.70 55.7％ 4 HTSP2-D24 10 6.81 71.8％ 5 HTSP2-D25 30 6.83 88.9％ 6 HTSP2-D26 70 6.90 98.2％ 7 HTSP2-D27 100 6.91 98.7％

[0108] A comparison of the relevant data in Table 2 and Table 2-1 shows that if a mixture of palladium chloride and nickel chloride is used as a catalyst, the deuteration reaction is basically complete after 70 hours, with a deuteration rate greater than 98%.

[0109] Example 2-2

[0110] This embodiment provides a deuterated mixture of the HTSP2-D series, which differs from Example 2-1 only in that the amount of anhydrous nickel chloride added is 0.0002 mol (in this case, the molar ratio of palladium chloride to nickel chloride is 1:2), and the other conditions are the same as in Example 2-1.

[0111] The products prepared at different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 2-2 below:

[0112] Table 2-2

[0113]

[0114]

[0115] Example 3

[0116] This embodiment provides a HTSP3-D series deuterated mixture, the reaction equation of which is as follows:

[0117]

[0118] Where a1, b1, c1 are selected from integers from 0 to 4; d1, g2 are selected from integers from 0 to 3; e1 is selected from integers from 0 to 5; f1, h2 are selected from integers from 0 to 4; m is selected from integers from 0 to 3; n is selected from integers from 0 to 3, and a1+b1+c1+d1+e1+g2+h2+3-m+3-n≥1.

[0119] The preparation method of the above-mentioned HTSP2-D series deuterated mixture is the same as that in Example 2-1, except that HTSP2 is replaced with an equal amount of HTSP3, and other conditions are the same as in Example 2-1.

[0120] The products obtained from different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 3 below:

[0121] Table 3

[0122] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTSP3-D01 4 6.68 50.1％ 2 HTSP3-D02 10 6.72 68.8％ 3 HTSP3-D03 30 6.81 89.1％ 4 HTSP3-D04 80 6.83 98.6％

[0123] As shown in Table 3, when a mixture of palladium chloride and nickel chloride is used as a catalyst, the deuteration reaction is basically complete after 80 hours, with a deuteration rate greater than 98%.

[0124] Example 4-1

[0125] This embodiment provides a deuterated mixture of the HTSP4-D series, and its reaction equation is as follows:

[0126]

[0127] Where b1 is selected from integers from 0 to 4; c1, a1, d1, g2 are selected from integers from 0 to 3; e1 is selected from integers from 0 to 5; f1, h2 are selected from integers from 0 to 4; m, n, p, q, r, s, t, u are selected from integers from 0 to 3, and a1+b1+c1+d1+e1+f1+g2+h2+3-m+3-n+p+q+r+s+t+u≥1.

[0128] The preparation method of the above-mentioned HTSP4-D series deuterated mixture is the same as that of the preparation method of HTSP2-D series deuterated mixture provided in Example 2-1, except that HTSP2 is replaced with an equal amount of HTSP4, and other conditions are the same as in Example 2-1.

[0129] The products obtained from different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 4-1 below:

[0130] Table 4-1

[0131] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTSP4-D01 4 7.65 21.1％ 2 HTSP4-D02 30 7.69 46.8％ 3 HTSP4-D03 80 7.78 58.6％ 4 HTSP4-D04 120 7.61 64.1％

[0132] A comparison of the data in Tables 2-1 and 4-1 shows that if a mixture of palladium chloride and nickel chloride is used as a catalyst, its catalytic efficiency for HTSP4 compounds is low, and the deuteration rate of the product is still <65% after 120 h of reaction.

[0133] NMR analysis was performed on HTSP4-D04. 1 H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3) showed only a single peak at δ 1.31, with no other clear peaks for H atoms. This confirmed that the hydrogen atom on the tert-butyl group in the HTSP4 molecule had not been replaced by a deuterium atom.

