Organic electroluminescent devices, organic electroluminescent apparatus and photoelectric equipment

Abstract

The present invention relates to an organic electroluminescent device, an organic electroluminescent apparatus and an optoelectronic device, and belongs to the technical field of organic electroluminescent device, the organic electroluminescent device comprises a first electrode, a second electrode opposite to the first electrode, a light-emitting layer between the first electrode and the second electrode, and a hole transport region between the first electrode and the light-emitting layer, the hole transport region comprises a hole injection layer, a first hole transport layer and a second hole transport layer. The present invention provides an organic electroluminescent device manufactured by a specific combination of a specific arylamine derivative in the hole transport region and a dual host red light material in the light-emitting layer, the manufactured organic electroluminescent device has a high turn-on voltage and a relatively low driving voltage at the same time, and retains the advantages of the high efficiency and long service life of the dual host red light device, and improves the turn-on voltage of the red light device, thereby mitigating the reddish phenomenon caused by crosstalk.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to the technical field of organic electroluminescence devices, in particular to organic electroluminescent devices, organic electroluminescence apparatus and photoelectric equipment.

[0002] [Background technology] Organic electroluminescent display (OLED) is an active light-emitting display device. At present, small and medium-sized OLED display screens have been applied in large scale in high-end smartphones manufactured by companies such as Huawei, Xiaomi, and Samsung, and obtaining optimal luminous efficiency of the device under the condition of low operating voltage is a general need in the OLED field. Reducing the driving voltage is an important means of reducing power consumption and improving the luminous efficiency and stability of the device. At present, relatively many methods are used to realize low-voltage driving of the device and further improve the luminous efficiency, one of which is to adopt exciplex-forming cohost, i.e., double host material. It is usually composed of a hole-transporting host material (P-type) and an electron-transporting host material (N-type). Companies such as Rohm and Haas have launched a series of products that have already been applied in production lines to achieve the effects of low driving voltage, high efficiency, and long service life.

[0003] The turn-on voltage is the voltage at which the device emits light with a luminance of 1 cd / m 2It is defined as the voltage that needs to be applied when the pixel voltage reaches 1 V. In existing OLED display devices, the turn-on voltages of the RGB three-color subpixels are not consistent. Specifically, the turn-on voltage of the blue subpixel>the turn-on voltage of the green subpixel>the turn-on voltage of the red subpixel. In practical applications, the blue subpixel has a relatively large efficiency difference under different driving voltage conditions. Under low driving voltage, the luminous efficiency of the blue subpixel is relatively low. However, the driving voltage of the red subpixel and the green subpixel are relatively low, and they can emit light normally under low driving voltage. Therefore, in the case of low gray scale, the luminous efficiency of the red subpixel is higher than that of the green subpixel and the blue subpixel, which causes a reddish phenomenon on the screen body and a crosstalk phenomenon.

[0004] The turn-on voltage of the red light device is improved to alleviate the reddish phenomenon caused by crosstalk, and although the turn-on voltage of the single-host red light device is higher than that of the dual-host red light device, it has the problems of low luminous efficiency and short service life, while the improvement of the turn-on voltage of the dual-host red light device is usually accompanied by an increase in the driving voltage.

[0005] Summary of the Invention SUMMARY OF THE DISCLOSURE The present invention aims to provide an organic electroluminescent device, an organic electroluminescent apparatus and a photoelectric device to solve the problems posed by the background art.

[0006] In order to achieve the above object, the present invention provides the following technical solutions.

[0007] An organic electroluminescent device comprising a first electrode, a second electrode opposite the first electrode, an emissive layer between the first electrode and the second electrode, and a hole transport section between the first electrode and the emissive layer, the hole transport section comprising a hole injection layer, a first hole transport layer, and a second hole transport layer.

[0008] The general structural formula of the second hole transport layer is as shown in Formula I:

[0009] [ka]

[0010] Among them, Ar'1 and Ar'2 each independently represent a substituted or unsubstituted C6 to C24 aryl group or a substituted or unsubstituted 3- to 24-membered heteroaryl group; R'1 to R'3 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C18 aryl group, a substituted or unsubstituted 3 to 18 membered heteroaryl group, a substituted or unsubstituted C3 to C12 cycloalkyl group, or a substituted or unsubstituted C1 to C6 alkoxy group; R'4 is hydrogen, a methyl group, an ethyl group, a phenyl group, or a biphenyl group; R'1 to R'4 are linked to the benzene ring in such a manner as to form a substituted or fused ring; the light-emitting layer comprises a P-type host material and an N-type host material, The general structural formula of the P-type host material is as shown in Formula II:

[0011] [ka]

[0012] Among them, Y1 and Y2 are selected from the following combinations: Y1 is N and Y2 is O; Y1 is N and Y2 is S; Y1 is O and Y2 is N; Y1 is S and Y2 is N; L1 is a bond, a substituted or unsubstituted C6 to C18 arylene group, or a substituted or unsubstituted 3- to 18-membered heteroarylene group; Ar1 to Ar3 are each independently a substituted or unsubstituted C6 to C24 aryl group or a substituted or unsubstituted 3- to 24-membered heteroaryl group; Ar1 to Ar3 are linked to the benzene ring in a manner to form a substituted or fused ring; The general structural formula of the N-type host material is as shown in Formula III:

[0013] [ka]

[0014] Among them, X1 is selected from O or S; One of m, n, and p is 1 and the rest are 0, Z1 to Z3 are each independently N or C, and at least one is N; Ar4 to Ar5 are each independently a substituted or unsubstituted C6 to C24 aryl group or a substituted or unsubstituted 3- to 24-membered heteroaryl group; L2 is a bond, a substituted or unsubstituted C6 to C18 arylene group, or a substituted or unsubstituted 3 to 18 membered heteroarylene group.

