Organic light emitting device, display device including the same, and compound

Abstract

The present invention relates to an organic light emitting device, to a display device comprising the organic light emitting device, and to a compound.

Description

[0001] This invention relates to an organic light-emitting device and a display device comprising the organic light-emitting device. The invention also relates to a compound. Background Technology

[0002] Organic semiconductor devices, such as organic light-emitting diodes (OLEDs), are self-emissive devices that possess wide viewing angles, excellent contrast ratios, fast response times, high brightness, superior operating voltage characteristics, and excellent color reproduction. A typical OLED comprises an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When a voltage is applied to the anode and cathode, holes injected from the anode move to the EML via the HTL, and electrons injected from the cathode move to the EML via the ETL. Holes and electrons recombine in the EML to generate excitons. When the excitons descend from the excited state to the ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that OLEDs with the above structure exhibit excellent efficiency and / or long lifetime.

[0004] The performance of organic light-emitting diodes can be affected by the characteristics of the organic semiconductor layer, which in turn can be affected by the characteristics of the organic materials in the organic semiconductor layer.

[0005] In particular, there is a need to develop organic semiconductor layers that can improve electron mobility while simultaneously increasing electrochemical stability, so that organic semiconductor devices such as organic light-emitting diodes can be applied to large flat panel displays.

[0006] Therefore, one object of the present invention is to provide an organic light-emitting diode (OLED) that overcomes the disadvantages of the prior art and a compound for preparing the OLED, particularly a compound for use in an OLED that contributes to improving its performance, especially in terms of efficiency and / or operating voltage. Summary of the Invention

[0007] This objective is achieved through an organic light-emitting device comprising an anode, a cathode, a light-emitting layer, a hole-blocking layer, and an electron transport layer. in - A light-emitting layer, a hole-blocking layer, and an electron transport layer are arranged between the anode and the cathode; - A hole blocking layer and an electron transport layer are arranged between the light-emitting layer and the cathode; - A hole blocking layer is positioned between the light-emitting layer and the electron transport layer; - The hole blocking layer is in direct contact with the electron transport layer; - The hole blocking layer does not contain electrical dopants; - Hole-blocking layer containing compound of formula (I) (I) In equation (I) - m and n are 0 or 1 independently; - p is 0 or 1; - m+n+p≥1; - R 1 and R 3 Independently, C6 to C6 are substituted or unsubstituted. 18 Aryl; - R 2 and R 4 Independently, C6 to C6 are substituted or unsubstituted. 18 Aranediol; - R 5 It is substituted or unsubstituted C6 to C 18 Aranediol; - R 6 Selected from benzene, pyrazine, and anthracene groups; - R 7 It is unreplaced C6 to C 18 Aryl; - R 8 To R 11 Independently selected from H and unsubstituted C6 to C 18 Aryl; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

[0008] This objective is also achieved by an apparatus comprising an organic light-emitting device according to the invention, wherein the apparatus is a display device or a lighting device.

[0009] This objective is also achieved through compounds of formula (II). (II) In equation (II) - m and n are 0 or 1 independently; - p is 0, 1, or 2; - m+n+p≥1; - R1 and R 3 It is either a substituted or unsubstituted phenyl group; - R 2 and R 4 It is either a substituted or unsubstituted phenylene group; - Each R 5 It is either a substituted or unsubstituted phenylene group; - R 6 Selected from benzene, pyrazine, and anthracene groups; - R 7 It is an unsubstituted phenyl group; - R 8 To R 11 Independently selected from H and unsubstituted phenyl groups; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

[0010] Compound of formula (I)

[0011] Organic light-emitting devices contain compounds of formula (I) in their undoped hole-blocking layers. (I).

[0012] Unless otherwise explicitly stated, all compounds, especially compounds, groups, parts, substituents, etc. of formula (I) shown herein, particularly those of formula (I) shown by structural formula, systematic name, etc., encompass their respective parts and fully deuterated derivatives, where it may be specified that substitutions other than deuteration are excluded. If a compound, group, part, substituent, etc., is mentioned as unsubstituted, this does not preclude D-substitution.

[0013] According to this disclosure, as an exemplary example, the use of any group A in the formula illustrates the following binding scenarios:

[0014] Group A can bind to any suitable binding site.

[0015] m and n are independently 0 or 1.

[0016] p is 0 or 1.

[0017] m+n+p≥1. (m+n+p) can be an integer from 1 to 3. (m+n+p) can be 1 or 2.

[0018] R 1 and R 3 Independently, C6 to C6 are substituted or unsubstituted. 18 Aryl. R 1 and R 3 It can be independently substituted or unsubstituted C6 to C 12 Aryl. R 1 and R 3 It can be independently substituted or unsubstituted C6 to C 10 Aryl. R 1 and R 3 It can be either substituted or unsubstituted phenyl.

[0019] In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C5 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C4 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C3 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C2 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, each of the one or more substituents may be a methyl group.

[0020] In R 1 and R 3 If one or more of them are replaced, the corresponding R 1 and / or R 3 (Including all substituents) can be independently selected from the following groups Ia-1 to Ia-8. Ia-1、 Ia-2, Ia-3 Ia-4 Ia-5 Ia-6 Ia-7 Ia-8, in" " is the binding position in equation (I), that is, with R 2 (for R) 1 ) or R 4 (for R) 3 The combination position of ).

[0021] In R 1 and R 3 If one or more of them are replaced, the corresponding R 1 and / or R 3 (Including all substituents) can be independently selected from the following groups Ia-2 to Ia-8. Ia-2, Ia-3 Ia-4 Ia-5 Ia-6 Ia-7 Ia-8, in" " is the binding position in equation (I), that is, with R 2 (for R) 1 ) or R 4 (for R) 3 The combination position of ).

[0022] In R 1 and R 3 If one or more of them are replaced, the corresponding R 1 and / or R 3 (Including all substituents) can be independently selected from the following groups Ia-1 to Ia-3.

[0023] Ia-1、 Ia-2, Ia-3, in" " is the binding position in equation (I), that is, with R 2 (for R) 1 ) or R 4 (for R) 3 The combination position of ).

[0024] It may be specified that one or more of the CH3 groups in Ia-1 to Ia-8 are replaced by C2 to C6 alkyl, C2 to C4 alkyl, C2 to C3 alkyl or C2 alkyl.

[0025] R 2and R 4 Independently, C6 to C6 are substituted or unsubstituted. 18 Aranediol. R 2 and R 4 It can be independently substituted or unsubstituted C6 to C 12 Aranediol. R 2 and R 4 It can be independently substituted or unsubstituted C6 to C 10 Aranediol. R 2 and R 4 It can be a substituted or unsubstituted phenylene group, independently. R 2 and R 4 It can be either substituted or unsubstituted meta-phenylene group.

[0026] R 2 and R 4 It can be independently unsubstituted C6 to C 18 Aranediol. R 2 and R 4 It can be independently unsubstituted C6 to C 12 Aranediol. R 2 and R 4 It can be independently unsubstituted C6 to C 10 Aranediol. R 2 and R 4 It can be an unsubstituted phenylene group independently. R 2 and R 4 Each of them is an unsubstituted meta-phenylene group.

[0027] R 5 It is substituted or unsubstituted C6 to C 18 Aranediol. R 5 It can be substituted or unsubstituted C6 to C 12 Aranediol. R 5 It can be a substituted or unsubstituted benzene group, or a substituted or unsubstituted biphenyl group.

[0028] R 5 The following groups can be selected from Ib-1 to Ib-6. Ib-1, Ib-2, Ib-3, Ib-4, Ib-5, Ib-6, in" "1" is the binding position of the following groups in formula (I).

[0029] and" 2” is related to R 6 The binding sites, where the corresponding Ib-1 to Ib-6 may or may not be substituted.

[0030] In R 2 R 4 and R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups. In R 2 R 4 and R 5 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C5 alkyl groups. In R 2 R 4 and R 5 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C4 alkyl groups. In R 2 R 4 and R 5 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C3 alkyl groups. In R 2 R 4 and R 5 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C2 alkyl groups. In R 2 R 4 and R 5 If one or more of the components are substituted, the one or more substituents can be methyl.

[0031] In R 2 R 4 and R 5 If one or more of them are replaced, the corresponding R 2 R 4 and R 5 (Including all substituents) may be independently selected from the following groups Ic-1 to Ic-9, or contain one of the following groups Ic-1 to Ic-9. Ic-1 Ic-2 Ic-3 Ic-4 Ic-5 Ic-6 Ic-7 Ic-8 Ic-9, in" 1” and “ 2” is the position where it connects with the rest of the equation (I).

[0032] Including all substituents (if any), R 5 It can be selected from one of the following groups Id-1 to Id-6. Id-1 Id-2, Id-3 ID-4 ID-5 ID-6 in" "1" is the binding position of the following groups in formula (I).

[0033] and" 2” is related to R 6 The position of the combination.

[0034] R 6 Selected from phenylene group, pyrazine group, and anthracene group. R 6 It can be selected from benzene and pyrazine.

[0035] R 6 It can be selected from one of the following groups Ie-1 to Ie-7. Ie-1 Ie-2, Ie-3, Ie-4 Ie-5 Ie-6 Ie-7, in" 1” is in equation (I) and R 5 The binding position, and " 2” is related to R 7 The position of the combination.

[0036] R 6 It can be selected from one of the following groups Ie-1 to Ie-6. Ie-1, Ie-2, Ie-3, Ie-4 Ie-5 Ie-6, in" 1” is in equation (I) and R 5 The binding position, and " 2” is related to R 7 The position of the combination.

[0037] In Ie-1 to Ie-7, R 8 To R 11 Can be used with anything other than those marked " 1” and “ It can bond with any carbon atom other than the 2” carbon atom. If it can bond with R 8 To R 11 If there are fewer than four carbon atoms bonded, then R 8 To R 11 One or more of them may not exist. For example, if it is possible to be with R 8 To R 11 There are only two carbon atoms involved in the bonding, such as in Ie-4, then R 10 and R 11 It does not exist, and the corresponding group has the following formula Ie-4.1 Ie-4.1.

[0038] R 7 It is unreplaced C6 to C 18 Aryl. R 7 It can be unsubstituted C6 to C 12 Aryl. R 7 It can be unsubstituted C6 to C 10 Aryl. R 7 It can be an unsubstituted phenyl group.