[0134] Example 4-2

[0135] This embodiment provides a deuterated mixture of the HTSP4-D series, and its reaction equation is as follows:

[0136]

[0137] Where b1 is selected from integers from 0 to 4; c1, a1, d1, g2 are selected from integers from 0 to 3; e1 is selected from integers from 0 to 5; f1, h2 are selected from integers from 0 to 4; m, n, p, q, r, s, t, u are selected from integers from 0 to 3, and a1+b1+c1+d1+e1+f1+g2+h2+3-m+3-n+p+q+r+s+t+u≥1.

[0138] The preparation method of the HTSP4-D series deuterated mixture in this embodiment is the same as that of the preparation method of the deuterated mixture in Example 4-1. The only difference is that the catalyst in this embodiment is palladium chloride (0.0177g, 0.0001mol), anhydrous nickel chloride (0.013g, 0.0001mol), and triphenylphosphine (0.1g, 0.0004mol). Other conditions are the same as in Example 4-1.

[0139] The products prepared at different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 4-2 below:

[0140] Table 4-2

[0141] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTSP4-D21 4 7.58 38.8％ 2 HTSP4-D22 30 7.61 66.9％ 3 HTSP4-D23 60 7.90 96..9％ 4 HTSP4-D24 80 8.17 98.9％

[0142] As shown in Table 4-2, if a mixture of palladium chloride, nickel chloride, and triphenylphosphine is used as a catalyst, its catalytic efficiency for HTSP4 compounds is high. After 60-80 hours of reaction, the deuteration reaction is basically complete, and the deuteration rate of the product is >95%.

[0143] Example 4-3

[0144] The reaction equation for the HTSP4-D series deuterated mixture in this embodiment is as follows:

[0145]

[0146] Where b1 is selected from integers from 0 to 4; c1, a1, d1, g2 are selected from integers from 0 to 3; e1 is selected from integers from 0 to 5; f1, h2 are selected from integers from 0 to 4; m, n, p, q, r, s, t, u are selected from integers from 0 to 3, and a1+b1+c1+d1+e1+f1+g2+h2+3-m+3-n+p+q+r+s+t+u≥1;

[0147] P(o-Tol)3 is tri-o-tolylphosphine, with the following structural formula:

[0148] In this embodiment, the preparation method of the HTSP4-D series deuterated mixture is the same as that of the preparation method of the deuterated mixture in Example 4-2, except that triphenylphosphine is replaced with an equal amount of tri-o-tolylphosphine, and other conditions are the same as in Example 4-2.

[0149] The products prepared at different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 4-3 below:

[0150] Table 4-3

[0151] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTSP4-D31 4 7.62 58.18％ 2 HTSP4-D32 20 7.86 89.2％ 3 HTSP4-D33 30 8.11 98..8％

[0152] As shown in Table 4-3, if a mixture of palladium chloride, nickel chloride, and tri-o-tolylphosphine is used as a catalyst, the deuteration reaction is basically complete after 30 hours of reaction, and the deuteration rate of the product is >95%.

[0153] As shown in Tables 4-1, 4-2 and 4-3, the mixture of palladium chloride, nickel chloride and tri-o-tolylphosphine as catalyst has good catalytic efficiency for HTSP4. After 30 hours of deuteration reaction, the reaction is basically complete and the deuteration rate is >98%.

[0154] Example 4-4

[0155] The HTSP4-D series deuterated mixture in this embodiment differs from that in Examples 4-3 only in that 0.0004 mol of tri-o-tolylphosphine is replaced with 0.0002 mol of tri-o-tolylphosphine, while the other conditions are the same as in Examples 4-3.

[0156] The products prepared at different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 4-4 below:

[0157] Table 4-4

[0158] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTSP4-D41 4 7.33 28.6％ 2 HTSP4-D42 50 7.62 35.7％ 3 HTSP4-D43 80 7.77 41.2％ 4 HTSP4-D44 120 7.82 46.1％

[0159] Examples 4-5

[0160] The only difference between this HTSP4-D series deuterated mixture and Examples 4-3 is that 0.0004 mol of tri-o-tolylphosphine is replaced with 0.0006 mol of tri-o-tolylphosphine; all other conditions are the same as in Examples 4-3.