[0015] As a further technical solution of the present invention, the second hole transport layer is selected from one of the following formulas I-1 to I-3:

[0016] [ka]

[0017] Among them, R'1 and R'2 each independently represent hydrogen, deuterium, a methyl group, an ethyl group, an isopropyl group, a propyl group, a tert-butyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridinyl group, a methoxy group, a phenanthryl group, a dibenzofuran group, or a dimethylfluorenyl group; R'3 is deuterium, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridinyl group, a methoxy group, a phenanthryl group, a dimethylfluorenyl group, or a furan group; Ar'1 and Ar'2 are linked to N at any substitutable position; Ar'1 and Ar'2 each independently represent one of the following groups or a combination of the following groups:

[0018] [ka]

[0019] As a further technical solution of the present invention, the second hole transport layer is selected from one of the following HT-1 to HT-56:

[0020] [ka] JPEG2025515400000008.jpg246169JPEG2025515400000009.jpg72169

[0021] In a further technical solution of the present invention, the P-type host material is selected from one of the following formulas II-a to II-d:

[0022] [ka]

[0023] Among them, L1 is a bond, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridinyl group, a phenanthryl group, a dibenzofuran group, a dibenzothienyl group, or a dimethylfluorenyl group; Ar1 to Ar3 are each independently a phenyl group, a methylphenyl group, an ethylphenyl group, an isopropylphenyl group, a tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridinyl group, a phenanthryl group, a dibenzofuran group, a dibenzothienyl group, a dimethylfluorenyl group, or a carbazole group.

[0024] In a further technical solution of the present invention, the P-type host material is selected from one of the following formulas RH1-1 to RH1-85:

[0025] [ka] JPEG2025515400000012.jpg249169JPEG2025515400000013.jpg245169JPEG2025515400000014.jpg161169

[0026] In a further technical solution of the present invention, the N-type host material is selected from one of the following formulae III-a to III-c:

[0027] [ka]

[0028] Among them, L2 is a bond, a phenyl group, a naphthyl group, a biphenyl group, a pyridinyl group, a phenanthryl group, a dibenzofuran group, a dibenzothienyl group, or a dimethylfluorenyl group; Ar4 to Ar5 are each independently a phenyl group, a methylphenyl group, an ethylphenyl group, an isopropylphenyl group, a tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridinyl group, a phenanthryl group, a dibenzofuran group, a dibenzothienyl group, a dimethylfluorenyl group, or a carbazolyl group.

[0029] In a further technical solution of the present invention, the N-type host material is selected from one of the following RH2-1 to RH2-96:

[0030] [ka] JPEG2025515400000017.jpg248169JPEG2025515400000018.jpg249169JPEG2025515400000019.jpg217169

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows: provide an organic electroluminescent device that is made with a specific combination of containing specific arylamine derivative in hole transporting region and containing dual host red light material in light emitting layer, the organic electroluminescent device made has high turn-on voltage and at the same time has relatively low driving voltage, and retains the advantages of high efficiency and long service life of dual host red light device, and improves the turn-on voltage of red light device, thereby mitigating the reddish phenomenon caused by crosstalk.

[0032] In this specification, the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the following, and means substituted with deuterium, a halogen group, a nitrile group, a silyl group, a boron group, a C1-C6 alkyl group, a C3-C10 cycloalkyl group, a C6-C18 aryl group, a C3-C30 heterocyclic group, or a substituent in which two or more of the above-listed substituents are linked together, or has no substituent.

[0033] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a turn-on voltage diagram of the organic electroluminescent devices prepared in Application Example 4 and Comparative Example 2.

[0034] [Mode for carrying out the invention] An organic electroluminescent device comprising a first electrode, a second electrode opposite the first electrode, an emissive layer between the first electrode and the second electrode, and a hole transport section between the first electrode and the emissive layer, the hole transport section comprising a hole injection layer, a first hole transport layer, and a second hole transport layer.

[0035] The general structural formula of the second hole transport layer is as shown in Formula I:

[0036] [ka]

[0037] Specifically, one of the following HT-1 to HT-56 is selected,

[0038] [ka] JPEG2025515400000022.jpg246169JPEG2025515400000023.jpg171169

[0039] the light-emitting layer comprises a P-type host material and an N-type host material, The general structural formula of the P-type host material is as shown in Formula II:

[0040] [ka]

[0041] Specifically, it is selected from one of the following formulas RH1-1 to RH1-85,

[0042] [ka] JPEG2025515400000026.jpg245169JPEG2025515400000027.jpg245169JPEG2025515400000028.jpg161169

[0043] The general structure of the N-type host material is as shown in Formula III:

[0044] [ka]

[0045] Specifically, the present invention is characterized in that the polymer is selected from one of the following RH2-1 to RH2-96:

[0046] [ka] JPEG2025515400000031.jpg243169JPEG2025515400000032.jpg231169JPEG2025515400000033.jpg187169