[0039] R 8 To R 11 Independently selected from H and unsubstituted C6 to C 18 Aryl. R 8 To R 11 It can be independently selected from H and unsubstituted C6 to C. 12 Aryl. R 8 To R 11 It can be independently selected from H and unsubstituted C6 to C. 10 Aryl. R 8 To R 11 It can be independently selected from H and unsubstituted phenyl groups.

[0040] If R 6 If it is a benzene group, then R can be specified. 8 To R 11 One, two, or three of them are H, and the rest are R. 8 To R 11 It is unreplaced C6 to C 18 Aryl. If R 6 If it is a benzene group, then R can be specified. 8 To R 11 One, two, or three of them are H, and the rest are R. 8 To R11 It is unreplaced C6 to C 12 Aryl. If R 6 If it is a benzene group, then R can be specified. 8 To R 11 One, two, or three of them are H, and the rest are R. 8 To R 11 It is unreplaced C6 to C 10 Aryl. If R 6 If it is a benzene group, then R can be specified. 8 To R 11 One, two, or three of them are H, and the rest are R. 8 To R 11 It is an unsubstituted phenyl group.

[0041] If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least one of them is unsubstituted C6 to C6. 18 aryl, and the unsubstituted C6 to C 18 The aryl group is located in the benzene group (R 6 ) and R 5 The adjacent positions of the binding position. If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least one of them is unsubstituted C6 to C6. 12 aryl, and the unsubstituted C6 to C 12 The aryl group is located in the benzene group (R 6 ) and R 5 The adjacent positions of the binding position. If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least one of them is unsubstituted C6 to C6. 10 aryl, and the unsubstituted C6 to C 10 The aryl group is located in the benzene group (R 6 ) and R 5 The adjacent positions of the binding position. If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least one of them is an unsubstituted phenyl group, and the unsubstituted phenyl group is located in the phenylene group (R). 6 ) and R 5 The adjacent position of the combination position.

[0042] If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least two of them are unsubstituted C6 to C6. 18Aryl groups, and these unsubstituted C6 to C6 groups 18 The aryl groups are adjacent to each other. If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least two of them are unsubstituted C6 to C6. 12 Aryl groups, and these unsubstituted C6 to C6 groups 12 The aryl groups are adjacent to each other. If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least two of them are unsubstituted C6 to C6. 10 Aryl groups, and these unsubstituted C6 to C6 groups 10 The aryl groups are adjacent to each other. If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least two of them are unsubstituted phenyl groups, and these unsubstituted phenyl groups are in the ortho position relative to each other.

[0043] As mentioned in the two paragraphs above, R 8 To R 11 At least one of them is an aryl group and is in the phenylene group (R 6 ) and R 5 The characteristics of the adjacent positions of the binding position, and R 8 To R 11 At least two of them are aryl groups and these aryl groups can be used alternatively or together (and / or) with respect to features that are adjacent to each other.

[0044] If R 6 If it is a benzene group, then " "is with R" 5 The following part of the joint position

[0045] It can be one of the following groups: If-1 to If-3. If-1、 If-2、 If-3.

[0046] If R 6 If it is a pyrazine subunit, then " "is with R" 5 The following part of the joint position

[0047] It could be Ig-1, Ig-1.

[0048] If R 6 If it is anthracene subunit, then " "is with R" 5 The following part of the joint position

[0049] It can be Ih-1, Ih-1.

[0050] R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 2 R 4 and R 5 At least one of them is substituted with at least one C1 to C6 alkyl substituent. In one embodiment, R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 5 It is substituted with at least one C1 to C6 alkyl substituent. In one embodiment, R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 2 R 4 and R 5 At least one of them is substituted with at least one C1 to C6 alkyl substituent. In one embodiment, R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 5 It is substituted with at least one C1 to C6 alkyl substituent. In one embodiment, R 1 and R 3 At least one of them is substituted by one or two C1 to C6 alkyl substituents; and / or R 5 It is substituted with one or two C1 to C6 alkyl substituents. In this respect, the C1 to C6 alkyl substituents can be selected independently as described above.

[0051] In one embodiment, the hole-blocking layer comprises a compound of formula (I). (I) In equation (I) - m and n are 0 or 1 independently; - p is 0 or 1; - m+n+p≥1; - R 1 and R 3 Independently, C6 to C6 are substituted or unsubstituted.18 Aryl; - R 2 and R 4 Independently, C6 to C6 are substituted or unsubstituted. 18 Aranediol; - R 5 It is substituted or unsubstituted C6 to C 18 Aranediol; - R 6 Selected from benzene, pyrazine, and anthracene groups; - R 7 It is unreplaced C6 to C 18 Aryl; - R 8 To R 11 Independently selected from H and unsubstituted C6 to C 18 Aryl; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

[0052] In this implementation method, m, n, p, and R 1 To R 11 As described above.

[0053] In one embodiment, the hole-blocking layer comprises a compound of formula (I). (I) In equation (I) - m and n are 0 or 1 independently; - p is 0 or 1; - m+n+p≥1; - R 1 and R 3 Independently, C6 to C6 are substituted or unsubstituted. 18 Aryl; - R 2 and R 4 Independently, C6 to C6 are substituted or unsubstituted. 18 Aranediol; - R 5 It is substituted or unsubstituted C6 to C 18 Aranediol; - R 6 Selected from phenylene group and pyrazine group; - R 7 It is unreplaced C6 to C 18 Aryl; - R 8 To R 11 Independently selected from H and unsubstituted C6 to C 18 Aryl; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

[0054] In this implementation method, m, n, p, and R 1 To R 11 As described above.

[0055] In one embodiment, the hole-blocking layer comprises a compound of formula (I). (I) In equation (I) - m and n are 0 or 1 independently; - p is 0 or 1; - m+n+p≥1; - R 1 and R 3 Independently, C6 to C6 are substituted or unsubstituted. 18 Aryl; - R 2 and R 4 Independently, C6 to C6 are substituted or unsubstituted. 18 Aranediol; - R 5 It is substituted or unsubstituted C6 to C 18 Aranediol; - R 6 Selected from phenylene group and pyrazine group; - R 7 It is unreplaced C6 to C 18 Aryl; - R 8 To R 11 Independently selected from H and unsubstituted C6 to C18 Aryl; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

[0056] In this implementation method, m, n, p, and R 1 To R 11 As described above.

[0057] Compounds of formula (I) may contain a total of 7 or more but 12 or fewer aromatic and heteroaromatic rings, and in particular may not contain a total of more than 12 aromatic and heteroaromatic rings. Compounds of formula (I) may contain a total of 8 or more but 11 or fewer aromatic and heteroaromatic rings, and in particular may not contain a total of more than 11 aromatic and heteroaromatic rings.

[0058] Compounds of formula (I) may contain one or more but three or fewer heteroaromatic rings in total, and in particular may not contain more than three aromatic and heteroaromatic rings in total. Compounds of formula (I) may contain one or two heteroaromatic rings in total, and in particular may not contain more than two heteroaromatic rings in total.

[0059] Compounds of formula (I) may have a molecular weight of 600 g / mol or greater but 1200 g / mol or less, 600 g / mol or greater but 1000 g / mol or less, or 600 g / mol or greater but 900 g / mol or less, such as about 640 g / mol to 880 g / mol.

[0060] It can be specified that the compound of formula (I) does not contain a triarylamine moiety and does not contain a carbazole moiety.

[0061] Compounds of formula (I) may have a triplet T1 energy level of 1.5 eV or greater, such as 1.5 eV or greater but 3.0 eV or less.

[0062] Compounds of formula (I) may have LUMO levels of -2.0 eV or greater but -1.6 eV or less, -1.9 eV or greater but -1.7 eV or less, or -1.85 eV or greater but -1.7 eV or less.

[0063] Compounds of formula (I) may have HOMO levels of -5.90 eV or greater but -5.10 eV or less, such as -5.85 eV or greater but -5.60 eV or less.

[0064] The compounds of formula (I) may have a band gap of 3.20 eV or greater but 4.10 eV or less, or 3.29 eV or greater but 4.07 eV or less, such as 3.73 eV or greater but 4.07 eV or less.

[0065] Compounds of formula (I) may have a dipole moment of 0 or greater but 2 D or less, such as 1.8 D or greater but 1.21 D or less.

[0066] The compounds of formula (I) may have a glass transition temperature (Tg) of 90°C or greater but less than 160°C, such as 98°C or greater but less than 150°C.

[0067] The compounds of formula (I) can be selected from E-1 to E-10. E-1 E-2 E-3 E-4 E-5 E-6 E-7 E-8 E-9 E-10.

[0068] Organic light-emitting devices

[0069] The organic light-emitting device according to the present invention comprises an anode, a cathode, a light-emitting layer, a hole-blocking layer, and an electron transport layer.

[0070] Organic light-emitting devices can be organic light-emitting diodes (OLEDs). OLEDs can be single-layer or multi-layer OLEDs.

[0071] Cavity barrier

[0072] Organic light-emitting devices include a hole-blocking layer, which is disposed between the light-emitting layer and the electron transport layer. The hole-blocking layer can also be referred to as an auxiliary electron transport layer.

[0073] A hole blocking layer may contain a compound of formula (I) according to the invention in an amount of at least 50% by weight relative to the total weight of the hole blocking layer. A hole blocking layer may contain a compound of formula (I) according to the invention in an amount of at least 60% by weight relative to the total weight of the hole blocking layer. A hole blocking layer may contain a compound of formula (I) according to the invention in an amount of at least 70% by weight relative to the total weight of the hole blocking layer. A hole blocking layer may contain a compound of formula (I) according to the invention in an amount of at least 80% by weight relative to the total weight of the hole blocking layer. A hole blocking layer may contain a compound of formula (I) according to the invention in an amount of at least 90% by weight relative to the total weight of the hole blocking layer. A hole blocking layer may contain a compound of formula (I) according to the invention in an amount of at least 95% by weight relative to the total weight of the hole blocking layer. A hole blocking layer may contain a compound of formula (I) according to the invention in an amount of at least 98% by weight relative to the total weight of the hole blocking layer. The hole blocking layer may contain a compound of formula (I) according to the invention in an amount of at least 99% by weight relative to the total weight of the hole blocking layer. The hole blocking layer may consist of a compound of formula (I) (or a mixture of two or more compounds falling within the definition of formula (I)).