[0161] The products obtained at different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 4-5 below:

[0162] Table 4-5

[0163] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTSP4-D51 4 7.51 59.1％ 2 HTSP4-D52 20 7.98 89.2％ 3 HTSP4-D53 30 7.60 78..2％ 4 HTSP4-D54 50 7.87 76.1％

[0164] As can be seen from Tables 4-3, 4-4, and 4-5, if a mixture of palladium chloride, nickel chloride, and tri-o-tolylphosphine is used as a catalyst, and the amount of tri-o-tolylphosphine is small (Example 4-4), the deuteration reaction proceeds slowly, and the deuteration rate of the product remains low even after a long reaction time; if the amount of tri-o-tolylphosphine is large (Example 4-5), although the deuteration reaction proceeds faster, the side reactions also increase, and the deuteration rate of the product decreases after 30 hours of reaction.

[0165] Example 5

[0166] This embodiment provides a deuterated mixture of the HTCZ1-D series, and its reaction equation is as follows:

[0167]

[0168] Where a3 and f3 are selected from integers from 0 to 5, b3, d3, e3, and h3 are selected from integers from 0 to 4, c3, g3, p, and q are selected from integers from 0 to 3, and a3+b3+c3+d3+e3+f3+g3+h3+p+q≥1.

[0169] The preparation method of the above-mentioned HTCZ1-D series deuterated mixture is the same as that of the preparation method of the deuterated mixture provided in Example 2-1, except that HTSP2 is replaced with an equal amount of HTCZ1, and other conditions are the same as in Example 2-1.

[0170] The products obtained at different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 5 below:

[0171] Table 5

[0172] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTCZ1-D01 4 6.81 50.3％ 2 HTCZ1-D02 10 6.91 77.8％ 3 HTCZ1-D03 30 7.00 92.6％ 4 HTCZ1-D04 80 7.02 99.1％

[0173] Example 6

[0174] This embodiment provides a deuterated mixture of the HTCZ2-D series, and its reaction equation is as follows:

[0175]

[0176] Where a4 and b4 are selected from integers from 0 to 5, c4, f4, e4, and d4 are selected from integers from 0 to 4, h4 and g4 are selected from integers from 0 to 3, and a4+b4+c4+d4+e4+f4+g4+h4≥1.

[0177] The preparation method of the above-mentioned HTCZ2-D series deuterated mixture is the same as that of the preparation method of the deuterated mixture provided in Example 2-1, except that HTSP2 is replaced with an equal amount of HTCZ2, and other conditions are the same as in Example 2-1.

[0178] The products obtained from different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 6 below:

[0179] Table 6

[0180] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTCZ2-D01 4 6.19 58.1％ 2 HTCZ2-D02 10 6.33 80.3％ 3 HTCZ2-D03 30 6.35 95.8％ 4 HTCZ2-D04 80 6.48 98.5％

[0181] Example 7

[0182] This embodiment provides a deuterated mixture of the HTBP1-D series, and its reaction equation is as follows:

[0183]

[0184] In HTBP1-D, at least one H atom is replaced by D.

[0185] The preparation method of the above-mentioned HTBP1-D series deuterated mixture is the same as that of the preparation method of the deuterated mixture provided in Example 2-1, except that HTSP2 is replaced with an equal amount of HTBP1, and other conditions are the same as in Example 2-1.

[0186] The products obtained from different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 7 below:

[0187] Table 7

[0188] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTBP1-D01 4 7.91 55.8％ 2 HTBP1-D02 10 8.03 71.3％ 3 HTBP1-D03 30 8.11 85.8％ 4 HTBP1-D04 60 8.13 98.1％

[0189] Example 8

[0190] This embodiment provides a deuterated mixture of the HTBP2-D series, and its reaction equation is as follows:

[0191]

[0192] In HTBP2-D, at least one H atom is replaced by D.

[0193] The preparation method of the above-mentioned HTBP2-D series deuterated mixture is the same as that of the preparation method of the deuterated mixture provided in Example 2-1, except that HTSP2 is replaced with an equal amount of HTBP2, and other conditions are the same as in Example 2-1.