[0047] The synthesis route of the second hole transport layer in the above organic electroluminescent device is as follows:

[0048] [ka]

[0049] Under N2 protection, reactant A (1.0 eq), reactant B (1.0-1.3 eq), tetrakis(triphenylphosphine)palladium (0.01-0.05 eq), and potassium carbonate (2.0-2.5 eq) were added to a reaction vessel in toluene, ethanol, water (V), and toluene / water (V). トルエン :V エタノール :V 水 The mixture was added to a mixed solvent of 1:200 / m2 (2:4:1:1), heated to 90-110°C, and reacted for 6-10 hours. After the reaction was completed, the mixture was cooled to room temperature. After the solid was completely precipitated, the mixture was filtered by suction. The filter cake was dried and recrystallized in 1,4-dioxane to obtain formula I.

[0050] Hal1 is Cl, Br, and I.

[0051] The synthesis route of the P-type host material in the above organic electroluminescent device is as follows: If L1 is not a bond,

[0052] [ka]

[0053] Under N2 protection, reactant C (1.0 eq), reactant D (1.0-1.2 eq), tetrakis(triphenylphosphine)palladium (0.01-0.04 eq), and potassium carbonate (2.0-2.4 eq) were added to a reaction vessel in toluene, ethanol, water (V), and toluene / ethanol, respectively. トルエン :V エタノール :V 水 The mixture was added to a mixed solvent of 1:200 / m2 (2:4:1:1), heated to 90-110°C, and reacted for 6-10 hours. After the reaction was completed, the mixture was cooled to room temperature. After the solid was completely precipitated, the mixture was filtered by suction. The filter cake was dried and recrystallized in 1,4-dioxane to obtain the compound II.

[0054] If L1 is a bond,

[0055] [ka]

[0056] Under N2 protection, reactant C (1.0 eq), reactant D (1.0-1.2 eq), Pd(OAc)2 (0.01-0.04 eq), P(t-Bu)3 (0.05-0.1 eq), NaOtBu (2.0-2.5 eq), and o-xylene were added to a reaction vessel to dissolve, and the mixture was heated to 135-145°C and reacted for 2-4 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate and separated by column chromatography to obtain formula II.

[0057] Hal2 is Cl, Br, I.

[0058] The synthesis route of the N-type host material in the above organic electroluminescent device is as follows:

[0059] [ka]

[0060] Under N2 protection, reactant E (1.0 eq), reactant F (1.0-1.2 eq), tetrakis(triphenylphosphine)palladium (0.01-0.04 eq), and potassium carbonate (2.0-2.4 eq) were added to a reaction vessel in toluene, ethanol, water (V トルエン :V エタノール :V 水 The mixture was added to a mixed solvent of 1:200 / m2 (COOH / water = 2-4:1:1), heated to 90-110°C, and reacted for 6-10 hours. After the reaction was completed, the mixture was cooled to room temperature. After the solid was completely precipitated, the mixture was filtered by suction, dried, and recrystallized in 1,4-dioxane to obtain the formula III.

[0061] Hal3 is Cl, Br, I.

[0062] Example 1: Synthesis of second hole transport layer HT-13

[0063] [ka]

[0064] CAS:HT-13-B:55135-66-5 Under N2 protection, reactant HT-13-A (40 mmol), reactant HT-13-B (48 mmol), tetrakis(triphenylphosphine)palladium (0.04 mmol) and potassium carbonate (88 mmol) were added to a reaction vessel in a mixed solvent of toluene (90 mL), ethanol (30 mL) and water (30 mL), respectively, and the mixture was heated to 100°C and reacted for 8 h. After the reaction was completed, the mixture was cooled to room temperature, and after the precipitation of the solid was completed, the mixture was filtered by suction, the filter cake was dried, and the mixture was recrystallized in 1,4-dioxane to obtain compound HT-13 (24.37 g, yield 88%).

[0065] Characterization HPLC purity >99.8%, Mass spectrometry test: Theoretical value 691.92, Test value 692.26, elemental analysis Theoretical values: C, 92.00, H, 5.97, N, 2.02. Test values: C, 91.70, H, 6.25, N, 2.14.

[0066] Example 2: Synthesis of second hole transport layer HT-24

[0067] [ka]

[0068] CAS:HT-24-A:1959599-90-6 CAS:HT-24-B:55135-66-5 CAS:HT-24:2227490-15-3 Under N2 protection, reactant HT-24-A (40 mmol), reactant HT-24-B (48 mmol), tetrakis(triphenylphosphine)palladium (0.04 mmol) and potassium carbonate (88 mmol) were added to a reaction vessel in a mixed solvent of toluene (90 mL), ethanol (30 mL) and water (30 mL), respectively, and the temperature was raised to 100°C and reacted for 8 h. After the reaction was completed, the mixture was cooled to room temperature, and after the precipitation of the solid was completed, it was filtered by suction, the filter cake was dried, and recrystallized by placing it in 1,4-dioxane to obtain compound HT-24 (24.37 g, yield 85%).

[0069] Characterization HPLC purity >99.7%, Mass spectrometry test: theoretical value 677.89, test value 678.30, elemental analysis Theoretical values: C, 92.13, H, 5.80, N, 2.07. Test values: C,91.93, H,6.02, N,2.15.