[0074] The hole blocking layer is in direct contact with the electron transport layer. The hole blocking layer can also be in direct contact with the light-emitting layer. Alternatively, the hole blocking layer can be sandwiched between the light-emitting layer and the electron transport layer.

[0075] The hole blocking layer does not contain electrical dopants, that is, it does not contain electrical dopants such as n-type dopants, especially redox n-type dopants.

[0076] In this regard, the term "free of" does not exclude impurities. Impurities have no technical impact on the objectives achieved by this invention. During processing, impurities are not intentionally added to the layers.

[0077] The term “free of” a compound means that such a compound is not intentionally added to the layer during processing.

[0078] Electro-dopers, especially n-type dopers, should be understood as compounds that, when embedded in an electron transport matrix, can improve the electronic properties of the resulting organic material compared to a pure matrix under the same physical conditions, particularly improving electronic properties in terms of electron injection and / or electronic conductivity.

[0079] In the context of this invention, "embedded in the electron transport matrix" means uniformly mixed with the electron transport matrix.

[0080] The electrodopers discussed in this article are selected in particular from elemental metals, metal salts, metal complexes, and organic groups.

[0081] In one embodiment, the electrodoperbating agent is selected from alkali metal salts and alkali metal complexes; preferably from lithium salts and lithium organo-complexes; more preferably from lithium halides and lithium organo-chelates; even more preferably from lithium fluoride, lithium quinoline, lithium borate, lithium phenolate, lithium pyridyl alcohol, or from lithium complexes having Schiff base ligands; most preferably, - Lithium complexes have formula II, III, or IV:

[0082] in

[0083] A1 to A6 are selected from CH, CR, N, and O, either identically or independently. R is selected, either identically or independently, from hydrogen, halogen, alkyl, aryl, or heteroaryl groups having 1 to 20 carbon atoms; more preferably, A1 to A6 are CH. - The boronic ester / salt organic ligand is tetrakis(1H-pyrazol-1-yl)boronic ester / salt. - Phenolic esters / salts are 2-(pyridin-2-yl)phenolic esters / salts, 2-(diphenylphosphoyl)phenolic esters / salts, imidazole phenolic esters / salts, 2-(pyridin-2-yl)phenolic esters / salts, or 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolic esters / salts. - Pyridine alcohol ester / salt is 2-(diphenylphospho)pyridine-3-ol ester / salt, - Lithium Schiff bases have structures 100, 101, 102, or 103: .

[0084] According to one embodiment of the present invention, the hole blocking layer of the present invention does not contain lithium organic complexes or lithium 8-hydroxyquinoline (=LiQ).

[0085] According to one embodiment of the present invention, the hole blocking layer is metal-free, wherein the metal is preferably selected from alkali metals, alkaline earth metals, rare earth metals, and metals of the first transition period, such as Ti, V, Cr, and Mn, particularly selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, and Yb; more preferably selected from Li, Na, K, Rb, Cs, Mg, and Yb; even more preferably selected from Li, Na, Cs, and Yb; and most preferably selected from Li, Na, and Yb.

[0086] The most practical benchmark for the strength of n-type dopants is their redox potential. There are no particular restrictions on how negative the redox potential can be.

[0087] Since the reduction potential of a typical electron transport matrix used in organic semiconductors is generally in the range of about -0.8 V to about -3.1 V if measured by cyclic voltammetry relative to a ferrocene / ferrocene cation reference redox pair, the practically applicable range of the redox potential of an n-type dopant that can effectively n-type dope such a matrix is ​​a slightly wider range, namely about -0.5 V to about -3.3 V.

[0088] The measurement of redox potential is actually performed on the corresponding redox pairs composed of the reduced and oxidized forms of the same compound.

[0089] When the n-type dopant is an electrically neutral metal complex and / or an electrically neutral organic radical, its redox potential is actually measured against a redox pair formed by: (i) Electroneutral metal complexes and their cationic radicals formed by the separation of an electron from an electron from an electronneutral metal complex, or (ii) Electroneutral organic radicals and the cations formed by the separation of an electron from an electron-neutral organic radical.

[0090] Preferably, for the corresponding redox pairs consisting of the following, if measured by cyclic voltammetry relative to a ferrocene / ferrocene cation reference redox pair, the redox potential of the electrically neutral metal complex and / or the electrically neutral organic radical may have a value more negative than -0.5 V, preferably more negative than -1.2 V, more preferably more negative than -1.7 V, even more preferably more negative than -2.1 V, and most preferably more negative than -2.5 V: (i) Electroneutral metal complexes and their cationic radicals formed by the separation of an electron from an electron from an electronneutral metal complex, or (ii) Electroneutral organic radicals and the cations formed by the separation of an electron from an electron-neutral organic radical.

[0091] In a preferred embodiment, the redox potential of the n-type dopant is between a value that is about 0.5 V more positive than the reduction potential of the selected electron transport matrix and a value that is about 0.5 V more negative than it.

[0092] Suitable electrically neutral metal complexes as n-type dopants can be, for example, strongly reducing complexes of certain low oxidation state transition metals. As described in more detail in WO 2005 / 086251, particularly strong n-type dopants can be selected from, for example, Cr(II), Mo(II) and / or W(II) guanidine complexes, such as W2(hpp)4.

[0093] As described in more detail in EP 1 837 926 B1, WO 2007 / 107306, or WO 2007 / 107356, a neutral organic radical suitable as an n-type dopant can be, for example, an organic radical generated by supplying additional energy from its stable dimer, oligomer, or polymer. Elemental metal should be understood as a metal in a pure metallic state, a metallic alloy state, or a state of free atoms or metal clusters. It should be understood that a metal deposited from a metallic phase, such as a pure bulk metal, by vacuum thermal evaporation vaporizes in its elemental form. It should also be understood that if the vaporized elemental metal is deposited together with a covalent matrix, the metal atoms and / or clusters are embedded in the covalent matrix. In other words, it should be understood that any metal-doped covalent material prepared by vacuum thermal evaporation contains at least partially a metal in its elemental form.

[0094] For use in user electronic products, only metals containing stable nuclides or nuclides with extremely long radioactive decay half-lives are suitable. The nuclear stability of natural potassium is an acceptable level.

[0095] In one embodiment, the electropositive dopant absent in the hole-blocking layer is an electropositive metal selected from alkali metals, alkaline earth metals, rare earth metals, and first transition period metals Ti, V, Cr, and Mn. Preferably, the n-type dopant is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, and Yb; more preferably from Li, Na, K, Rb, Cs, Mg, and Yb; even more preferably from Li, Na, Cs, and Yb; and most preferably from Li, Na, and Yb.

[0096] The hole blocking layer may have a thickness of <50 nm, optionally between 1 nm and 30 nm, optionally between 1 nm and 10 nm, or optionally between 1 nm and 5 nm.

[0097] Other layers

[0098] According to the present invention, in addition to the layers already mentioned above, the organic light-emitting device may also include other layers. Exemplary embodiments of each layer are described below: base The substrate can be any substrate commonly used to manufacture electronic devices such as organic light-emitting diodes (OLEDs). If light is emitted through the substrate, it should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is emitted through the top surface, the substrate can be a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate. It may be specified that the substrate is opaque.

[0099] Anode electrode

[0100] The organic light-emitting device of the present invention includes an anode (anode electrode). The anode electrode can be formed by deposition or sputtering of a material used to form the anode electrode. The material used to form the anode electrode can be a high work function material to facilitate hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZnO), and zinc oxide (ZnO) can be used to form the anode electrode. The anode electrode can also be formed using metals, typically silver (Ag), gold (Au), or metal alloys.

[0101] Hole injection layer

[0102] Hole-injected layers (HILs) can be formed on the anode electrode via vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When using vacuum deposition to form HILs, the deposition conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, typically, vacuum deposition conditions can include deposition temperatures ranging from 100°C to 500°C, and 10... -8 Up to 10 -3 The pressure was 1 Torr (1 Torr equals 133.322 Pa) and the deposition rate was 0.1 nm / s to 10 nm / s.

[0103] When spin coating or printing is used to form HILs, the coating conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, heat treatment is performed to remove the solvent.

[0104] HILs can be formed from any compound commonly used to form HILs. Examples of compounds that can be used to form HILs include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethimidedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0105] HILs may contain or be composed of p-type dopants, and the p-type dopants may be selected from, but are not limited to, tetrafluorotetracyanoquinone dimethyl ether (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diethylenedipropylene nitrile) or 2,2',2''-(cyclopropane-1,2,3-triethylenedipropylene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). HILs may be selected from hole transport matrix compounds doped with p-type dopants. Typical examples of known doped hole transport materials are: copper phthalocyanine (CuPc) with a HOMO level of approximately -5.2 eV; tetrafluorotetracyanoquinone dimethane (F4TCNQ) doped with a LUMO level of approximately -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; and α-NPD doped with 2,2'-(perfluoronaphthyl-2,6-diethylenediamine)dimalonitrile. The concentration of the p-type dopant can be selected from 1 wt% to 20 wt%, more preferably from 3 wt% to 10 wt%.

[0106] The thickness of the HIL can range from about 1 nm to about 100 nm, for example, from about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL can have excellent hole injection characteristics without substantially impairing the driving voltage.

[0107] Hole transport layer

[0108] Hole transport layers (HTLs) can be formed on hollow inlets (HILs) via vacuum deposition, spin coating, slot die coating, printing, casting, and Langmuir-Blodgett (LB) deposition. When forming HTLs via vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0109] HTLs can be formed from any compound commonly used to form HTLs. Suitable compounds are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, which are incorporated herein by reference. Examples of compounds that can be used to form HTLs are: carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives, such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthyl-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine compounds, such as 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA). In these compounds, TCTA can transport holes and inhibit exciton diffusion into the EML.

[0110] The thickness of the HTL can be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, and further about 120 nm to about 140 nm. The preferred thickness of the HTL can be from 170 nm to 200 nm.

[0111] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without substantially damaging the driving voltage.