[0194] The products obtained from different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 8 below:

[0195] Table 8

[0196] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTBP2-D01 4 4.69 39.9％ 2 HTBP2-D02 10 4.78 62.3％ 3 HTBP2-D03 30 4.82 79.8％ 4 HTBP2-D04 60 4.89 97.9％

[0197] Example 9

[0198] This embodiment provides a deuterated mixture of the HTTPA1-D series, and its reaction equation is as follows:

[0199]

[0200] In HTTPA1-D, at least one H atom is replaced by D.

[0201] The preparation method of the above-mentioned HTBP2-D series deuterated mixture is the same as that of the preparation method of the deuterated mixture provided in Examples 4-3, except that HTSP4 is replaced with an equal amount of HTTPA1, and other conditions are the same as those in Examples 4-3.

[0202] The products prepared at different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same testing method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 9 below:

[0203] Table 9

[0204] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTTPA1-D01 4 7.71 59.2％ 2 HTTPA1-D02 20 7.83 81.3％ 3 HTTPA1-D03 30 7.89 98.8％

[0205] Example 10

[0206] This embodiment provides a deuterated mixture of the HTTPA2-D series, and its reaction equation is as follows:

[0207]

[0208] In HTTPA2-D, at least one H atom is replaced by D.

[0209] The preparation method of the above-mentioned HTTPA2-D series deuterated mixture is the same as that of the preparation method of the deuterated mixture provided in Example 2-1, except that HTSP2 is replaced with an equal amount of HTTPA2, and other conditions are the same as in Example 2-1.

[0210] The products prepared at different reaction times were weighed, sublimated, and then their deuteration rate was determined (using the same method as above). The values ​​of reaction time and deuteration rate of the products are shown in Table 10 below:

[0211] Table 10

[0212] Serial Number Deuterated composition Reaction time (h) Product weight (g) Deuteration rate 1 HTBPA2-D01 4 5.11 39.9％ 2 HTBPA2-D02 10 5.32 68.1％ 3 HTBPA2-D03 30 5.33 95.1％ 4 HTBPA2-D04 60 5.34 98.9％

[0213] In the process of fabricating OLED devices, the deuterated composition provided in this invention needs to be deposited by vapor deposition. Therefore, it is necessary to ensure that the composition of the vapor deposition remains relatively stable. Thus, the following vapor deposition experiment was conducted: 2g each of HTSP2-D05, HTSP4-D21, HTCZ1-D02, and HTSP2-D01 were placed in the crucible of the vapor deposition machine, and then deposited at a temperature of 1×10⁻⁶. -6 Pa~9×10 -5 Under Pa pressure and heated to 300℃, the material in the crucible was sequentially vapor-deposited onto glass substrates numbered 1-9 until approximately 10% of the material remained in the crucible. Based on the order of vapor deposition, a total of 9 glass substrates were obtained. The deuteration rate of the material on these 9 glass substrates was analyzed, as shown in Table 11 below:

[0214] Table 11

[0215]

[0216] As can be seen from the table above, the deuteration rate of the material deposited on the glass substrate at different time periods is basically the same, indicating that the composition of the deuterated composition provided by the present invention can remain relatively stable during the evaporation process.

[0217] The specific structures of the compounds used in the following application examples are shown below:

[0218]

[0219]

[0220] The synthesis methods for D8-HTSP2, D8-HTSP3, D8-HTSP4, D8-HTCZ1, and D18-HTCZ2 are as follows:

[0221] (I) Synthesis of D8-HTSP2:

[0222]

[0223] Under nitrogen protection, 200 mL of dry toluene, 5.0 g (0.0095 mol) of the compound shown in MA, 2.4 g (0.0099 mol) of 2-bromodeuterated biphenyl, 0.0575 g (0.0001 mol) of Pd(dba)2 (bis(dibenzylacetone palladium)), 0.4 g (0.0002 mol) of a toluene solution containing 10% by mass of tri-tert-butylphosphine, and 1.44 g (0.015 mol) of sodium tert-butoxide were added to a 500 mL three-necked flask. The mixture was heated to reflux and reacted for 12 h. After cooling to room temperature, water was added to dissolve the mixture. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and separated by silica gel column chromatography. The solution was eluted with petroleum ether to give 5.1 g of compound D8-HTSP2.