[0070] Example 3: Synthesis of P-type host material RH1-32

[0071] [ka]

[0072] CAS:RH1-32-C:2085325-16-0 CAS:RH1-32-D:2230816-66-5 Under N2 protection, reactant RH1-32-C (40 mmol), reactant RH1-32-D (44 mmol), Pd(OAc)2 (0.4 mmol), P(t-Bu)3 (2 mmol), NaOtBu (88 mmol), and o-xylene were added to a reaction vessel and dissolved, then heated to 140 °C and reacted for 4 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate and separated by column chromatography to obtain compound RH1-32 (19.62 g, yield 78%).

[0073] Characterization HPLC purity >99.7%, Mass spectrometry test: theoretical value 628.73, test value 629.01, elemental analysis Theoretical values: C, 85.97; H, 4.49; N, 4.46; O, 5.09. Test values: C,85.82, H,4.62, N,4.52, O,5.16.

[0074] Example 4: Synthesis of P-type host material RH1-50

[0075] [ka]

[0076] CAS:RH1-50-C:2085325-18-2 CAS:RH1-50-D:2222194-15-0 CAS:RH1-50:2649505-53-1 Under N2 protection, reactant RH1-50-C (40 mmol), reactant RH1-50-D (48 mmol), tetrakis(triphenylphosphine)palladium (0.6 mmol) and potassium carbonate (84 mmol) were added to a reaction vessel in a mixed solvent of toluene (90 mL), ethanol (30 mL) and water (30 mL), respectively, and the mixture was heated to 95 °C and reacted for 10 h. After the reaction was completed, the mixture was cooled to room temperature, and after the solid precipitation was completed, the mixture was filtered by suction, the filter cake was dried and recrystallized in 1,4-dioxane to obtain compound RH1-50 (20.13 g, yield 80%).

[0077] Characterization HPLC purity >99.8%, Mass spectrometry test: theoretical value 628.73, test value 629.01, elemental analysis Theoretical values: C, 85.97; H, 4.49; N, 4.46; O, 5.09. Test values: C,85.82, H,4.62, N,4.52, O,5.16.

[0078] Example 5: Synthesis of P-type host material RH1-57

[0079] [ka]

[0080] Under N2 protection, reactant RH1-57-C (40 mmol), reactant RH1-57-D (45 mmol), tetrakis(triphenylphosphine)palladium (0.4 mmol) and potassium carbonate (84 mmol) were added to a reaction vessel in a mixed solvent of toluene (90 mL), ethanol (30 mL) and water (30 mL), respectively, and the mixture was heated to 95 °C and reacted for 8 h. After the reaction was completed, the mixture was cooled to room temperature, and after the solid precipitation was completed, the mixture was filtered by suction, the filter cake was dried and recrystallized in 1,4-dioxane to obtain compound RH1-57 (22.98 g, yield 83%).

[0081] Characterization HPLC purity >99.8%, Mass spectrometry test: Theoretical value 691.83, Test value 692.19, elemental analysis Theoretical values: C, 86.81, H, 4.81, N, 6.07, O, 2.31. Test values: C, 86.58, H, 4.98, N, 6.12, O, 2.39.

[0082] Example 6: Synthesis of N-type host material RH2-5

[0083] [ka]

[0084] CAS:RH2-5-E:2204284-97-7 CAS:RH2-5-F:1970122-69-0 CAS:RH2-5:2649505-87-1 Under N2 protection, reactant RH2-5-E (40 mmol), reactant RH2-5-F (48 mmol), tetrakis(triphenylphosphine)palladium (0.4 mmol) and potassium carbonate (84 mmol) were added to a reaction vessel in a mixed solvent of toluene (90 mL), ethanol (30 mL) and water (30 mL), respectively, and the mixture was heated to 95°C and reacted for 8 h. After the reaction was completed, the mixture was cooled to room temperature, and after the solid precipitation was completed, the mixture was filtered by suction, the filter cake was dried and recrystallized in 1,4-dioxane to obtain compound RH2-5 (17.28 g, yield 75%).

[0085] Characterization HPLC purity >99.7%, Mass spectrometry test: Theoretical value 575.67, Test value 576.13, elemental analysis Theoretical values: C, 85.54; H, 4.38; N, 7.30; O, 2.78. Test values: C,85.29, H,4.62, N,7.35, O,2.84.

[0086] Example 7: Synthesis of N-type host material RH2-29

[0087] [ka]

[0088] CAS:RH2-29:2649507-42-4 Under N2 protection, reactant RH2-29-E (40 mmol), reactant RH2-29-F (48 mmol), tetrakis(triphenylphosphine)palladium (0.4 mmol) and potassium carbonate (84 mmol) were added to a reaction vessel in a mixed solvent of toluene (90 mL), ethanol (30 mL) and water (30 mL), respectively, and the mixture was heated to 90 °C and reacted for 8 h. After the reaction was completed, the mixture was cooled to room temperature, and after the solid precipitation was completed, the mixture was filtered by suction, the filter cake was dried and recrystallized in 1,4-dioxane to obtain compound RH2-29 (18.20 g, yield 79%).

[0089] Characterization HPLC purity >99.7%, Mass spectrometry test: Theoretical value 575.67, Test value 576.07, elemental analysis Theoretical values: C, 85.54; H, 4.38; N, 7.30; O, 2.78. Test values: C, 85.39, H, 4.50, N, 7.36, O, 2.84.