[0112] Electron blocking layer

[0113] The function of the electron blocking layer (EBL) is to prevent electrons from transferring from the emissive layer to the hole transport layer, thereby confining electrons within the emissive layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer contains a triarylamine compound. The LUMO level of the triarylamine compound can be closer to the vacuum level than the LUMO level of the hole transport layer. Compared to the HOMO level of the hole transport layer, the electron blocking layer can have a HOMO level further away from the vacuum level. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0114] If an electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0115] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency from the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds whose triplet energy level is higher than that of the phosphorescent emitter in the adjacent emitting layer. EP 2 722 908 A1 describes compounds suitable for triplet control layers, particularly triarylamine compounds.

[0116] Emissive Layer (EML)

[0117] The light-emitting layer in the organic light-emitting device according to the present invention can be a blue light-emitting layer or a green light-emitting layer.

[0118] EML can be formed on HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When using vacuum deposition or spin coating to form EML, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0119] It can be specified that the luminescent layer does not contain compounds of formula (I).

[0120] The luminescent layer (EML) can be formed by a combination of a host and a luminescent dopant. Examples of hosts are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4"-tris(carbazole-9-yl)triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis-2-naphthylanthracene (TBADN), stilbeneyl arylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolic acid)zinc (Zn(BTZ)2).

[0121] The luminescent dopant can be a phosphorescent or fluorescent luminescent material. Phosphorescent luminescent materials and those emitting light via thermally activated delayed fluorescence (TADF) are preferred due to their higher efficiency. The luminescent material can be a small molecule or a polymer.

[0122] Examples of red-emitting dopants include PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited to these. These compounds are phosphorescent; however, fluorescent red-emitting dopants can also be used.

[0123] Examples of phosphorescent green luminescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0124] Examples of phosphorescent blue emitting electron dopants are F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃, as well as terfluorene. Examples of fluorescent blue emitting electron dopants are 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe).

[0125] Based on 100 parts by weight of the host, the amount of luminescent dopant can range from about 0.01 parts by weight to about 50 parts by weight. Alternatively, the luminescent layer can be composed of a luminescent polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can exhibit excellent luminescence without substantially impairing the driving voltage.

[0126] Hole blocking layer (HBL)

[0127] In particular, if the organic light-emitting device is a series OLED or other device containing multiple stacked layers, the organic light-emitting device may contain more than one hole transport layer, that is, one or more other hole transport layers.

[0128] The hole-blocking layer can be a hole-blocking layer as defined above. Alternatively, for other HBLs, any compound commonly used to form HBLs can be used. Examples of compounds used to form HBLs include diazole derivatives, triazole derivatives, and phenanthroline derivatives.

[0129] Hole blocking layers (HBLs) can be formed on EMLs using methods such as vacuum deposition, spin coating, slot die coating, printing, casting, and LB deposition to prevent holes from diffusing into ETLs. When the EML contains phosphorescent dopants, the HBL can also have triplet exciton blocking functionality.

[0130] HBLs can have a thickness in the range of about 5 nm to about 100 nm, for example, in the range of about 5 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without substantially impairing the driving voltage.

[0131] Electron Transport Layer (ETL)

[0132] The OLED according to the present invention includes an electron transport layer (ETL).

[0133] By appropriately adjusting the energy levels of specific ETL layers, electron injection and transport can be controlled, and holes can be effectively blocked. Therefore, OLEDs can have a long lifespan.

[0134] The electron transport layer may comprise ETM materials known in the art. There are no particular limitations on compounds suitable for use in ETMs.

[0135] It can be specified that ETL includes an electron transport matrix compound and an electric dopant.

[0136] In one embodiment, the electron transport matrix compound consists of covalently bonded atoms. Preferably, the electron transport matrix compound comprises a conjugated system with at least 6 delocalized electrons, more preferably at least 10 delocalized electrons. In one embodiment, as disclosed, for example, in documents EP 1 970 371 A1 or WO 2013 / 079217 A1, the conjugated system of delocalized electrons may be contained in an aromatic or heteroaromatic structural moiety.

[0137] ETLs can contain electrically dopants, such as n-type dopants, especially redox n-type dopants.

[0138] Electro-dopers, especially n-type dopers, should be understood as compounds that, when embedded in an electron transport matrix, improve the electronic properties of the resulting organic material compared to a pure matrix under the same physical conditions, particularly improving electronic properties in terms of electron injection and / or electronic conductivity.

[0139] In the context of this invention, "embedded in the electron transport matrix" means uniformly mixed with the electron transport matrix.

[0140] Electrodopers can be selected from elemental metals, metal salts, metal complexes, and organic groups.

[0141] In one embodiment, the electrodoperbating agent is selected from alkali metal salts and alkali metal complexes; preferably from lithium salts and lithium organo-complexes; more preferably from lithium halides and lithium organo-chelates; even more preferably from lithium fluoride, lithium quinoline, lithium borate, lithium phenolate, lithium pyridyl alcohol, or from lithium complexes having Schiff base ligands; most preferably, - Lithium complexes have formula II, III, or IV:

[0142] in

[0143] A1 to A6 are selected from CH, CR, N, and O, either identically or independently. R is selected, either identically or independently, from hydrogen, halogen, alkyl, aryl, or heteroaryl groups having 1 to 20 carbon atoms; more preferably, A1 to A6 are CH. - The boronic ester / salt organic ligand is tetrakis(1H-pyrazol-1-yl)boronic ester / salt. - Phenolic esters / salts are 2-(pyridin-2-yl)phenolic esters / salts, 2-(diphenylphosphoyl)phenolic esters / salts, imidazole phenolic esters / salts, 2-(pyridin-2-yl)phenolic esters / salts, or 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolic esters / salts. - Pyridine alcohol ester / salt is 2-(diphenylphospho)pyridine-3-ol ester / salt, - Lithium Schiff bases have structures 100, 101, 102, or 103: .

[0144] According to one embodiment of the present invention, the electrodopermeable is a lithium organic complex, such as lithium 8-hydroxyquinoline (=LiQ).

[0145] It can be specified that ETL does not contain compounds of formula (I).

[0146] Electron Injection Layer (EIL)

[0147] An electron transport layer (EIL) that facilitates electron injection from the cathode into the electron transport layer stack can be formed on, preferably directly on, the electron transport layer. Examples of materials used to form the EIL or materials included in the EIL include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming a high-level electron transport layer (HIL), but the deposition and coating conditions may vary depending on the material used to form the EIL. The EIL may contain an organic matrix material doped with an n-type dopant. The matrix material may be selected from materials conventionally used as matrix materials for electron transport layers.

[0148] An EIL can be composed of multiple individual EIL sublayers. When an EIL is composed of multiple individual EIL sublayers, the number of sublayers is preferably two. Each individual EIL sublayer can contain different materials used to form the EIL.

[0149] The thickness of the EIL can be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection performance without substantially impairing the driving voltage.

[0150] It can be specified that the electron injection layer does not contain compounds of formula (I).

[0151] cathode electrode

[0152] The cathode (cathode) is formed on the electron transport layer (EIL, if present) or on the electron transport layer (ETL), preferably directly on the EIL, and preferably in direct contact with the EIL. In the context of this invention, the cathode and EIL can be considered as a functional component enabling the injection of electrons into the electron transport layer stack. The cathode electrode can be formed from a metal, alloy, conductive compound, or mixture thereof. The cathode electrode can have a low work function. For example, the cathode electrode can be formed from lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc., for example, from an alloy of Ag and Mg, such as Ag:Mg 90:10 weight / weight. Alternatively, the cathode electrode can be formed from a transparent conductive oxide such as ITO or IZO.

[0153] The thickness of the cathode electrode can range from about 5 nm to about 1000 nm, for example, from about 10 nm to about 100 nm. When the thickness of the cathode electrode is in the range of about 5 nm to about 50 nm, it can be transparent or translucent even if the cathode electrode is formed of metal or metal alloy. A transparent or translucent cathode can promote the emission of light through the cathode.

[0154] Charge generation layer (CGL)

[0155] The charge generation layer (CGL) may comprise a p-type charge generation layer (p-CGL) and an n-type charge generation layer (n-CGL). An intermediate layer may be arranged between the p-CGL and the n-CGL.

[0156] Typically, the charge generation layer is a pn junction connecting the n-type charge generation layer (electron generation layer) and the hole generation layer. Electrons are generated on the n-side of the pn junction and injected into the adjacent layer in the direction of the anode. Similarly, holes are generated on the p-side of the pn junction and injected into the adjacent layer in the direction of the cathode.

[0157] The charge-generating layer is used in series and stacked devices, such as in series or stacked OLEDs containing two or more light-emitting layers between two electrodes. In a series or stacked OLED containing two light-emitting layers, the n-type charge-generating layer provides electrons to a first light-emitting layer disposed near the anode, while the hole-generating layer provides holes to a second light-emitting layer disposed between the first light-emitting layer and the cathode.

[0158] The matrix material suitable for the hole generation layer can be any material conventionally used as a matrix material for hole injection and / or hole transport. Furthermore, the p-type dopant used for the hole generation layer can be a conventional material. For example, the p-type dopant can be selected from one of the following: tetrafluoro-7,7,8,8-tetracyanoquinone dimethyl ether (F4-TCNQ), derivatives of tetracyanoquinone dimethyl ether, axialene derivatives, iodine, FeCl3, FeF3, and SbCl5. Additionally, the host material can be selected from one of the following: N,N'-di(naphthyl-1-yl)-N,N-diphenyl-benzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD), and N,N',N'-tetranaphthyl-benzidine (TNB). The p-type charge generation layer can be composed of CNHAT.

[0159] The n-type charge generation layer may be a layer comprising a compound of formula (I). The n-type charge generation layer may be a pure n-type dopant layer, such as a metal layer, or may consist of an organic matrix material doped with an n-type dopant. In one embodiment, the n-type dopant may be an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, a transition metal, a transition metal compound, or a rare earth metal. In another embodiment, the metal may be selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. More specifically, the n-type dopant may be selected from the group consisting of Li, Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. The matrix material suitable for the electron generation layer may be a material conventionally used as a matrix material for electron injection or electron transport layers. The matrix material may be, for example, selected from the group consisting of triazine compounds, hydroxyquinoline derivatives such as tris(8-hydroxyquinoline)aluminum, benzo[a]azole derivatives, and silanecyclopentane derivatives.

[0160] According to one aspect of the invention, an electron transport layer comprising a compound of formula (I) is disposed between a first light-emitting layer and a second light-emitting layer, and an electron transport layer comprising a compound of formula (I) is disposed between the second light-emitting layer and the cathode.