[0224] Mass spectrometry analysis of compound D8-HTSP2 revealed a mass-to-charge ratio (m / z) of 684.35.

[0225] (II) Synthesis of D8-HTSP3:

[0226]

[0227] Following the synthetic method of D8-HTSP2, replace the compound shown in MA with an equal amount of... D8-HTSP3 was obtained.

[0228] Mass spectrometry analysis of compound D8-HTSP3 revealed a mass-to-charge ratio (m / z) of 684.35.

[0229] (III) Synthesis of D8-HTSP4:

[0230] (1) Synthesis of intermediate M-1

[0231]

[0232] Under nitrogen protection, 200 mL of dry toluene, 10 g (0.048 mol) of 2-amino-9,9-dimethylfluorene, 11.6 g (0.048 mol) of 2-bromodeuterated biphenyl, 0.1725 g (0.0003 mol) of Pd(dba)2 (bis(dibenzylacetone palladium), 1.2 g (0.0006 mol) of a toluene solution containing 10% by weight of tri-tert-butylphosphine, and 5.76 g (0.06 mol) of sodium tert-butoxide were added to a 500 mL three-necked flask. The mixture was heated to reflux and reacted for 12 h. After cooling to room temperature, water was added to dissolve the mixture. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and separated by silica gel column chromatography. The eluent was petroleum ether:ethyl acetate = 20:1 (v / v) to give 6.9 g of intermediate M-1.

[0233] Mass spectrometry analysis of intermediate M-1 revealed a mass-to-charge ratio (m / z) of 370.24, confirming the product's molecular formula as C1. 27 H 14 D9N.

[0234] (2) Synthesis of D8-HTSP4:

[0235]

[0236] Following the synthetic method of D8-HTSP2, replace the compound shown in MA with an equal amount of the compound shown in M-1, and replace the 2-bromodeuterated biphenyl with an equal amount of... D8-HTSP4 was obtained.

[0237] Mass spectrometry analysis of compound D8-HTSP4 revealed a mass-to-charge ratio (m / z) of 796.47.

[0238] (IV) Synthesis of D8-HTCZ1:

[0239]

[0240] Following the synthetic method of D8-HTSP2, replace the compound shown in MA with an equimolar amount. Replacing 2-bromodeuterated biphenyl with an equal amount of 4-bromodeuterated biphenyl yields D8-HTCZ1.

[0241] Mass spectrometry analysis of compound D8-HTCZ1 yielded a mass-to-charge ratio (m / z) of 687.36.

[0242] Synthesis of (V)D18-HTCZ2:

[0243]

[0244] Following the synthetic method of D8-HTSP2, replace the compound shown in MA with an equimolar amount. 2-bromodeuterium biphenyl is replaced with 4-bromodeuterium biphenyl, and the amount of 4-bromodeuterium biphenyl is... The amount of sodium tert-butoxide is twice the amount of its original substance. The amount of substance was 2.2 times that of the substance, and the reaction time was 36 hours to obtain D18-HTCZ2.

[0245] Mass spectrometry analysis of compound D18-HTCZ2 revealed a mass-to-charge ratio (m / z) of 654.37.

[0246] Application Example 1

[0247] This application example provides an organic electroluminescent device with the following structure: ITO / HTL:HI-2(5%) (20nm) / HTL(50nm) / HTSP3(20nm) / BH257:BD-2(5%) (20nm) / ETL-1(30nm) / EIL-1(1nm) / Al(150nm);

[0248] The specific preparation process is as follows: each layer of material is placed in a vacuum chamber, and the vacuum is evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa is sequentially vacuum-deposited onto a cleaned ITO substrate. For example, HTL:HI-2(5%) (20nm) refers to the co-evaporation of HTL and HI-2 in a volume ratio of 95:5 to form a hole injection layer in the device, with a hole injection layer thickness of 20nm.

[0249] In this application example, the HTL material is the deuterated mixture HTSP1-D01 provided in Example 1.