[0090] Example 8: Synthesis of N-type host material RH2-78

[0091] [ka]

[0092] Under N2 protection, reactant RH2-78-E (40 mmol), reactant RH2-78-F (48 mmol), tetrakis(triphenylphosphine)palladium (0.4 mmol) and potassium carbonate (84 mmol) were added to a reaction vessel in a mixed solvent of toluene (90 mL), ethanol (30 mL) and water (30 mL), respectively, and the mixture was heated to 95 °C and reacted for 8 h. After the reaction was completed, the mixture was cooled to room temperature, and after the solid precipitation was completed, the mixture was filtered by suction, the filter cake was dried and recrystallized in 1,4-dioxane to obtain compound RH2-78 (17.28 g, yield 72%).

[0093] Characterization HPLC purity >99.8%, Mass spectrometry test: theoretical value 727.87, test value 728.23, elemental analysis Theoretical values: C, 87.46, H, 4.57, N, 5.77, O, 2.20, Test values: C,87.72, H,4.67, N,5.84, O,2.27.

[0094] The present invention provides an organic electroluminescent device, which is made with a specific combination of the specific arylamine derivatives in hole transporting region and the dual host red light material in light emitting layer, and has a high turn-on voltage and at the same time has a relatively low driving voltage, and retains the advantages of the high efficiency and long life of the dual host red light device, and improves the turn-on voltage of the red light device, thereby mitigating the reddish phenomenon caused by crosstalk.

[0095] The organic electroluminescent device according to the present invention comprises a first electrode, a second electrode opposite the first electrode, a light-emitting layer between the first and second electrodes, and a hole-transporting section between the first electrode and the light-emitting layer.

[0096] The hole transport section of the present invention includes a hole injection layer, a first hole transport layer, and a second hole transport layer, and the second hole transport layer material may also be used as a light-emitting auxiliary layer material or an electron blocking layer material.

[0097] The second hole transport layer material of the present invention comprises a compound according to Formula I:

[0098] The host material of the present invention is a red light dual host material and comprises the compounds represented by formulae II and III.

[0099] The organic electroluminescent device of the present invention may be a top-emitting, bottom-emitting or bidirectional emitting device. The device of the present invention may be used in organic light-emitting devices, organic solar cells, electronic paper, organic photoreceptors or organic thin film transistors.

[0100] The organic electroluminescent device of the present invention comprises a first electrode, a second electrode opposite the first electrode, a light-emitting layer between the first electrode and the second electrode, a hole-transporting section between the first electrode and the light-emitting layer, and an electron-transporting section between the light-emitting layer and the second electrode, one of the first electrode and the second electrode being an anode and the other being a cathode.

[0101] The organic light-emitting device may have a structure including, as organic layers, a hole injection layer, a hole transport layer, an electron blocking layer, a second hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. However, the structure of the organic light-emitting device is not limited thereto, and may include fewer or more organic layers.

[0102] The organic light emitting device may be fabricated by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate, or by physical vapor deposition (PVD) such as sputtering or ebeam evaporation.

[0103] A first electrode is formed on a substrate by depositing a metal or a conductive metal oxide or an alloy thereof, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer is formed on the first electrode, and a material usable as a second electrode is deposited on the organic layer. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a second electrode material, an organic layer and a first electrode material on a substrate.

[0104] In addition, the compounds represented by Formula I, Formula II, and Formula III can be used to form an organic layer in the manufacture of an organic light-emitting device by using not only a vacuum deposition method but also a solution coating method, among which the solution coating method refers to, but is not limited to, a spin coating method, a dip coating method, a blade coating method, an inkjet printing method, a screen printing method, a spray method, a roll coating method, etc.

[0105] In the present invention, the first electrode is an anode and the second electrode is a cathode.

[0106] As the anode material, a material with a large work function is usually preferred so that holes can be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof, metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO), combinations of metals and oxides such as ZnO:A1 or SnO2:Sb, and conductive polymers such as polypyrrole and polyaniline.

[0107] The cathode material is preferably a material with a small work function so that electrons can be easily injected into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof such as LiF / A1 or LiO2 / A1, and multilayer structures such as Mg / Ag.

[0108] The hole transport region refers to a region in which holes are transported between the first electrode and the light-emitting layer. The hole transport region is a region that receives holes from the hole injection layer and transports them to the light-emitting layer. The hole transport region may be disposed between the anode (or the hole injection layer) and the light-emitting layer. The hole transport region may facilitate the transport of holes transferred from the anode to the light-emitting layer and block electrons transferred from the cathode so that they remain in the light-emitting layer.

[0109] The hole transport section of the present invention includes a hole injection layer, a first hole transport layer, and a second hole transport layer, and the second hole transport layer material may also be used as a light-emitting auxiliary layer material or an electron blocking layer material.

[0110] The second hole transport layer material of the present invention comprises a compound represented by Formula I: In the present invention, the hole injection layer is preferably a p-doped hole injection layer, and the p-doped hole injection layer means a hole injection layer doped with a p-dopant. The p-dopant is a material that can impart p-type semiconductor properties. The p-type semiconductor properties refer to the property of injecting or transporting holes at the HOMO energy level, i.e., the property of a material having high hole conductivity.

