Organic electroluminescent device and deuterated mixture

Abstract

The invention provides an organic light-emitting device and a deuterated mixture, the deuterated mixture comprises a deuterated mixture prepared from a compound A through a deuteration reaction, and the organic light-emitting device comprises an anode, a cathode and an organic layer located between the anode and the cathode; the material of the organic layer comprises a deuterated mixture and a doping material; the deuterated mixture comprises a deuterated mixture prepared from a compound A through a deuterated reaction. The organic light-emitting device provided by the invention has relatively low voltage and relatively long service life.

Description

Technical Field

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

[0002] The phenomenon of organic electroluminescence was discovered as early as 1963, but it did not attract much attention at the time. It was not until 1987 that the Tang research team at Eastman Kodak published a high-brightness, high-efficiency thin-film organic electroluminescent device (OLED) made of organic fluorescent materials and hole materials and driven by low DC voltage that the technology regained attention 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 luminous, etc. It can be compatible with various existing standards and technologies to make low-cost light-emitting devices, showing broad application prospects in realizing color flat-panel displays. In the past few decades, OLED, as a new display technology, has made great progress and has been widely used in the fields of flat-panel displays, flexible displays, solid-state lighting and vehicle displays.

[0004] Therefore, developing organic electroluminescent devices with excellent performance and the materials used therein is the research focus in this field. Summary of the invention

[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide an organic electroluminescent device and a deuterated mixture.

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

[0007] In one aspect, the present invention provides an organic electroluminescent device, comprising an anode, a cathode, and an organic layer between the anode and the cathode;

[0008] The material of the organic layer includes a deuterated mixture and a doping material;

[0009] The deuterated mixture includes a deuterated mixture prepared by a deuterated reaction of compound A;

[0010] The compound A is selected from any one of the following structures;

[0011]

[0012] The doping material has a structure shown in the following formula I or formula II:

[0013]

[0014] Where X is selected from O, S, * indicates the connection site; Y is selected from O and S;

[0015] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 Each is independently selected from a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;

[0016] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 The substituted substituent is selected from at least one of a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;

[0017] All hydrogen atoms in the compounds of formula I and formula II can be independently replaced by one of deuterium atoms, F, CN, C1-C12 alkyl groups, C6-C30 aryl groups, or C3-C30 heteroaryl groups.

[0018] Preferably, the deuterium substitution rate of the deuterated mixture is 10% to 99%, for example, it can be 12.5%, 13.6%, 16.7%, 18.2%, 20.8%, 22.7%, 25%, 27.3%, 29.2%, 31.8%, 33.3%, 36.4%, 37.5%, 40.9% or 41.7%, 45.5, 45.8%, 50%, 54.2, 54.5%, 58.3, 59.1%, 62.5%, 63.6%, 66.7%, 68.2%, 70.8%, 72.7%, 77.3%, 75%, 79.2%, 81.8%, 83.3%, 86.4%, 87.5%, 90.9%, 91.7%, 95.5%, 95.8%, etc. More preferably, the deuterium substitution rate of the deuterated mixture is 22% to 88%. More preferably, the deuterium substitution rate of the deuterated mixture is 40 to 88%.

[0019] Preferably, the doping material is selected from any one of the following compounds:

[0020]

[0021]

[0022] More preferably, the doping material is selected from compound 47 and compound 48:

[0023]

[0024] More preferably, the doping material is selected from compound 47:

[0025]

[0026] Preferably, the organic layer of the organic electroluminescent device includes a light-emitting layer; the material of the light-emitting layer includes a main material and a doping material, the main material includes a deuterated mixture prepared by a deuteration reaction of compound A, and the doping material has a structure shown in Formula I or Formula II.

[0027] Preferably, the organic layer further comprises at least one of a hole injection layer, a hole transport layer, and an electron blocking layer), at least one of a hole blocking layer, an electron transport layer, and an electron injection layer.