[0250] In this device, HTL:HI-2 (5%) (20nm) is the hole injection layer, HTL (50nm) is the hole transport layer, and HTSP3 (20nm) is the electron blocking layer. HTSP1-D01 is used as both the hole injection material and the hole transport material in this device.

[0251] Similarly, BH257:BD-2(5%) (20nm) means that in the device, BH257 and BD-2 are co-evaporated in a volume ratio of 95:5 to form a light-emitting layer with a thickness of 20nm.

[0252] Application Example 2-11

[0253] Application Examples 2-11 provide an organic electroluminescent device, which differs from Application Example 1 only in that the HTL material is different (the specific composition and volume are as described in Table 12 below), while the other preparation steps are the same as in Application Example 1.

[0254] Compare and contrast examples 1-7

[0255] Comparative Application Examples 1-7 provide an organic electroluminescent device, which differs from Application Example 1 only in that the HTL material is different (the specific composition and volume are as described in Table 12 below), while the other preparation steps are the same as in Application Example 1.

[0256] Performance testing

[0257] Test Method: The OLED-1000 multi-channel accelerated aging lifetime and photoluminescence performance analysis system manufactured by Hangzhou Yuanfang was used for testing. The test items included the brightness, driving voltage, current efficiency, and LT80 of the organic electroluminescent device; where LT80 refers to maintaining the device's initial brightness of 1000 cd / m². 2 With the current density remaining constant, the device efficiency drops to the initial luminance of 1000 cd / m². 2 The time required to achieve 80% of the corresponding efficiency.

[0258] The specific test results are shown in Table 12 below:

[0259] Table 12

[0260]

[0261]

[0262] As can be seen from Application Examples 1-4 and Comparative Application Examples 1-3, with the increase of deuteration rate, the voltage first decreases and then increases, the current efficiency gradually increases, and the lifetime first increases and then decreases. However, for roughly the same deuteration rate (e.g., comparing Comparative Application Example 2 with Application Example 1, Comparative Application Example 3 with Application Example 2, and Comparative Application Example 5 with Application Example 6), the organic electroluminescent device prepared using the deuterated mixture provided by the present invention as the hole layer material has better overall performance. The reason is that even with roughly the same deuteration rate, such as D8-HTSP1 and HTSP1-D03, HTSP1-D03 is a mixture of multiple components, while D8-HTSP1 is a single component. HTSP1-D03 has poorer crystallinity, better film-forming properties, and higher hole mobility, thus improving the device performance.

[0263] Meanwhile, data from Application Examples 5-8 and Comparative Application Examples 4-5, as well as data from Application Examples 9-11 and Comparative Application Examples 6-7, show that the organic electroluminescent devices prepared using the deuterated mixture provided by the present invention as the hole layer material have good overall performance.

[0264] Application Example 12

[0265] This application example provides an organic electroluminescent device with the following structure: ITO / HTL:HI-3(5%) (20nm) / HTL(50nm) / HTSP3(20nm) / BH21:BD-2(5%) (20nm) / ETL-1(30nm) / EIL-1(1nm) / Al(150nm);

[0266] The specific preparation process is as follows: each layer of material is placed in a vacuum chamber, and the vacuum is evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa is sequentially vacuum-deposited onto the cleaned ITO substrate. Here, HTL:HI-3 (5%) (20nm) refers to the fact that in the device, HTL and HI-3 are co-evaporated at a volume ratio of 95:5 to form a hole injection layer, with a thickness of 20nm.

[0267] In this application example, the HTL material is the deuterated mixture HTCZ1-D01 provided in Example 5.

[0268] In this device, HTL:HI-2 (5%) (20nm) is the hole injection layer, HTL (50nm) is the hole transport layer, and HTSP3 (20nm) is the electron blocking layer. HTCZ1-D01 is used as both the hole injection material and the hole transport material in this device.

[0269] Similarly, BH21:BD-2(5%) (20nm) means that in the device, BH21 and BD-2 are co-evaporated in a volume ratio of 95:5 to form a light-emitting layer with a thickness of 20nm.