[0161] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an auxiliary electron transport layer, an electron transport layer comprising a compound of formula (I); and a cathode electrode.

[0162] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an auxiliary electron transport layer, an electron transport layer comprising a compound of formula (I), an electron injection layer; and a cathode electrode.

[0163] According to various embodiments of the present invention, OLED layers can be provided disposed between the aforementioned layers, on a substrate, or on a top electrode.

[0164] In one embodiment, the organic light-emitting device according to the invention further comprises a layer containing an axialene compound and / or a quinone dimethane compound.

[0165] In one embodiment, the axial alkene compound and / or quinone dimethane compound may be substituted with one or more halogen atoms and / or with one or more electron-withdrawing groups. The electron-withdrawing group may be selected from a nitrile group, a haloalkyl group, a perhaloalkyl group, or a perfluoroalkyl group. Other examples of the electron-withdrawing group may be an acyl group, a sulfonyl group, or a phosphoryl group.

[0166] Alternatively, the acyl group, sulfonyl group, and / or phosphoryl group may comprise a halogenated and / or a perhalogenated hydrocarbon group. In one embodiment, the perhalogenated hydrocarbon group may be a perfluorohydrocarbon group. Examples of perfluorohydrocarbon groups may be perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorophenyl, and perfluorotolyl; examples of sulfonyl groups comprising halogenated hydrocarbon groups may be trifluoromethylsulfonyl, pentafluoroethylsulfonyl, pentafluorophenylsulfonyl, heptafluoropropylsulfonyl, nonafluorobutylsulfonyl, etc.

[0167] In one embodiment, the hole injection layer, hole transport layer, and / or hole generation layer may contain axial ene compounds and / or quinone dimethane compounds.

[0168] In one embodiment, the axial ene compound may have formula (XX) and / or the quinone dimethane compound may have formula (XXIa) or (XXIb): (XX) (XXIa) (XXIb), Wherein (as an exception to the above description) R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 11 R 12 R 15R 16 R 20 R 21 Independently selected from the above electron-withdrawing groups, and R 9 R 10 R 13 R 14 R 17 R 18 R 19 R 22 R 23 and R 24 It is independently selected from H, halogens and the above-mentioned electron-withdrawing groups.

[0169] Methods for fabricating organic light-emitting devices

[0170] According to another aspect, the present invention relates to a method for preparing an organic light-emitting device according to the invention, wherein the method includes the step of depositing a compound of formula (I) according to the invention onto a solid support.

[0171] Methods for deposition may include: - Deposition via vacuum thermal evaporation; - Deposition via solution processing, preferably the processing being selected from spin coating, printing, casting; and / or - Slit-type die coating.

[0172] Device

[0173] According to another aspect, the present invention relates to a display device or lighting device comprising an organic light-emitting device according to the invention, preferably comprising at least two organic light-emitting devices according to the invention.

[0174] The display device can be a television, tablet computer, or mobile phone.

[0175] Compound of formula (II)

[0176] According to another aspect, the present invention relates to a compound of formula (II). (II).

[0177] Unless otherwise explicitly stated, all compounds, especially those of formula (II) shown herein, including compounds, groups, parts, substituents, etc., particularly those of formula (II) shown by structural formula, systematic name, etc., encompass their respective parts and fully deuterated derivatives, where it may be specified that substitutions other than deuteration are excluded. If a compound, group, part, substituent, etc., is mentioned as unsubstituted, this does not exclude deuteration substitution.

[0178] m and n are independently 0 or 1.

[0179] p is 0, 1, or 2.

[0180] m+n+p≥1. (m+n+p) can be an integer from 1 to 4. (m+n+p) can be an integer from 1 to 3. (m+n+p) can be 1 or 2.

[0181] R 1 and R 3 It is either a substituted or unsubstituted phenyl group.

[0182] In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C5 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C4 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C3 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C2 alkyl groups. In R 1 and R 3 In the case where one or more of the components are substituted, each of the one or more substituents may be a methyl group.

[0183] In R 1 and R 3 If one or more of them are replaced, the corresponding R 1 and / or R 3 (Including all substituents) can be independently selected from the following groups IIa-1 to IIa-8. IIa-1, IIa-2, IIa-3, IIa-4, IIa-5, IIa-6 IIa-7 IIa-8, in" " is the binding position in equation (II), that is, with R 2 (for R) 1 ) or R 4 (for R) 3 The combination position of ).

[0184] In R 1 and R 3 If one or more of them are replaced, the corresponding R 1 and / or R 3 (Including all substituents) can be independently selected from the following groups IIa-2 to IIa-8. IIa-2, IIa-3, IIa-4, IIa-5, IIa-6 IIa-7 IIa-8, in" " is the binding position in equation (II), that is, with R 2 (for R) 1 ) or R 4 (for R) 3 The combination position of ).

[0185] In R 1 and R 3 If one or more of them are replaced, the corresponding R 1 and / or R 3 (Including all substituents) can be independently selected from the following groups IIa-1 to IIa-3.

[0186] IIa-1, IIa-2, IIa-3, in" " is the binding position in equation (II), that is, with R 2 (for R) 1 ) or R 4 (for R) 3 The combination position of ).

[0187] It may be specified that one or more of the CH3 groups in IIa-1 to IIa-8 are replaced by C2 to C6 alkyl, C2 to C4 alkyl, C2 to C3 alkyl or C2 alkyl.

[0188] R 2 and R 4Independently, it is either a substituted or unsubstituted phenylene group. R 2 and R 4 It can be a substituted or unsubstituted phenylene group, independently. R 2 and R 4 It can be an unsubstituted phenylene group independently. R 2 and R 4 Each of them is an unsubstituted meta-phenylene group.

[0189] If p is 1, then R 5 The following groups, IIb-1 and IIb-2, can be selected. IIb-1, IIb-2, One of them is " 1” is the binding position of the following groups in formula (II).

[0190] and" 2” is related to R 6 The binding sites, wherein the corresponding IIb-1 to IIb-6 may or may not be substituted.

[0191] If p is 2, then the two R 5 They can be combined to form parts IIb-3 to IIb-5. IIb-3, IIb-4, IIb-5, One of them is " 1” is the binding position of the following groups in formula (II).

[0192] and" 2” is related to R 6 The binding sites, wherein the corresponding IIb-3 to IIb-6 may or may not be substituted.

[0193] In R 2 R 4 and R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups. In R 2 R 4 and R 5 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C5 alkyl groups. In R 2 R 4 and R 5In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C4 alkyl groups. In R 2 R 4 and R 5 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C3 alkyl groups. In R 2 R 4 and R 5 In the case where one or more of the components are substituted, the one or more substituents may independently be C1 to C2 alkyl groups. In R 2 R 4 and R 5 In the case where one or more of the components are substituted, each of the one or more substituents may be a methyl group.

[0194] In R 2 R 4 and R 5 If one or more of them are replaced, the corresponding R 2 R 4 and R 5 (Including all substituents) may be independently selected from the following groups IIc-1 to IIc-9, or contain one of the following groups IIc-1 to IIc-9. IIc-1, IIc-2, IIc-3, IIc-4, IIc-5, IIc-6 IIc-7 IIc-8, IIc-9, in" 1” and “ 2” is the position where it connects with the rest of the equation (II).

[0195] Including all substituents (if any), if p=1, then R 5 It can be selected from one of the following groups, IId-4 or IId-5; or, in the case of p=2, both R 5 It can be combined to form any one of IId-1 to IId-3 (including all substituents). IId-1, IId-2, IId-3, IId-4, IId-5, in" 1” is the binding position of the following groups in formula (II).

[0196] and" 2” is related to R 6 The position of the combination.

[0197] R 6 Selected from phenylene group, pyrazine group, and anthracene group. R 6 It can be selected from benzene and pyrazine.

[0198] R 6 It can be selected from one of the following groups IIe-1 to IIe-7. IIe-1, IIe-2, IIe-3, IIe-4, IIe-5, IIe-6 IIe-7, in" 1” is in equation (II) and R 5 The binding position, and " 2” is related to R 7 The position of the combination.

[0199] R 6 It can be selected from one of the following groups IIe-1 to IIe-6. IIe-1, IIe-2, IIe-3, IIe-4, IIe-5, IIe-6, in" 1” is in equation (II) and R 5 The binding position, and " 2” is related to R 7 The position of the combination.

[0200] In IIe-1 to IIe-7, R 8 To R 11 Can be used with anything other than those marked " 1” and “ It can bond with any carbon atom other than the 2” carbon atom. If it can bond with R 8 To R11 If there are fewer than four carbon atoms bonded, then R 8 To R 11 One or more of them may not exist. For example, if it is possible to be with R 8 To R 11 There are only two carbon atoms involved in the bonding, such as in IIe-4, then R 10 and R 11 It does not exist, and the corresponding group has the following formula IIe-4.1 IIe-4.1.

[0201] R 7 It is an unsubstituted phenyl group.

[0202] R 8 To R 11 Independently selected from H and unsubstituted phenyl groups.

[0203] If R 6 If it is a benzene group, then R can be specified. 8 To R 11 One, two, or three of them are H, and the rest are R. 8 To R 11 It is an unsubstituted phenyl group.

[0204] If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least one of them is an unsubstituted phenyl group, and the unsubstituted phenyl group is located in the phenylene group (R). 6 ) and R 5 The adjacent position of the combination position.

[0205] If R 6 If it is a benzene group, then R can be specified. 8 To R 11 At least two of them are unsubstituted phenyl groups, and these unsubstituted phenyl groups are in the ortho position relative to each other.

[0206] As mentioned in the two paragraphs above, R 8 To R 11 At least one of them is an aryl group and is in the phenylene group (R 6 ) and R 5 The characteristics of the adjacent positions of the binding position, and R 8 To R 11 At least two of them are phenyl and these phenyl groups can be used alternatively or together (and / or) with respect to features that are adjacent to each other.

[0207] If R 6 If it is a benzene group, then " "is with R" 5The following part of the joint position

[0208] It can be one of the following groups IIf-1 to IIf-3. IIf-1、 IIf-2、 IIf-3.

[0209] If R 6 If it is a pyrazine subunit, then " "is with R" 5 The following part of the joint position

[0210] It could be I1g-1 IIg-1.