[0028] In a second aspect, the present invention provides a deuterated mixture, wherein the deuterated mixture comprises a deuterated mixture prepared by a deuterated reaction of compound A;

[0029] The compound A is selected from any one of the following structures;

[0030]

[0031] In the present invention, by subjecting an anthracene compound (compound A) with a specific structure to a deuteration reaction, tedious purification work is avoided, the preparation method is simple, the reaction conditions are mild, and the post-treatment is simple. Moreover, a deuterated mixture can be obtained by subjecting an anthracene compound (compound A) with a specific structure to a deuteration reaction. When the prepared deuterated mixture is used as the main material of the light-emitting layer, the prepared OLED light-emitting device has good comprehensive performance, low driving voltage, and long service life.

[0032] It should be noted that in the organic reaction process, when there is no significant difference in the reactive sites on the reaction molecules, it is difficult to carry out substitution reactions at the characteristic reaction sites. Therefore, in the present invention, after deuteration reaction of compound A, a mixture (deuterated mixture) is obtained. Even if only one H atom on the reactant molecule is replaced by a deuterium atom, because there is no significant difference in the activity of each H atom on the reactant, the mixture obtained at this time, if subjected to mass spectrometry, has an increase of 1 in the molecular distance from the main peak compared with the reactant. However, the mixture obtained at this time is a mixture of various isomers obtained by substitution of single deuterium atoms.

[0033] The following examples are given below. Although the following structures are not mixtures of the present invention, they can illustrate the problem:

[0034]

[0035] For BH1, it contains 24 hydrogen atoms, one of which is replaced by a deuterium atom, resulting in isomers including but not limited to the following:

[0036]

[0037] When the above compounds are present in a deuterated composition, the mass spectrum peak molecular ion peak m / z is the same.

[0038] For BH1, it contains 24 hydrogen atoms, 23 of which are replaced by deuterium atoms, resulting in isomers including but not limited to the following:

[0039]

[0040] When the above compounds exist in a deuterated mixture, the mass spectrum peak molecular ion peak m / z is the same.

[0041] Similarly, for BH1, which contains 24 hydrogen atoms, 2-22 of which are replaced by deuterium atoms, the resulting isomers are numerous and complex, and those skilled in the art can draw the specific structure based on common knowledge.

[0042] As long as the deuteration reaction proceeds and as long as the deuteration rate is not 0 or 100%, the obtained deuterated composition will inevitably contain a variety of components.

[0043] As long as the deuteration reaction proceeds, the deuterated combination may contain any one of the products in which 1 H atom is replaced by deuterium, the products in which 2 H atoms are replaced by deuterium, the products in which 3 H atoms are replaced by deuterium, the products in which 4 H atoms are replaced by deuterium, the products in which 5 H atoms are replaced by deuterium, the products in which 6 H atoms are replaced by deuterium, the products in which 7 H atoms are replaced by deuterium, the products in which 8 H atoms are replaced by deuterium, the products in which 9 H atoms are replaced by deuterium, ..., the products in which 24 H atoms are replaced by deuterium, or a combination of at least two of them.

[0044] Moreover, in the deuteration reaction conditions of the present invention, assuming that the deuteration rate of BH1 is 12.5%, theoretically, 3 H atoms are replaced by deuterium atoms. According to the reaction principle and common knowledge, not all BH1 molecules have 3 H atoms replaced by deuterium atoms. There must be products in which 2 H, 1 H, 4 H, and 5 H are replaced by deuterium atoms. In this case, if the mass spectrum m / z of BH1 is represented by M, the deuterated composition with a deuteration rate of 12.5% ​​has at least 5 mass spectrum peaks m / z on the far right of the mass spectrum, namely M+1, M+2, M+3, M+4, and M+5, and there are two peaks of M+6 and M+7, which are isotope peaks. Of course, it can be judged based on common knowledge in the art whether the two peaks of M+6 and M+7 are the contributions of the separate isotopes of M+4 and M+5, or the products of 6 H being replaced by deuterium atoms or 7 H being replaced by deuterium atoms in the deuterated composition.

[0045] As a preferred technical solution of the present invention, the compound A is selected from any one of the following compounds:

[0046]

[0047] As a preferred technical solution of the present invention, the deuteration reaction comprises the following steps:

[0048] In the presence of a catalyst, compound A is placed in D2O and a solvent to carry out a deuteration reaction to obtain the deuterated mixture.

[0049] Preferably, the solvent is selected from any one of benzene, toluene, ethyl acetate or C6D6 or a combination of at least two thereof, and more preferably C6D6.