[0270] Application Example 13

[0271] Application Example 13 provides an organic electroluminescent device, which differs from Application Example 1 only in that the HTL material is different (the specific composition and volume are as described in Table 13 below), while the other preparation steps are the same as in Application Example 12.

[0272] Compare and contrast with example 8-11

[0273] Comparative Application Examples 8-11 provide an organic electroluminescent device, which differs from Application Example 1 only in that the HTL material is different (the specific composition and volume are as described in Table 13 below), while the other preparation steps are the same as in Application Example 12.

[0274] Performance testing

[0275] Test Method: The OLED-1000 multi-channel accelerated aging lifetime and photoluminescence performance analysis system manufactured by Hangzhou Yuanfang was used for testing. The test items included the brightness, driving voltage, current efficiency, and LT80 of the organic electroluminescent device; where LT80 refers to maintaining the device's initial brightness of 1000 cd / m². 2 With the current density remaining constant, the device efficiency drops to the initial luminance of 1000 cd / m². 2 The time required to achieve 80% of the corresponding efficiency.

[0276] The specific test results are shown in Table 13 below:

[0277] Table 13

[0278]

[0279] As shown in Table 13, when the deuteration rates of the HTL materials are approximately the same (for example, comparing Application Example 11 and Application Example 13), the organic electroluminescent devices prepared using the deuterated mixture provided by this invention as the hole layer material exhibit better overall performance. This is because even with approximately the same deuteration rate, such as D18-HTCZ2 and HTCZ2-D01, HTCZ2-D01 is a mixture of multiple components, while D18-HTCZ2 is a single component. HTCZ2-D01 has poorer crystallinity, better film-forming properties, and higher hole mobility, thus improving device performance.

[0280] Meanwhile, data from Application Examples 12-13 and Comparative Application Examples 8-11 show that the organic electroluminescent devices prepared using the deuterated mixture provided by the present invention as the hole layer material have better overall performance.

[0281] Application Example 14

[0282] This application example provides an organic electroluminescent device with the following structure: ITO / HIL02 (100nm) / HTSP2 (30nm) / EBL (20nm) / BH21:BD-2 (5%) (20nm) / ETL-1 (30nm) / EIL-1 (1nm) / Al (150nm);

[0283] The specific preparation process is as follows: each layer of material is placed in a vacuum chamber, and the vacuum is evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa is sequentially vacuum-deposited onto the cleaned ITO substrate.

[0284] In this application example, the HTL (hole transport layer) material is compound HTSP2; the EBL material is the deuterated mixture HTTPA1-D01 provided in Example 9.

[0285] BH21:BD-2(5%) (20nm) refers to the process in which BH21 and BD-2 are co-evaporated in a volume ratio of 95:5 to form a light-emitting layer with a thickness of 20nm.

[0286] Application Examples 15-17

[0287] Application Examples 15-17 provide an organic electroluminescent device, which differs from Application Example 14 only in that the EBL material is different (the specific composition and volume are as described in Table 14 below), while the other preparation steps are the same as in Application Example 14.

[0288] Compare and contrast examples 12-13

[0289] Comparative Application Examples 12-13 provide an organic electroluminescent device, which differs from Application Example 14 only in that the EBL material is different (the specific composition and volume are as described in Table 14 below), while the other preparation steps are the same as in Application Example 14.

[0290] Performance testing

[0291] Test Method: The OLED-1000 multi-channel accelerated aging lifetime and photoluminescence performance analysis system manufactured by Hangzhou Yuanfang was used for testing. The test items included the brightness, driving voltage, current efficiency, and LT80 of the organic electroluminescent device; where LT80 refers to maintaining the device's initial brightness of 1000 cd / m². 2 With the current density remaining constant, the device efficiency drops to the initial luminance of 1000 cd / m². 2 The time required to achieve 80% of the corresponding efficiency.

[0292] The specific test results are shown in Table 14 below:

[0293] Table 14

[0294]

[0295] As can be seen from Table 14, the organic electroluminescent devices prepared using the deuterated mixture provided by the present invention as EBL (electron blocking layer) materials have good overall performance.