[0211] If R 6 If it is anthracene subunit, then " "is with R" 5 The following part of the joint position

[0212] It can be IIh-1 IIh-1.

[0213] R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 2 R 4 and R 5 At least one of them is substituted with at least one C1 to C6 alkyl substituent. In one embodiment, R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 5 It is substituted with at least one C1 to C6 alkyl substituent. In one embodiment, R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 2 R 4 and R 5 At least one of them is substituted with at least one C1 to C6 alkyl substituent. In one embodiment, R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 5It is substituted with at least one C1 to C6 alkyl substituent. In one embodiment, R 1 and R 3 At least one of them is substituted by one or two C1 to C6 alkyl substituents; and / or R 5 It is substituted with one or two C1 to C6 alkyl substituents. In this respect, the C1 to C6 alkyl substituents can be selected independently as described above.

[0214] According to one embodiment, a compound of formula (II) is provided. (II) In equation (II) - m and n are 0 or 1 independently; - p is 0, 1, or 2; - m+n+p≥1; - R 1 and R 3 It is either a substituted or unsubstituted phenyl group; - R 2 and R 4 It is either a substituted or unsubstituted phenylene group; - Each R 5 It is either a substituted or unsubstituted phenylene group; - R 6 Selected from benzene, pyrazine, and anthracene groups; - R 7 It is an unsubstituted phenyl group; - R 8 To R 11 Independently selected from H and unsubstituted phenyl groups; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

[0215] In this implementation method, m, n, p, and R 1 To R 11 As described above.

[0216] According to one embodiment, a compound of formula (II) is provided. (II) In equation (II) - m and n are 0 or 1 independently; - p is 0, 1, or 2; - m+n+p≥1; - R 1 and R 3 It is either a substituted or unsubstituted phenyl group; - R 2 and R 4 It is either a substituted or unsubstituted phenylene group; - Each R 5 It is either a substituted or unsubstituted phenylene group; - R 6 Selected from phenylene group and pyrazine group; - R 7 It is an unsubstituted phenyl group; - R 8 To R 11 Independently selected from H and unsubstituted phenyl groups; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

[0217] In this implementation method, m, n, p, and R 1 To R 11 As described above.

[0218] According to one embodiment, a compound of formula (II) is provided. (II) In equation (II) - m and n are 0 or 1 independently; - p is 0, 1, or 2; - m+n+p≥1; - R 1 and R 3 It is either a substituted or unsubstituted phenyl group; - R 2 and R 4 It is either a substituted or unsubstituted phenylene group; - Each R 5It is either a substituted or unsubstituted phenylene group; - R 6 Selected from phenylene group and pyrazine group; - R 7 It is an unsubstituted phenyl group; - R 8 To R 11 Independently selected from H and unsubstituted phenyl groups; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

[0219] In this implementation method, m, n, p, and R 1 To R 11 As described above.

[0220] Compounds of formula (II) may contain a total of 7 or more but 12 or fewer aromatic and heteroaromatic rings, and in particular may not contain a total of more than 12 aromatic and heteroaromatic rings. Compounds of formula (II) may contain a total of 8 or more but 11 or fewer aromatic and heteroaromatic rings, and in particular may not contain a total of more than 11 aromatic and heteroaromatic rings.

[0221] Compounds of formula (II) may contain one or more but three or fewer heteroaromatic rings in total, and in particular may not contain more than three aromatic and heteroaromatic rings in total. Compounds of formula (II) may contain one or two heteroaromatic rings in total, and in particular may not contain more than two heteroaromatic rings in total.

[0222] Compounds of formula (II) may have a molecular weight of 600 g / mol or greater but 1200 g / mol or less, 600 g / mol or greater but 1000 g / mol or less, or 600 g / mol or greater but 900 g / mol or less, such as about 640 g / mol to 880 g / mol.

[0223] The compound of formula (II) may be specified to not contain a triarylamine moiety and not contain a carbazole moiety.

[0224] Compounds of formula (II) may have a triplet T1 energy level of 1.5 eV or greater, such as 1.5 eV or greater but 3.0 eV or less.

[0225] Compounds of formula (II) may have LUMO levels of -2.0 eV or greater but -1.6 eV or less, -1.9 eV or greater but -1.7 eV or less, or -1.85 eV or greater but -1.7 eV or less.

[0226] Compounds of formula (II) may have HOMO levels of -5.90 eV or greater but -5.10 eV or less, such as -5.85 eV or greater but -5.60 eV or less.

[0227] Compounds of formula (II) may have a band gap of 3.20 eV or greater but 4.10 eV or less, or 3.29 eV or greater but 4.07 eV or less, such as 3.73 eV or greater but 4.07 eV or less.

[0228] Compounds of formula (II) may have a dipole moment of 0 or greater but 2 D or less, such as 1.8 D or greater but 1.21 D or less.

[0229] Compounds of formula (II) may have a glass transition temperature (Tg) of 90°C or greater but less than 160°C, such as 98°C or greater but less than 150°C.

[0230] The compounds of formula (II) may be selected from E-2 to E-10. E-2 E-3 E-4 E-5 E-6 E-7 E-8 E-9 E-10.

[0231] General definition

[0232] Unless otherwise explicitly stated, the parts of the compounds described herein, especially the parts of the compounds of formulas (I) and (II), may be substituted with one or more D (deuterium).

[0233] In this specification, unless otherwise defined, "alkyl group" may refer to an aliphatic hydrocarbon group. An alkyl group may refer to a "saturated alkyl group" without any double or triple bonds. As used herein, the term "alkyl" should encompass straight-chain as well as branched and cyclic alkyl groups. For example, C3-alkyl may be selected from n-propyl and isopropyl. Similarly, C4-alkyl encompasses n-butyl, sec-butyl, and tert-butyl. Likewise, C6-alkyl encompasses n-hexyl and cyclohexyl.

[0234] Unless otherwise explicitly stated, as indicated by the asterisk used in this article. "" indicates the bonding position where the corresponding marked part is bonded to another part.

[0235] As used herein, the term "aryl" or "arylene" shall encompass phenyl (C6-aryl), fused aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, and tetraphenylene. It also encompasses biphenyl and oligophenyl or polyphenylene such as terphenyl, phenyl-substituted biphenyl, phenyl-substituted terphenyl (e.g., tetraphenylphenyl group), etc. "Arylene," and correspondingly "heteroarylene," refers to a group connected to two additional moieties. In this specification, the term "aryl group" or "arylene group" may refer to a group comprising at least one hydrocarbon aromatic moiety, and all elements of said hydrocarbon aromatic moiety may have conjugated p orbitals, such as phenyl groups, naphthyl groups, anthracene groups, phenanthryl groups, pyrene groups, fluorene groups, etc. It also encompasses spirocyclic compounds in which two aromatic moieties are connected to each other via spiro atoms, such as 9,9'-spirodi[9H-fluorene]yl. Aryl or arylene groups may contain monocyclic or polycyclic (i.e., linked by sharing adjacent carbon atom pairs) functional groups.

[0236] As used herein, the term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a heteroatom. The term "heteroaryl" can refer to an aromatic heterocycle having at least one heteroatom, and all elements of the hydrocarbon heteroaromatic moiety may have conjugated p orbitals. The heteroatom may be selected from N, O, S, B, Si, P, Se, preferably from N, O, and S. The heteroaromatic alkyl ring may contain at least 1 to 3 heteroatoms. Preferably, the heteroaromatic alkyl ring may contain at least 1 to 3 heteroatoms independently selected from N, S, and / or O. As in the case of "aryl" / "aromatic alkyl alkyl," the term "heteroaryl" includes, for example, a spirocyclic compound in which two aromatic moieties are linked to each other, such as spiro[fluorene-9,9'-xanthine]. Other exemplary heteroaryl groups are diazine, triazine, dibenzofuran, dibenzothiofuran, acridine, benzoacridine, dibenzoacridine, etc.

[0237] As used herein, the term "alkenyl" refers to a group containing a carbon-carbon double bond -CR 1 =CR 2 R 3 .

[0238] As used herein, the term "fully halogenated" refers to a hydrocarbon group in which all hydrogen atoms in the hydrocarbon group are replaced by halogen (F, Cl, Br, I) atoms.

[0239] As used herein, the term "alkoxy" refers to a structural segment of the formula –OR, where R is a hydrocarbon group, preferably an alkyl or cycloalkyl group.

[0240] As used herein, the term "thioalkyl" refers to a structural segment of formula -SR, where R is a hydrocarbon group, preferably an alkyl or cycloalkyl group.

[0241] C n - The subscript 'n' in a heteroaryl group refers only to the number of carbon atoms, excluding the number of heteroatoms. In this context, it is clear that C3 heteroaryl groups are aromatic compounds containing three carbon atoms, such as pyrazoles, imidazoles, thiazoles, etc.

[0242] As used herein, the term "heteroaryl" should encompass pyridine, quinoline, benzoquinoline, quinazoline, benzoquinazoline, pyrimidine, pyrazine, triazine, benzimidazole, benzothiazole, benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, xanthan, phenazine, benzoacridine, dibenzoacridine, etc.

[0243] In this specification, the term single bond refers to a direct bond.

[0244] As used herein, the term "fluorinated" refers to a hydrocarbon group in which at least one hydrogen atom is replaced by a fluorine atom. A fluorinated group in which all hydrogen atoms are replaced by fluorine atoms is called a perfluorinated group, and is specifically referred to by the term "fluorinated".

[0245] According to the present invention, if one of the hydrogen atoms contained in the group is replaced by another group, the group is "replaced" by another group, wherein the other group is a substituent.

[0246] According to this disclosure, as an exemplary example, the use of any group A in the formula illustrates the following binding scenarios:

[0247] Group A can bind to any suitable bonding site. This applies when the bond of A crosses more than one ring.

[0248] Group A can bind to any suitable bonding site on any of the rings through which the bond passes.

[0249] According to the present invention, the expression "between" regarding a layer being between two other layers does not preclude the existence of an additional layer that may be arranged between one of the two other layers. According to the present invention, the expression "direct contact" regarding two layers in direct contact with each other means that no other layer is arranged between the two layers. A layer deposited on top of another layer is considered to be in direct contact with that layer.

[0250] The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with the two adjacent layers.