[0050] It should be noted that C6D6 is the product in which all hydrogen atoms on benzene are replaced by deuterium atoms.

[0051] Preferably, the solvent is C6D6, and the volume ratio of D2O to C6D6 is 1:(4-6), for example, it can be 1:4, 1:4.2, 1:4.4, 1:4.6, 1:4.8, 1:5, 1:5.2, 1:5.4, 1:5.6, 1:5.8 or 1:6, etc.

[0052] Preferably, the reaction is carried out in the presence of a catalyst, and the catalyst is selected from any one or a combination of at least two of an inorganic salt of a metal, an organic salt of a metal, or a metal complex, wherein the metal in the inorganic salt of a metal, the organic salt of a metal, or the metal complex is independently selected from palladium, platinum, rhodium, ruthenium, iridium, iron, copper, cobalt or nickel; the catalyst is further preferably PdCl2.

[0053] Preferably, the reaction is carried out in a hydrogen atmosphere.

[0054] Preferably, the temperature of the deuteration reaction is 60-200°C, for example, it can be 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C, etc.

[0055] Preferably, the deuteration reaction time is 1 to 80 h, for example, it can be 1 h, 2 h, 4 h, 6 h, 10 h, 12 h, 16, 24 h, 30 h, 36, 40 h, 50 h, 60 h, 70 h or 80 h.

[0056] Preferably, the pressure of the deuteration reaction is 0.01-2 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.

[0057] Preferably, the deuterium substitution rate of the deuterated mixture is 10% to 99%, for example, it can be 12.5%, 13.6%, 16.7%, 18.2%, 20.8%, 22.7%, 25%, 27.3%, 29.2%, 31.8%, 33.3%, 36.4%, 37.5%, 40.9% or 41.7%, 45.5, 45.8%, 50%, 54.2, 54.5%, 58.3, 59.1%, 62.5%, 63.6%, 66.7%, 68.2%, 70.8%, 72.7%, 77.3%, 75%, 79.2%, 81.8%, 83.3%, 86.4%, 87.5%, 90.9%, 91.7%, 95.5%, 95.8%, etc. Preferably, the deuteration rate of the deuterated mixture is 22% to 88%; more preferably, the deuteration rate of the deuterated mixture is 40 to 88%.

[0058] In the present invention, the deuterium substitution rate refers to the percentage of the number of deuterium atoms (D) in the composition or compound to the total number of deuterium atoms and hydrogen atoms (H), that is, deuterium substitution rate = y / (x+y)*100%, wherein y is the number of deuterium atoms in the composition or compound, and x is the number of hydrogen atoms in the composition or compound. Assuming that the composition or compound is all H and there is no D, its deuterium substitution rate is 0%. If all H in the composition or compound is replaced by D, its deuterium substitution rate is 100%.

[0059] It should be noted that the deuteration reaction of the present invention is also carried out in the presence of activated carbon. At the same time, after the deuteration reaction of the present invention is completed, a post-treatment step is also included. The post-treatment method includes cooling, filtering, liquid separation, and drying.

[0060] In a third aspect, the present invention provides a display device, comprising the organic electroluminescent device as described in the first aspect and / or the deuterated mixture as described in the second aspect.

[0061] Compared with the prior art, the present invention has the following beneficial effects:

[0062] The organic electroluminescent device of the present invention uses a combination of a specific deuterated mixture and a compound represented by formula I or formula II to prepare the organic electroluminescent device, and the obtained device has a lower voltage and a longer life. DETAILED DESCRIPTION

[0063] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0064] Example 1

[0065] This embodiment provides a series of deuterated mixtures of A-11D, which are prepared by deuterated reaction of compound A-11. The preparation method is as follows:

[0066]

[0067] The product on the right represents a deuterated mixture obtained by replacing H atoms at unspecified positions of the raw material A-11 with deuterium atoms.