[0296] In summary, this invention involves a deuteration reaction of compound A to obtain a deuterated mixture, which is then used as the hole layer material. The resulting OLED device exhibits lower driving voltage, higher current efficiency, and longer lifetime. Furthermore, the deuteration reaction process for preparing the deuterated mixture in this invention is simple, the reaction conditions are mild, no complicated purification process is required, and the post-processing is straightforward, making it suitable for preparing organic electroluminescent devices.

[0297] 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 from compound A via a deuteration reaction; The compound A has the structure shown in Formula I: Formula I; Wherein, Ar is selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl; Ar 21 Ar 22 Each is independently selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiopheneyl; Ar 21 Ar 22 The substituents described in Ar are each independently selected from at least one of methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, and 1-methylcyclohexyl; Ar 11 Ar 12 Each is independently selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C12-C20 heteroaryl groups; n is selected from 0; Ar 11 Ar 12 The substituents described herein are each independently selected from at least one of C1-C12 alkyl, C1-C12 alkoxy, and C6-C12 aryl groups; The deuteration reaction includes the following steps: In the presence of a catalyst, compound A is placed in D2O and a solvent to undergo a deuteration reaction, yielding the deuterated mixture. The catalyst is selected from any one of PdCl2, a combination of PdCl2 and NiCl2, a combination of PdCl2 and NiCl2 and triphenylphosphine, or a combination of PdCl2 and NiCl2 and tri-o-tolylphosphine. The solvent is selected from any one or a combination of at least two of benzene, toluene, ethyl acetate, or C6D6; The deuteration reaction was carried out in a hydrogen atmosphere; The pressure of the deuteration reaction is 0.01~2 MPa; The deuteration rate of the deuterated mixture is 28% to 70%.

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

3. The deuterated composition according to claim 1, characterized in that, The molar ratio of PdCl2 to NiCl2 in the combination of PdCl2 and NiCl2 is (1~2):

1.

4. The deuterated composition according to claim 3, characterized in that, The molar ratio of PdCl2 to NiCl2 in the combination of PdCl2 and NiCl2 is 1:

1.

5. The deuterated composition according to claim 1, characterized in that, In the combination of PdCl2, NiCl2 and triphenylphosphine, the ratio of the amount of triphenylphosphine to the sum of the amounts of PdCl2 and NiCl2 is (1~3):

1.

6. The deuterated composition according to claim 5, characterized in that, In the combination of PdCl2, NiCl2 and triphenylphosphine, the ratio of the amount of triphenylphosphine to the sum of the amounts of PdCl2 and NiCl2 is (2~2.5):

1.

7. The deuterated composition according to claim 1, characterized in that, In the combination of PdCl2, NiCl2 and tri-o-tolylphosphine, the ratio of the amount of tri-o-tolylphosphine to the sum of the amounts of PdCl2 and NiCl2 is (1~3):

1.

8. The deuterated composition according to claim 7, characterized in that, In the combination of PdCl2, NiCl2 and tri-o-tolylphosphine, the ratio of the amount of tri-o-tolylphosphine to the sum of the amounts of PdCl2 and NiCl2 is (2~2.2):

1.

9. The deuterated composition according to claim 1, characterized in that, The solvent is selected from C6D6.

10. The deuterated composition according to claim 1, characterized in that, The temperature for the deuteration reaction is 60~200℃.

11. The deuterated composition according to claim 1, characterized in that, The deuterated composition also includes compound B; Compound B is selected from any one of the following HI-1 to HI-9 compounds: 。 12. The deuterated composition according to claim 11, characterized in that, The volume percentage of compound B in the deuterated composition is 3-5%.

13. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode; The material of the organic thin film layer includes the deuterated composition as described in any one of claims 1-12.

14. The organic electroluminescent device according to claim 13, characterized in that, The organic thin film layer includes a hole layer, which comprises a hole injection layer, a hole transport layer, and an electron blocking layer.

15. The organic electroluminescent device according to claim 14, characterized in that, The material of the cavity layer includes the deuterated composition as described in any one of claims 1-12.

16. A display device, characterized in that, The display device includes an organic electroluminescent device as described in any one of claims 13-15.

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