[0111] The second hole transport layer may be disposed between the anode and the light emitting layer, or between the cathode and the light emitting layer. When disposed between the anode and the light emitting layer, the second hole transport layer may be used to facilitate hole injection and / or hole transport or to prevent electron overflow. When disposed between the cathode and the light emitting layer, the second hole transport layer may be used to facilitate electron injection and / or electron transport or to prevent hole overflow.

[0112] The luminescent material of the luminescent layer is a material that can receive holes and electrons from the hole transport layer and electron transport layer, respectively, and combine them to emit light in the visible light region, and is preferably a material with high quantum efficiency for fluorescence or phosphorescence.

[0113] The light-emitting layer may include a host material and a dopant material.

[0114] The host material of the present invention is a red light dual host material comprising compounds represented by formulas II and III, The electron transport region may include at least one of an electron buffer layer, a hole blocking layer, an electron transport layer and an electron injection layer, and is preferably at least one of an electron transport layer and an electron injection layer. The electron transport region is a layer that can improve the problem of degradation of luminance caused by the change of current characteristics in the device when the device is exposed to high temperatures in the panel manufacturing process, and can control the flow characteristics of charges.

[0115] Except for the specific combination of Formula I in the second hole transport layer and Formula II and Formula III in the light emitting layer disclosed herein, there is no particular limitation on the materials of other layers in the OLED device. Existing hole injection materials, hole transport materials, dopant materials, hole blocking layer materials, electron transport layer materials and electron injection materials may be used.

[0116] The hole injection layer material may be metal porphyrin, oligothiophene, arylamine derivatives, hexanitrile hexaazatriphenylene organic compounds, quinacridone organic compounds, perylene organic compounds, anthraquinone, polyaniline, and polythiophene conductive polymers, and the p-doped p-dopant may be exemplified by the following compounds, but is not limited thereto.

[0117] [ka]

[0118] The first hole transport material may be selected from arylamine derivatives, conductive polymers, and block copolymers in which a conjugated portion and a non-conjugated portion exist simultaneously. Specifically, the first hole transport layer material is selected from the following compounds, but is not limited thereto.

[0119] [ka] JPEG2025515400000048.jpg155169

[0120] The second hole transport layer of the present invention is a compound represented by general formula I:

[0121] The red light dual host material of the present invention is a compound represented by general formula II and general formula III.

[0122] The dopant material of the present invention is selected as a red light dopant material, and includes aromatic amine derivatives, styrylamine compounds, iodine compounds, fluoranthene compounds, metal compounds, etc. Specifically, the red light dopant material of the present invention is selected from the following compounds, but is not limited thereto:

[0123] [ka]

[0124] Materials for the electron transport layer (hole blocking layer) include derivatives of oxazole, imidazole, thiazole, triazine, etc., metal chelates, quinoline derivatives, quinoxaline derivatives, diazaanthracene derivatives, phenanthroline derivatives, silicon-containing heterocyclic compounds, perfluorooligomers, etc., and specifically, the electron transport layer material is selected from the following compounds, but is not limited thereto.

[0125] [ka] JPEG2025515400000051.jpg66169JPEG2025515400000052.jpg200169

[0126] Materials for the electron injection layer include, but are not limited to, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthrone and derivatives thereof, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, ytterbium, etc., or alloys, metal combinations, or nitrogen-containing five-membered ring derivatives thereof.

[0127] The organic electroluminescent composition and the organic electroluminescent device provided by the present invention will be described in detail below with reference to specific examples.

[0128] A method for manufacturing a red light organic electroluminescent device, comprising the steps of: a. ITO anode: An ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate with a coating thickness of 150 nm is washed twice with distilled water, ultrasonically washed for 30 min, then washed twice with distilled water, ultrasonically washed for 10 min, and after washing, it is transferred to a dehydrator for dehydration, and finally baked in a vacuum oven at 220°C for 2 hours. After baking, it can be used by lowering the temperature. The substrate is used as an anode to carry out a deposition device process using an evaporation machine, and other functional layers are sequentially deposited on it. b. HIL (hole injection layer) At a deposition rate of 1 Å / s, the hole injection layer materials HT1-12 and P-9 were vacuum-deposited, the chemical formula of which is as follows, the deposition rate ratio of the above HT1-12 and P-9 was 97:3, and the thickness was 10 nm; c. HTL (Hole Transport Layer) 125 nm of HT1-12 was vacuum-deposited as a hole transport layer on top of the hole injection layer at a deposition rate of 1.0 Å / s; d. Second hole transport layer: 90 nm of the compound of formula I of the present invention is vacuum-deposited on the hole transport layer at a deposition rate of 1.0 Å / s as a second hole transport layer; e. EML (light-emitting layer) Next, on the second hole transport layer, a host material (Host) and a dopant material (Dopant-R-1) represented by formula II and formula III were vacuum-deposited at a deposition rate of 1 Å / s to form a light-emitting layer having a total thickness of 40 nm, the chemical formulas of the Host and Dopant being as follows, wherein the deposition ratio of the host material of formula II and formula III was 4:6, and the deposition rate ratio of the Host and Dopant-R-1 was 97:3; f. HBL (Hole Blocking Layer) A hole blocking layer HB having a thickness of 5.0 nm was vacuum-deposited at a deposition rate of 0.5 Å / s. g. ETL (electron transport layer) ET-10 and Liq were vacuum-deposited to a thickness of 30 nm as an electron transport layer at a deposition rate of 1 Å / s, in which the deposition rate ratio of ET-10 to Liq was 1:1; h, EIL (electron injection layer) A 1.0 nm Yb film layer was evaporated at a deposition rate of 0.5 Å / s to form an electron injection layer; I. Cathode: 18 nm of magnesium and silver were evaporated at a deposition rate of 1 Å / s, with the deposition rate ratio being 1:9, to form a cathode; j. Light extraction layer: A CPL with a thickness of 70 nm was vacuum-deposited on the cathode as a light extraction layer at a deposition rate of 1 Å / s. k. The substrate after deposition is packaged. First, adhesive coating equipment is used to perform a coating process with UV adhesive on the cleaned cover plate. Then, the coated cover plate is transferred to the pressing stage, and the substrate after deposition is placed on the top of the cover plate. Finally, the substrate and the cover plate are bonded together by the action of bonding equipment, and at the same time, the UV adhesive is cured under light illumination.