[0251] Regarding the hole transport layer of the present invention, the compound mentioned in the experimental section is the most preferred.

[0252] Lighting devices can be any device used for illumination, irradiation, signal transmission, or projection. They are correspondingly classified as lighting devices, irradiation devices, signal transmission devices, and projection devices. Lighting devices typically consist of the following components: a light radiation source, a device that transmits radiant flux into space in the desired direction, and a housing that connects the components into a single unit and protects the radiation source and light transmission system from environmental damage and influences.

[0253] According to another aspect, the organic electroluminescent device according to the invention comprises two, three, or more light-emitting layers. OLEDs comprising more than one light-emitting layer are also described as tandem OLEDs or stacked OLEDs.

[0254] Organic light-emitting devices (OLEDs) can be bottom-emitting or top-emitting devices. OLEDs can emit light through a transparent anode or a transparent cathode.

[0255] Another aspect relates to a device comprising at least one organic light-emitting device (OLED).

[0256] Devices that include organic light-emitting diodes are, for example, displays or lighting panels.

[0257] In this invention, unless otherwise defined in the claims or elsewhere in this specification, the terms defined below shall be used with those definitions.

[0258] In the context of this specification, the terms “different” or “different from” in relation to matrix materials mean that the matrix materials are different in their structural formula.

[0259] The terms “OLED” and “organic light-emitting diode” are used together and have the same meaning. As used herein, the term “organic electroluminescent device” can include both organic light-emitting diodes and organic light-emitting transistors (OLETs).

[0260] As used herein, “percentage by weight,” “% by weight,” “percentage by weight,” “% by weight,” and variations thereof mean the weight of a composition, component, substance, or reagent expressed as the weight of the component, substance, or reagent of the corresponding electron transport layer divided by the total weight of the corresponding electron transport layer and multiplied by 100. It should be understood that the total weight percentage of all components, substances, and reagents of the corresponding electron transport layer and electron injection layer is selected so that it does not exceed 100% by weight.

[0261] As used herein, “volume percentage,” “volume %,” “percentage by volume,” “%volume,” and variations thereof mean the volume of a composition, component, substance, or reagent expressed as the volume of the component, substance, or reagent in the corresponding electron transport layer divided by the total volume of the corresponding electron transport layer and multiplied by 100. It should be understood that the total volume percentage of all components, substances, and reagents in the cathode layer is selected such that it does not exceed 100% volume.

[0262] Whether explicitly stated or not, this document assumes that all numerical values ​​are modified by the term "about". As used herein, the term "about" refers to a possible variation in quantity. Whether or not modified by the term "about", the claims include equivalents of the stated quantity.

[0263] It should be noted that, unless otherwise expressly stated, the singular forms “a,” “an,” “the,” and “the” used in this specification and claims include plural indicators.

[0264] The terms "does not contain," "does not contain," and "does not include" do not exclude impurities. Impurities have no technical impact on the objectives achieved by this invention.

[0265] In the context of this specification, the terms "substantially non-luminescent" or "non-luminescent" mean that the contribution of the compound or layer to the visible emission spectrum from the device is less than 10%, preferably less than 5%, relative to the visible emission spectrum. A visible emission spectrum is an emission spectrum having a wavelength of about ≥380 nm to about ≤780 nm.

[0266] Preferably, the hole-blocking layer comprising the compound of formula (I) is substantially non-luminescent or non-luminescent.

[0267] The operating voltage, also known as U, is 10 milliamperes per square centimeter (mA / cm²). 2 The following measurements are in volts (V).

[0268] Candela / Ampere efficiency is also known as cd / A efficiency or C eff At 10 mA / cm² 2 The following measurements are in units of candelas per ampere.

[0269] External quantum efficiency, also known as EQE, is measured as a percentage (%).

[0270] Color spaces are described using coordinates CIE-x and CIE-y (International Commission on Illumination 1931). CIE-y is particularly important for blue light emission. A smaller CIE-y value indicates a deeper blue. Efficiency values ​​are compared at the same CIE-y value.

[0271] The highest occupied molecular orbital, also known as the HOMO, and the lowest unoccupied molecular orbital, also known as the LUMO, are measured in electron volts (eV).

[0272] The terms “OLED,” “organic light-emitting diode,” “organic light-emitting device,” “organic optoelectronic device,” and “organic light-emitting diode” are used together and have the same meaning.

[0273] The terms “lifespan” and “service life” are used together and have the same meaning.

[0274] The anode and cathode can be described as an anode electrode / cathode, or an anode electrode / cathode, or an anode electrode layer / cathode electrode layer.

[0275] Room temperature, also known as ambient temperature, is 23°C.

[0276] In the following description, the implementation methods will be illustrated with reference to embodiments. However, the present invention is not limited to the following embodiments. Exemplary aspects will now be referred to in detail. Attached Figure Description

[0277] In the described embodiments, the components described above, as well as the claimed components and the components used according to the invention, have no particular exceptions in terms of their size, shape, material selection, and technical concept, thereby allowing the application of selection criteria known in the relevant field without limitation.

[0278] Further details, features, and advantages of the invention are disclosed in the dependent claims and the following description of the various accompanying drawings, which illustrate preferred embodiments of the invention by way of example. However, any embodiment is not necessarily representative of the full scope of the invention, and therefore the scope of the invention is to be interpreted with reference to the claims and this document. It should be understood that the foregoing general description and the following detailed description are merely exemplary and explanatory, and are intended to provide further explanation of the claimed invention.

[0279] Figure 1 This is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0280] Figure 2This is a schematic cross-sectional view of an OLED comprising a charge generation layer and two light-emitting layers according to an exemplary embodiment of the present invention.

[0281] The accompanying drawings will be described in more detail below with reference to embodiments. However, the present invention is not limited to the following drawings.

[0282] In this document, when a first element is referred to as being formed or arranged "on" or "above" a second element, the first element may be arranged directly on the second element, or one or more other elements may be arranged therebetween. When a first element is referred to as being "directly" formed or arranged "on" or "above" a second element, no other elements are arranged therebetween.

[0283] Figure 1 This is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emissive layer (EML) 150, a hole blocking layer (HBL) 155, and an electron transport layer (ETL) 160. The electron transport layer (ETL) 160 is formed on the HBL 155. The HBL 155 comprises a compound of formula (I). An electron injection layer (EIL) 180 is disposed on the electron transport layer (ETL) 160. A cathode 190 is directly disposed on the electron injection layer (EIL) 180.

[0284] Figure 2 This is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 2 and Figure 1 The difference is that, Figure 2 The OLED 100 also includes a charge generation layer (CGL) and a second light-emitting layer (151).

[0285] refer to Figure 2OLED 100 includes a substrate 110, an anode 120, a first hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first light-emitting layer (EML) 150, a first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, an n-type charge generation layer (n-type CGL) 185, a hole generation layer (p-type charge generation layer; p-type GCL) 135, a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second light-emitting layer (EML) 151, a second hole blocking layer (HBL) 156 as a hole blocking layer comprising a compound of formula (I), a second electron transport layer (ETL) 161, an alkali metal complex, a second electron injection layer (EIL) 181, and a cathode 190.

[0286] Despite Figure 1 and Figure 2 Not shown, but a sealing layer may be additionally formed on the cathode electrode 190 to seal the OLED 100. Furthermore, various other modifications may be made thereto.

[0287] The following describes the implementation in more detail with reference to the embodiments. However, this disclosure is not limited to the following embodiments.

[0288] Experimental Section

[0289] Melting point

[0290] The melting point (mp) was determined as the peak temperature based on the DSC curve measured by TGA-DSC as described above or a separate DSC measurement (MettlerToledo DSC822e, where the sample was heated from room temperature to complete melting at a heating rate of 10 K / min under a pure nitrogen flow. Samples of 4 to 6 mg were placed in a 40 µL covered Mettler Toledo aluminum dish with a <1 mm hole punched in the cover).

[0291] Glass transition temperature

[0292] As described in DIN EN ISO 11357 published in March 2010, the glass transition temperature (Tg) is measured in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen atmosphere and with a heating rate of 10 K / min.

[0293] Standard starting temperature

[0294] Standard starting temperature (T) ROThe concentration was determined by loading 100 mg of the compound into a VTE source. As a VTE source, a point source of organic materials provided by Kurt J. Lesker Company (www.Lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com) can be used. In amounts less than 10 mg... -5 The VTE source was heated at a constant rate of 15 K / min under a pressure of millibars, and the internal temperature of the source was measured using thermocouples. The evaporation of the compound was detected using a QCM detector, which also detected the deposition of the compound on a quartz crystal of the detector. The deposition rate on the quartz crystal was... Measurements were taken in units of / s. To determine the standard onset temperature, the deposition rate was plotted against the VTE source temperature. The standard onset is the temperature at which significant deposition occurs on the QCM detector. To obtain accurate results, the VTE source was heated and cooled three times, and only the results from the second and third runs were used to determine the standard onset temperature.

[0295] To effectively control the evaporation rate of organic compounds, a standard onset temperature can be set within the range of 200 to 255°C. If the standard onset temperature is below 200°C, evaporation may be too rapid and therefore difficult to control. If the standard onset temperature is above 255°C, the evaporation rate may be too low, which could result in a low cycle time, and the organic compounds in the VTE source may decompose due to prolonged exposure to high temperatures.

[0296] The standard onset temperature is an indirect measure of a compound's volatility. The higher the standard onset temperature, the lower the compound's volatility.

[0297] reduction potential

[0298] The redox potential was determined by cyclic voltammetry using a Metrohm PGSTAT30 potentiostat and MetrohmAutolab GPES software at room temperature. The redox potential given for a specific compound was measured as follows: in an argon-degassed, dry 0.1 M THF solution of the experimental material, under an argon atmosphere, with a 0.1 M tetrabutylammonium hexafluorophosphate supporting electrolyte between platinum working electrodes, and using an Ag / AgCl pseudo-standard electrode (Metrohm silver rod electrode) composed of silver wire coated with silver chloride and directly immersed in the measurement solution at a scan rate of 100 mV / s. The first run was performed within the widest range of potentials set on the working electrodes, and the range was adjusted appropriately in subsequent runs. The last three runs were performed by adding ferrocene (0.1 M concentration) as a standard. The average potential corresponding to the cathode and anodic peaks of the compound under study, after subtracting the value for the standard Fc, was calculated. +The values ​​reported above were finally obtained by averaging the observed cathode and anodic potentials of the / Fc redox couple. All the compounds studied, as well as the reported comparative compounds, exhibited well-defined reversible electrochemical behavior.