[0068] The specific preparation method of the above-mentioned A-11D series deuterated mixture is as follows:

[0069] At room temperature, compound A-11 (0.01 mol), palladium chloride (0.0001 mol), 0.2 g activated carbon, 10 ml D2O and 50 ml C6D6 were added to a 500 mL autoclave, and hydrogen was introduced to the autoclave until the pressure reached 0.02 MPa. The autoclave was heated to 90 °C for a certain period of time, cooled to room temperature, filtered and separated. The organic layer after separation was dried with magnesium sulfate, decolorized with a short silica gel column, concentrated to dryness, and vacuum dried for 24 h to obtain A-11D.

[0070] After the products prepared at different reaction times were sublimated, the deuteration rate was detected (the deuteration rate was tested by the internal standard method, for example, the test can be carried out according to the method described in the document "Wu Yurong, Chen Minzhu, Determination of the content of deuterated bromobenzene by 1HNMR method [J], Journal of Sichuan University: Natural Science Edition, 1997, 34 (6): 2"). The values ​​of the reaction time and the deuteration rate of the product are shown in Table 1 below:

[0071] Table 1

[0072]

[0073]

[0074] Example 2

[0075] This embodiment provides a series of deuterated mixtures of A-28D, which are prepared by deuterated reaction of compound A-28. The preparation method is as follows:

[0076]

[0077] The product on the right represents a deuterated mixture obtained by replacing H atoms at unspecified positions of the raw material A-8 with deuterium atoms.

[0078] The preparation method is similar to that of Example 1.

[0079] After the products prepared at different reaction times were sublimated, the deuteration rate was detected (the test method was the same as above). The values ​​of the reaction time and the deuteration rate of the product are shown in Table 2 below:

[0080] Table 2

[0081] Serial number Deuterated mixture Reaction time / (h) Deuterium substitution rate 1 A-28D01 8 25.00％ 2 A-28D02 16 41.67％ 3 A-28D03 24 50.00％ 4 A-28D04 36 62.47％ 5 A-28D05 60 79.17％ 6 A-28D06 80 95.83％

[0082] In the process of preparing OLED devices, the deuterated composition provided by the present invention needs to be evaporated by evaporation, so it is necessary to ensure that the components of the evaporation remain relatively stable. Therefore, the following evaporation experiment was conducted: 1.8 g of A-28D02 was placed in the crucible of the evaporation machine and heated to 1×10 -5 Pa~9×10 -5Pa pressure, heated to 300 ° C, the material in the crucible was sequentially evaporated onto the glass substrates numbered 1-5 until about 10% of the material in the crucible remained. According to the order of evaporation, a total of 5 glass substrates were obtained.

[0083] In addition, referring to the above method, A-28D03 and A-28D05 were measured, and a total of 10 glass substrates were obtained.

[0084] The deuterium substitution rates of the materials on these 15 glass substrates were analyzed separately, as shown in Table 3 below:

[0085] Table 3

[0086] Glass substrate serial number 1 2 3 4 5 A-28D02 deuterium substitution rate / (%) 41.67 41.65 41.62 41.71 41.69 A-28D03 deuterium substitution rate / (%) 50.06 50.07 50.03 49.97 49.99 A-28D05 deuterium substitution rate / (%) 79.13 79.09 79.14 79.11 79.13

[0087] It can be seen from the contents of Table 3 that the deuterated rates of the materials deposited on the glass substrate at different time periods are substantially the same, indicating that the components of the deuterated composition provided by the present invention can remain relatively stable during the deposition process.

[0088] Example 3

[0089] This embodiment provides a BH3D series deuterated mixture:

[0090]

[0091] The product on the right represents a deuterated mixture obtained by replacing H atoms at unspecified positions of the raw material BH3 with deuterium atoms.

[0092] The preparation method is similar to that of Example 1.

[0093] After the products prepared at different reaction times were sublimated, the deuteration rate was detected (the test method is the same as above). The values ​​of the reaction time and the deuteration rate of the product are shown in Table 4:

[0094] Table 4

[0095] Serial number Deuterated mixture Reaction time / (h) Deuterium substitution rate 1 BH3D01 8 22.97％ 2 BH3D02 16 41.03％ 3 BH3D03 24 54.71％ 4 BH3D04 36 64.03％ 5 BH3D05 60 77.32％ 6 BH3D06 80 95.49％

[0096] Example 4

[0097] This embodiment provides a BH4D series deuterated mixture:

[0098]

[0099] The product on the right represents a deuterated mixture obtained by replacing H atoms at unspecified positions of the raw material BH4 with deuterium atoms.