[0129] The device structure is as follows: ITO / Ag / ITO / HT1-12:P-9(10 nm) / HT1-12(125 nm) / Formula I(90 nm) / (Formula II+Formula III):Dopant-R-1(40 nm) / HB(5 nm) / ET-10:Liq(30 nm) / Yb(1 nm) / Mg:Ag(18 nm) / CPL(70 nm).

[0130] [Table 1] JPEG2025515400000054.jpg218169JPEG2025515400000055.jpg90169

[0131] Application Examples 1-9 According to the above-mentioned method for producing an organic electroluminescent device, the organic electroluminescent devices of Application Examples 1 to 9 are produced, and the compounds RH1-50 and RH2-29 shown in Table 1 are used as host materials, and HT-4, HT-9, HT-11, HT-13, HT-22, HT-24, HT-25, HT-38 and HT-52 are used as second hole transport layer materials.

[0132] Application example 10 According to the above-mentioned method for producing an organic electroluminescent device, an organic electroluminescent device of Application Example 10 is produced, and the compounds RH1-32 and RH2-78 shown in Table 1 are used as host materials, and HT-13 is used as a second hole transport layer material.

[0133] Application example 11 According to the above-mentioned method for producing an organic electroluminescent device, an organic electroluminescent device of Application Example 11 is produced, and the compounds RH1-57 and RH2-5 shown in Table 1 are used as host materials, and HT-13 is used as the second hole transport layer material.

[0134] Application example 12 According to the above-mentioned method for producing an organic electroluminescent device, an organic electroluminescent device of Application Example 12 is produced, and the compounds RH1-32 and RH2-78 shown in Table 1 are used as host materials, and HT-24 is used as the second hole transport layer material.

[0135] Application example 13 According to the above-mentioned method for producing an organic electroluminescent device, an organic electroluminescent device of Application Example 13 is produced, and the compounds RH1-57 and RH2-5 shown in Table 1 are used as host materials, and HT-24 is used as the second hole transport layer material.

[0136] Comparative Examples 1 to 3 According to the above-mentioned method for producing an organic electroluminescent device, the organic electroluminescent devices of Comparative Examples 1 to 3 are produced, and the compounds RH1-50 and RH2-29 shown in Table 1 are used as host materials, and the comparative compounds 1 to 3 are used as second hole transport layer materials.

[0137] Comparative Example 4 According to the above-mentioned method for producing an organic electroluminescent device, an organic electroluminescent device of Comparative Example 4 is produced, and the compounds RH1-32 and RH2-78 shown in Table 1 are used as host materials, and the comparative compound 2 is used as a second hole transport layer material.

[0138] Comparative Example 5 According to the above-mentioned method for producing an organic electroluminescent device, an organic electroluminescent device of Comparative Example 5 is produced, and the compounds RH1-57 and RH2-5 shown in Table 1 are used as host materials, and the comparative compound 2 is used as a second hole transport layer material.

[0139] For the test results of the driving voltage and turn-on voltage of the organic electroluminescent devices obtained in the above Device Application Examples 1 to 13 and Device Comparative Examples 1 to 5 at a luminance of 6000 (nits), see Table 2 and FIG.

[0140] [Table 2]

[0141] In the present invention, the voltage at 6000 nit of the red light device is taken as the driving voltage.

[0142] The starting voltage and driving voltage obtained from Table 2 show that the turn-on voltage is improved between 0.1-0.15 V, which is already a significant improvement in the field. The present invention provides an organic electroluminescent device manufactured with a specific combination of the specific arylamine derivative of the present disclosure of formula I in the hole transporting region and the dual host red light material of the present disclosure of formula II and formula III in the light emitting layer, which can improve the turn-on voltage and maintain a relatively low driving voltage.

[0143] Obviously, the above examples are merely illustrative for the purpose of clarifying the description, and are not intended to limit the embodiments. Those skilled in the art may make other different modifications or modifications based on the above description. It is not possible or necessary to list all the embodiments here. Any obvious changes or modifications drawn thereby still fall within the scope of the claims of the present invention. [Brief description of the drawings]

[0144] [Figure 1] FIG. 11 is a turn-on voltage diagram of the organic electroluminescent devices prepared in Application Example 4 and Comparative Example 2.