[0100] The preparation method is similar to that of Example 1.

[0101] After the products prepared at different reaction times were sublimated, the deuteration rate was detected (the test method was the same as above). The values ​​of the reaction time and the deuteration rate of the product are shown in Table 5:

[0102] Table 5

[0103] Serial number Deuterated mixture Reaction time / (h) Deuterium substitution rate 1 BH4D01 8 27.27％ 2 BH4D02 16 45.45％ 3 BH4D03 24 54.69％ 4 BH4D04 36 68.18％ 5 BH4D05 60 72.73％ 6 BH4D06 80 90.91％

[0104] Example 5

[0105] This embodiment provides a BH5D series deuterated mixture:

[0106]

[0107] The product on the right represents a deuterated mixture obtained by replacing H atoms at unspecified positions of the raw material BH5 with deuterium atoms.

[0108] The preparation method is similar to that of Example 1.

[0109] After the products prepared at different reaction times were sublimated, the deuteration rate was detected (the test method is the same as above). The values ​​of the reaction time and the deuteration rate of the product are shown in Table 6:

[0110] Table 6

[0111]

[0112]

[0113] Referring to the preparation method of Example 1, the compounds involved in the present invention were deuterated, and the deuteration rate was tested. The specific results are shown in Table 7:

[0114] Table 7

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] Example 6

[0122] This example provides compound 1 and a synthesis method thereof, and the synthesis method is as follows:

[0123]

[0124] (1) Synthesis of intermediate 1-1

[0125] Under nitrogen protection, 200 mL of dry toluene, 0.1 mol of 3-bromobenzofuran, 0.1 mol of 2-fluoro-9H-carbazole, 0.001 mol of Pd(dba)2 (bis(dibenzylideneacetonepalladium), 4 g of a 10% tri-tert-butylphosphine toluene solution (the amount of tri-tert-butylphosphine is 0.002 mol) and 0.3 mol of sodium tert-butoxide were added to a 500 mL three-necked flask, and the mixture was heated to reflux for 12 h, then cooled to room temperature, and water was added to separate the organic layer. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove the magnesium sulfate, concentrated to dryness, and crystallized with ethanol to obtain intermediate 1-1.

[0126] The intermediate 1-1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 301.1.

[0127] (2) Synthesis of intermediate 1-2

[0128] Under nitrogen protection, add 300 mL of dry DMF, 0.1 mol of intermediate 1-1, 0.3 mol of thiophenol, and 0.5 mol of potassium carbonate to a 500 mL three-necked flask, heat to 110 °C for 10 h, cool to room temperature, add water to separate, then wash the organic layer with water until neutral, dry with magnesium sulfate, filter to remove magnesium sulfate, concentrate to dryness, and crystallize with ethanol to obtain intermediate 1-2;

[0129] The intermediate 1-2 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 391.1.

[0130] (3) Synthesis of Compound 1

[0131] Under nitrogen protection and oil bath heating, 200 mL of dry o-dichlorobenzene, 0.01 mol of intermediate 1-2, and 0.00 6 mol of anhydrous nickel chloride were added to a 500 mL three-necked flask, stirred evenly, the temperature was maintained at 20°C-25°C, 20 mL of 1.0 M BBr3 dichloromethane solution (containing 0.02 mol of BBr3) was slowly added dropwise, and the temperature was slowly raised to 40°C for the oil bath to react for 2 h, and then slowly raised to 100°C for the oil bath. During the process, dichloromethane in the reaction system was distilled out, and then the oil bath was maintained at 100°C for reaction for 4 h, and then raised to 140°C for reaction for 12 h, and then cooled to room temperature, and 0.05 mol of N-ethyldiisopropylamine was slowly added to terminate the reaction; water was then added to separate, the organic layer was washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, separated by silica gel column chromatography, and eluted with petroleum ether: ethyl acetate = 20: 1 (volume ratio) to obtain compound 1.

[0132] The obtained compound 1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 399.1.

[0133] Example 7

[0134] This example provides compound 3 and its synthesis method, the synthesis method is as follows:

[0135]

[0136] Referring to the synthesis method of compound 1 provided in Synthesis Example 1, 3-bromobenzofuran was replaced with an equal amount of 3-bromobenzothiophene, and other conditions remained unchanged to obtain compound 3.

[0137] The obtained compound 3 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 415.1.

[0138] Example 8

[0139] This example provides compound 43 and its synthesis method, the synthesis method is as follows:

[0140]

[0141] (1) Synthesis of Intermediate 43-1

[0142] Under nitrogen protection, add 200 mL of dry xylene, 0.15 mol of 4-tert-butylphenol, 0.1 mol of di-tert-butyl bromide-1-carbazole, 0.001 mol of Pd(dba)2 (bis(dibenzylideneacetonepalladium)), and 0.3 mol of sodium tert-butoxide to a 500 mL three-necked flask, heat to reflux for 12 h, cool to room temperature, add water to separate, then wash the organic layer with water until neutral, dry with magnesium sulfate, filter to remove magnesium sulfate, concentrate to dryness, and crystallize with ethanol to obtain intermediate 43-1;

[0143] The intermediate 43-1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 427.3.

[0144] (2) Synthesis of Intermediate 43-2

[0145] Under nitrogen protection, 200 mL of dry toluene, 0.1 mol of intermediate 43-1, 0.15 mol of tert-butyl brominated benzothiophene, 0.001 mol of Pd(dba)2 (bis(dibenzylideneacetonepalladium), 4 g of 10% tri-tert-butylphosphine toluene solution (the amount of tri-tert-butylphosphine is 0.002 mol) and 0.3 mol of sodium tert-butoxide were added to a 500 mL three-necked flask, and the mixture was heated to reflux for 12 h, cooled to room temperature, and separated by adding water. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and crystallized with ethanol to obtain intermediate 43-2.

[0146] The intermediate 43-2 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 615.4.

[0147] (3) Synthesis of Compound 43

[0148] Referring to the synthesis method of Synthesis Example 1, intermediate 43-2 was used to replace intermediate 1-2, and other conditions remained unchanged to obtain compound 43.

[0149] Compound 43 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 623.3.

[0150] Example 9

[0151] This example provides compound 47 and its synthesis method, the synthesis method is as follows:

[0152]

[0153] Referring to the synthesis method of compound 1 in Synthesis Example 3, 4-tert-butylthiophenol was used instead of 4-tert-butylphenol, and other conditions remained unchanged, to obtain compound 47.

[0154] Compound 47 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 639.3.

[0155] Compounds 7, 13, 17, 40, 45, 48 and 55 were prepared by a similar preparation method and subjected to mass spectrometry detection. The test results are shown in Table 8 below.

[0156] Table 8

[0157]

[0158]

[0159] Other compounds for which specific synthesis steps are not listed can be prepared by common knowledge in the art in combination with conventional means in the art and the above synthesis examples.

[0160] The specific structures of other compounds used in the following application examples are shown below:

[0161]

[0162]

[0163] Application Example 1

[0164] This application example provides an organic electroluminescent device, and the structure of the organic electroluminescent device is: ITO / HT (40nm) light-emitting layer (30nm): 47 (3%) / TPBI (30nm) / LiF (0.5nm) / Al (150nm).

[0165] The preparation method of the organic electroluminescent device is as follows:

[0166] (1) a glass substrate coated with an ITO transparent conductive layer (as an anode) is ultrasonically treated in a cleaning agent, rinsed in deionized water, and then ultrasonically degreased in a mixed solvent of acetone and ethanol. After drying, the substrate is cleaned with ultraviolet light and ozone, and the surface is bombarded with a low-energy cation beam to improve the energy level properties of the ITO surface and enhance the binding ability with the hole injection layer;

[0167] (2) Place the glass substrate in a vacuum chamber and evacuate the chamber to a vacuum of 1×10 -5 ~1×10 -4 Pa, HT was vacuum evaporated on the anode as a hole transport layer, the evaporation rate was 0.01nm / s, and the evaporation film thickness was 40nm;

[0168] (3) vacuum evaporating a light-emitting layer on the hole transport layer, with a evaporation rate of 0.01 nm / s and a total evaporation film thickness of 30 nm. The main material of the light-emitting layer is A-11D01, the doping material is compound 47, and the volume ratio of the main material of the light-emitting layer to the doping material is 97:3;

[0169] (4) Vacuum evaporating TPBI on the organic light-emitting layer as an electron transport layer of the organic electroluminescent device; the evaporation rate is 0.01 nm / s, and the total evaporation film thickness is 30 nm;

[0170] (5) Vacuum evaporation was performed on the electron transport layer to form an electron injection layer and a cathode to obtain the organic electroluminescent device.