Claims

1. 1. An organic electroluminescent device comprising: a first electrode; a second electrode opposite the first electrode; a light-emitting layer between the first electrode and the second electrode; and a hole transport section between the first electrode and the light-emitting layer, the hole transport section comprising a hole injection layer, a first hole transport layer, and a second hole transport layer; The general structural formula of the second hole transport layer is as shown in Formula I: 【Chemistry 1】 Among them, Ar' 1 , Ar' 2 are each independently a substituted or unsubstituted C6 to C24 aryl group or a substituted or unsubstituted 3- to 24-membered heteroaryl group; R' 1 ~R' 3 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C18 aryl group, a substituted or unsubstituted 3- to 18-membered heteroaryl group, a substituted or unsubstituted C3-C12 cycloalkyl group, or a substituted or unsubstituted C1-C6 alkoxy group; R' 4 is hydrogen, a methyl group, an ethyl group, a phenyl group, or a biphenyl group, R' 1 ~R' 4 is linked to the benzene ring in a manner that forms a substituted or fused ring; the light-emitting layer comprises a P-type host material and an N-type host material; The general structural formula of the P-type host material is as shown in Formula II: 【Chemistry 2】 Among them, Y 1 , Y 2 is selected from the following combinations: Y 1 is N and Y 2 is O, Y 1 is N and Y 2 is S, Y 1 is O and Y 2 is N, Y 1 is S and Y 2 is N, L 1 is a bond, a substituted or unsubstituted C6 to C18 arylene group, or a substituted or unsubstituted 3- to 18-membered heteroarylene group, Ar 1 ~Ar 3 are each independently a substituted or unsubstituted C6 to C24 aryl group or a substituted or unsubstituted 3- to 24-membered heteroaryl group; Ar 1 ~Ar 3 is linked to the benzene ring in a manner that forms a substituted or fused ring; The general structural formula of the N-type host material is as shown in Formula III: 【Chemistry 3】 Among them, X 1 is selected from O or S, One of m, n, and p is 1 and the rest are 0, Z 1 ~Z 3 are each independently N or C, and at least one is N; Ar 4 ~Ar 5 are each independently a substituted or unsubstituted C6 to C24 aryl group or a substituted or unsubstituted 3- to 24-membered heteroaryl group; L 2 is a bond, a substituted or unsubstituted C6 to C18 arylene group, or a substituted or unsubstituted 3- to 18-membered heteroarylene group; Organic electroluminescent devices.

2. The second hole transport layer is selected from one of the following formulas I-1 to I-3: 【Chemistry 4】 Among them, R' 1 ~R' 2 are each independently hydrogen, deuterium, a methyl group, an ethyl group, an isopropyl group, a propyl group, a tert-butyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridinyl group, a methoxy group, a phenanthryl group, a dibenzofuran group, or a dimethylfluorenyl group; R' 3 is deuterium, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, pyridinyl, methoxy, phenanthryl, dimethylfluorenyl or furan, Ar' 1 and Ar' 2 is linked to N at any substitutable position, Ar' 1 , Ar' 2 are each independently one of the following groups or a combination of the following groups: 【Chemistry 5】 2. The organic electroluminescent device according to claim 1 .

3. The second hole transport layer is selected from one of the following HT-1 to HT-56, 【Chemistry 6】 【change】 【change】 3. The organic electroluminescent device according to claim 2 .

4. The P-type host material is selected from one of the following formulas II-a to II-d: 【Chemistry 7】 Among them, L 1 is a bond, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridinyl group, a phenanthryl group, a dibenzofuran group, a dibenzothienyl group, or a dimethylfluorenyl group, Ar 1 ~Ar 3 are each independently a phenyl group, a methylphenyl group, an ethylphenyl group, an isopropylphenyl group, a tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridinyl group, a phenanthryl group, a dibenzofuran group, a dibenzothienyl group, a dimethylfluorenyl group, or a carbazole group; 10. The organic electroluminescent device of claim 1.

5. The P-type host material is selected from one of the following formulas RH1-1 to RH1-85: 【Chemistry 8】 【change】 【change】 【change】 5. The organic electroluminescent device according to claim 4.

6. The N-type host material is selected from one of the following formulas III-a to III-c: 【Chemistry 9】 Among them, L 2 is a bond, a phenyl group, a naphthyl group, a biphenyl group, a pyridinyl group, a phenanthryl group, a dibenzofuran group, a dibenzothienyl group, or a dimethylfluorenyl group, Ar 4 ~Ar 5 are each independently a phenyl group, a methylphenyl group, an ethylphenyl group, an isopropylphenyl group, a tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a pyridinyl group, a phenanthryl group, a dibenzofuran group, a dibenzothienyl group, a dimethylfluorenyl group, or a carbazole group; 10. The organic electroluminescent device of claim 1.

7. The N-type host material is selected from one of the following formulas RH2-1 to RH2-96: 【Chemistry 10】 【change】 【change】 【change】 7. The organic electroluminescent device according to claim 6 .

8. An organic electroluminescent apparatus, characterized in that it comprises the organic electroluminescent device according to any one of claims 1 to 7, which is a top-emitting, bottom-emitting or bidirectional-emitting type. Organic electroluminescent device.

9. A photovoltaic device, comprising the organic electroluminescent device according to any one of claims 1 to 7, characterized in that the photovoltaic device is an organic light-emitting device, an organic solar cell, an electronic paper, an organic photoreceptor or an organic thin film transistor. Photoelectric equipment.

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