[0171] Application Example 2-7

[0172] Application Examples 2-7 respectively provide an organic electroluminescent device, which differs from Application Example 1 only in that the luminescent main material A-11D01 in Application Example 1 is replaced, and the doping material is replaced as needed (see Table 9 for details). Other structures, materials and preparation methods are the same as those in Application Example 1.

[0173] Comparative Application Examples 1-6

[0174] Comparative Application Examples 1-6 respectively provide an organic electroluminescent device, which differs from Application Example 1 only in that the luminescent main material A-11D01 in Application Example 1 is replaced, and the doping material is replaced as needed (see Table 9 for details). Other structures, materials and preparation methods are the same as those in Application Example 1.

[0175] Performance Test:

[0176] The driving voltage, current efficiency and life LT90 of the organic electroluminescent device provided above were tested; wherein LT90 refers to the time required for the brightness to drop to 90% of the original brightness while maintaining the current density unchanged when the initial brightness is 1000 nit. The specific test results are shown in Table 9, wherein the voltage and LT90 are relative values ​​(the comparison standard is the comparison application example 1).

[0177] Table 9

[0178]

[0179] It can be seen from Application Examples 1-6 that as the deuterium substitution rate increases, the voltage first decreases, and the voltage is relatively low when the deuterium substitution rate is between 40% and 88%; if the deuterium substitution rate increases further, the voltage increases instead.

[0180] It can be seen from Application Examples 1-6 that as the deuterium substitution rate increases, the lifespan increases, and the lifespan is higher when the deuterium substitution rate is between 40% and 88%. If the deuterium substitution rate increases further, the lifespan advantage does not change.

[0181] It should be noted that the deuteration rate of the deuterated mixture used in Application Example 5 is 86.36%. According to the conditions of the deuteration reaction in the embodiments of the present invention, combined with common knowledge, and comparing the data of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 of the present invention, it can be seen that, in general, with similar structures and the same reaction conditions, the deuteration rate of the obtained product will have some errors. Therefore, it is more reasonable to limit the above preferred deuteration rate to 40%-88%, rather than limiting it to 40%-86.36%.

[0182] By comparing Application Example 1 and Application Example 3, it can be seen that when the deuterium substitution rates are substantially the same, the device using the deuterium substituted mixture of the present invention has a lower voltage and a better lifespan.

[0183] Comparison between Application Example 5 and Application Example 7 shows that when the doping material is compound 48, the device performance is further optimized.

[0184] From the comparison between Application Example 5, Application Example 7, Comparative Application Example 2 and Comparative Application Example 3, it can be seen that when compound 47 or 48 is used as the doping material, the performance of the prepared structural device is better.

[0185] From the comparison between Application Examples 1-6 and Comparative Application Examples 4-6, it can be seen that when compound 47 is used as the doping material, the startup voltages of the device structures A-11D01 to A-11D06 are better than those of BH3D03, BH4D03, and BH5D03, and when the deuterium substitution rate of the deuterated mixture of A-11 is greater than 40%, the lifespan of the devices prepared with the deuterated mixture of A-11 as the main material is better than that of the devices prepared with BH3D03, BH4D03, and BH5D03 as the main material.

[0186] Application examples 8-10, compared with application example 7

[0187] Application Examples 8-11 and Comparative Application Example 7 respectively provide an organic electroluminescent device, which differs from Application Example 1 only in that the luminescent main material A-11D01 in Application Example 1 is replaced, and the doping material is replaced as needed (see Table 10 for details). Other structures, materials and preparation methods are the same as those in Application Example 1.

[0188] Performance Test:

[0189] The driving voltage, current efficiency and life LT90 of the organic electroluminescent device provided above were tested; wherein LT90 refers to the time required for the brightness to drop to 90% of the original brightness while maintaining the current density unchanged when the initial brightness is 1000 nit. The specific test results are shown in Table 10, wherein the voltage and LT90 are relative values ​​(the comparison standard is Comparative Application Example 7).

[0190] Table 10

[0191]

[0192] By comparing Application Examples 8-11 and Comparative Application Example 7, it can be seen that the voltage and life of the device structure prepared with the compounds involved in the application examples as the main material are better than the device structure prepared with P-2 as the main material. And by comparing Comparative Application Examples 9-11 and Application Example 8, the performance of the device structure prepared with the compounds A-28D03, A-28D04, and A-28D05 provided by the present invention as the main material is better than the device structure prepared with the compound A-32D provided by the present invention as the main material.

[0193] Application examples 12-16, comparative application examples 8-9

[0194] Application Examples 12-16 and Comparative Application Examples 8-9 respectively provide an organic electroluminescent device, which differs from Application Example 1 only in that the luminescent main material in Application Example 1 is replaced with A-11D01, and the doping material is replaced as needed (see Table 11 for details). Other structures, materials and preparation methods are the same as those in Application Example 1.

[0195] Performance Test:

[0196] The driving voltage, current efficiency and life LT90 of the organic electroluminescent device provided above were tested; wherein LT90 refers to the time required for the brightness to drop to 90% of the original brightness while maintaining the current density unchanged when the initial brightness is 1000 nit. The specific test results are shown in Table 11, wherein the voltage and LT90 are relative values ​​(the comparison standard is Comparative Application Example 9).

[0197] Table 11

[0198]

[0199] From the comparison between Application Examples 12-16 and Comparative Application Examples 8-9, it can be seen that the voltage and life of the device structure prepared with the compounds involved in the application examples as the main material are better than the device structure prepared with A-12D or A-14D as the main material.

[0200] The applicant declares that the present invention illustrates the organic electroluminescent device and the deuterated mixture of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic layer between the anode and the cathode; The material of the organic layer includes a deuterated mixture and a doping material; The deuterated mixture includes a deuterated mixture prepared by a deuterated reaction of compound A; The compound A is selected from any one of the following structures; The doping material has a structure shown in the following formula I or formula II: Where X is selected from O, S, * indicates the connection site; Y is selected from O and S; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 Each is independently selected from a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 The substituted substituent is selected from at least one of a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group; All hydrogen atoms in the compounds of formula I and formula II can be independently replaced by one of deuterium atoms, F, CN, C1-C12 alkyl groups, C6-C30 aryl groups, or C3-C30 heteroaryl groups.

2. The organic electroluminescent device according to claim 1, characterized in that: The deuterium substitution rate of the deuterated mixture is 10% to 99%; Preferably, the deuteration rate of the deuterated mixture is 22% to 88%; More preferably, the deuteration rate of the deuterated mixture is 40-88%.

3. The organic electroluminescent device according to claim 1 or 2, characterized in that: The doping material is selected from any one of the following compounds:

4. The organic electroluminescent device according to any one of claims 1 to 3, characterized in that: The doping material is selected from compound 47 and compound 48:

5. The organic electroluminescent device according to any one of claims 1 to 4, characterized in that: The doping material is selected from compound 47:

6. The organic electroluminescent device according to any one of claims 1 to 5, characterized in that: The organic layer of the organic electroluminescent device includes a light-emitting layer; The material of the light-emitting layer includes a main material, and the main material includes a deuterated mixture prepared by a deuterated reaction of compound A.

7. A deuterated mixture, characterized in that: The deuterated mixture includes a deuterated mixture prepared by a deuterated reaction of compound A; The compound A has one of the following structures; 8. The deuterated mixture according to claim 7, characterized in that The deuterium substitution rate of the deuterated mixture is 10% to 99%; Preferably, the deuteration rate of the deuterated mixture is 22% to 88%; More preferably, the deuteration rate of the deuterated mixture is 40-88%.

9. A display device, characterized in that: The display device comprises the organic electroluminescent device according to any one of claims 1 to 6.

10. A display device, characterized in that: The display device comprises the deuterated mixture according to claim 7 or 8.

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