[0299] dipole moment

[0300] The dipole moment of a molecule containing N atoms It is given by the following formula:

[0301] in and It represents the partial charge and position of atom i in the molecule.

[0302] The dipole moment is determined by the semi-empirical molecular orbital method.

[0303] As implemented in the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the hybrid functionals B3LYP and 6-31G are used in the gas phase. Basis sets are used to optimize the geometry of the molecular structure. If more than one conformation is feasible, the conformation with the lowest total energy is selected to determine the bond lengths of the molecule.

[0304] Calculated HOMO, LUMO, and T1 triplet energy levels

[0305] The HOMO, LUMO, and T1 triplet states were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The calculations were performed by applying the hybrid functionals B3LYP and 6-31G in the gas phase. The basis set determines the optimal geometry of the molecular structure and the HOMO, LUMO, and T1 triplet energy levels. If more than one conformation is feasible, the conformation with the lowest total energy is selected.

[0306] Synthesis steps

[0307] (E-1)-2-(3,5-dimethyl-4''-phenyl-[1,1':3',1'':3'',1'''-tetraphenyl]-5'-yl)-4,6-diphenyl-1,3,5-triazine

[0308] Step 1. 2-(4-Chlorophenyl)-3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazine

[0309] A three-necked round-bottom flask was rinsed with nitrogen and filled with 1 equivalent (100.0 g) of 2-(3-bromo-5-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (CAS 1073062-42-6), 1 equivalent (92.7 g) of 2-([1,1':2',1''-terphenyl]-4'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentane (CAS 2144472-52-4), 0.02 equivalent (5.5 g) of tetra(triphenylphosphine)palladium(0) (CAS 14221-01-3), and 2 equivalents (65.4 g) of potassium carbonate (CAS 584-08-7). A degassed mixture of 1 L THF and 250 mL water was added. The reaction was carried out overnight at 65 °C under a nitrogen atmosphere. After cooling to room temperature, a beige suspension was formed. The original solid material was filtered, washed with water and methanol, and dried under low pressure. The product was dissolved in 1.5 L of chloroform at elevated temperature and hot-filtered through a silica pad. After solvent evaporation, the product was obtained as a white powder. Yield: 101.0 g (75%). (LC-MS: 572.1).

[0310] Step 2. 2-(3,5-Dimethyl-4''-phenyl-[1,1':3',1'':3'',1'''-tetraphenyl]-5'-yl)-4,6-diphenyl-1,3,5-triazine

[0311] Rinse a three-necked round-bottom flask with nitrogen and add 1 equivalent (10.0 g) of 2-(5-chloro-4'-phenyl-[1,1':3',1''-terphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (CAS waiver), 1.1 equivalent (2.9 g) of 3,5-dimethylphenylboronic acid (CAS 172975-69-8), 0.02 equivalent (0.2 g) of chloro(crotonyl)(2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl)palladium(II) (CAS 1798781-99-3), and 2 equivalent (7.4 g) of potassium phosphate (CAS 7778-53-2). Add a degassed mixture of 80 ml dialkylene and 20 ml water. React under nitrogen atmosphere at reflux overnight. A thick suspension forms. The reaction mixture was cooled and filtered, and the original solid material was washed with dichloromethane, water, and methanol. The product was then dissolved in 400 mL of chloroform, dried over MgSO4, and filtered through a silica pad. Final purification was performed by sublimation. White powder. Yield: 7.8 g (71%). (LC-MS: 642.2).

[0312] (E-2)-2-(3,5-dimethylphenyl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-4'''-yl)-1,3,5-triazine

[0313] Step 1. 2-(4-chlorophenyl)-4-(3,5-dimethylphenyl)-6-phenyl-1,3,5-triazine

[0314] A three-necked round-bottom flask was rinsed with nitrogen and filled with 1 equivalent (30.0 g) of 2-chloro-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (CAS 30894-93-0), 1.1 equivalent (16.4 g) of 3,5-dimethylphenylboronic acid (CAS 172975-69-8), 0.02 equivalent (2.3 g) of tetra(triphenylphosphine)palladium(0) (CAS 14221-01-3), and 2 equivalent (27.4 g) of potassium carbonate (CAS 584-08-7). A degassed mixture of 400 ml dialkylene and 100 ml water was added. The reaction was carried out overnight at 65 °C under a nitrogen atmosphere. After cooling to room temperature, a yellow suspension was formed. The original solid material was filtered, washed with dialkylene, acetone, water, and methanol, and dried under low pressure. The product was dissolved in 1 L of DCM and filtered through a silica pad. After solvent evaporation, the product was obtained as a white powder. Yield: 28.9 g (78%). (LC-MS: 372.1).

[0315] Step 2. 2-(3,5-Dimethylphenyl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-4'''-yl)-1,3,5-triazine

[0316] Rinse the three-necked round-bottom flask with nitrogen and add 1.0 equivalent (12.4 g) of 2-(4-chlorophenyl)-4-(3,5-dimethylphenyl)-6-phenyl-1,3,5-triazine (no CAS), 1.05 equivalent (20.5 g) of 4,4,5,5-tetramethyl-2-(3',4',5'-triphenyl-[1,1':2',1''-terphenyl]-3-yl)-1,3,2-dioxaborane (CAS 872118-08-6), 0.02 equivalent (0.4 g) of chloro(crotonyl)(2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl)palladium(II) (CAS1798781-99-3), and 2.0 equivalent (14.1 g) of potassium phosphate (CAS 7778-53-2). Add 120 ml of a degassed mixture of dialkylene and 30 ml of water. Initiate the reaction at 70 °C for 2 hours under a nitrogen atmosphere. After cooling to room temperature, a thick gray suspension forms. Filter the original solid material and wash with dialkylene, water, and methanol. Dissolve the product in 850 ml of chloroform and filter through a silica pad. Remove the solvent under reduced pressure and stir the solid in a mixture of hexane and methanol (5%). Filter and dry under vacuum. Final purification is achieved by sublimation. White powder. Yield: 26.2 g (99%). (LC-MS: 794.3).

[0317] (E-3)-2-(2',6'-dimethyl-[1,1'-biphenyl]-3-yl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,5-triazine

[0318] Step 1. 2-(3-Chlorophenyl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,5-triazine

[0319] Rinse the three-necked round-bottom flask with nitrogen and fill it with 1.05 equivalents (8.3 g) of 2-chloro-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine (CAS 2125473-29-0), 1.0 equivalents (17.3 g) of 4,4,5,5-tetramethyl-2-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,2-dioxaboranecyclopentane (CAS2032365-26-5), 0.02 equivalents (0.4 g) of [1,1'-bis(diphenylphosphine)ferrocene]dichloropalladium(II) (CAS72287-26-4), and 2 equivalents (7.2 g) of potassium carbonate (CAS 584-08-7). A degassed mixture of 200 ml dialkylene and 50 ml water was added. The reaction was carried out overnight at 55 °C under a nitrogen atmosphere. After cooling to room temperature, an orange suspension was formed. The original solid material was filtered, washed with dialkylene, water, methanol, and hexane, and dried under low pressure. The product was dissolved in 500 ml DCM and filtered through a silica pad. The solvent was evaporated, and the solid was stirred in a mixture of 100 ml chloroform and 150 ml methanol. After filtration and drying, the product was given as a white powder. Yield: 15.6 g (75%). (LC-MS: 800.2).

[0320] Step 2. 2-(2',6'-dimethyl-[1,1'-biphenyl]-3-yl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,5-triazine

[0321] Rinse a three-necked round-bottom flask with nitrogen and fill it with 1.0 equivalent (5.5 g) of 2-(3-chlorophenyl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,5-triazine (CAS waiver), 2.5 equivalent (2.7 g) of 2,6-dimethylphenylboronic acid (CAS 100379-00-8), 0.02 equivalent (0.1 g) of chloro(crotonyl)(2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl)palladium(II) (CAS 1798781-99-3), and 4.0 equivalent (3.8 g) of potassium phosphate (CAS 7778-53-2). Add a degassed mixture of 100 ml dialkylene and 13 ml water. The reaction was carried out at 55°C for 3 days under a nitrogen atmosphere. After cooling to room temperature, a gray suspension was formed. The original solid material was filtered and washed with dichloromethane, water, and methanol. The product was then dissolved in 300 ml of chloroform and filtered through a silica pad. The solvent was removed under reduced pressure, and the solid was stirred in a mixture of 20 ml of chloroform and 80 ml of hexane. After filtration, it was dried under vacuum and finally purified by sublimation. White powder. Yield: 4.5 g (75%). (LC-MS: 870.4)

[0322] (E-4)-2-(3',5'-dimethyl-[1,1'-biphenyl]-3-yl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,5-triazine

[0323] Step 1. 2-(3-Chlorophenyl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,5-triazine

[0324] Rinse the three-necked round-bottom flask with nitrogen and fill it with 1.05 equivalents (8.3 g) of 2-chloro-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine (CAS 2125473-29-0), 1.0 equivalents (17.3 g) of 4,4,5,5-tetramethyl-2-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,2-dioxaboranecyclopentane (CAS2032365-26-5), 0.02 equivalents (0.4 g) of [1,1'-bis(diphenylphosphine)ferrocene]dichloropalladium(II) (CAS72287-26-4), and 2 equivalents (7.2 g) of potassium carbonate (CAS 584-08-7). A degassed mixture of 200 ml dialkylene and 50 ml water was added. The reaction was carried out overnight at 55 °C under a nitrogen atmosphere. After cooling to room temperature, an orange suspension was formed. The original solid material was filtered, washed with dialkylene, water, methanol, and hexane, and dried under low pressure. The product was dissolved in 500 ml DCM and filtered through a silica pad. The solvent was evaporated, and the solid was stirred in a mixture of 100 ml chloroform and 150 ml methanol. After filtration and drying, the product was given as a white powder. Yield: 15.6 g (75%). (LC-MS: 800.2).

[0325] Step 2. 2-(3',5'-dimethyl-[1,1'-biphenyl]-3-yl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,5-triazine

[0326] Rinse a three-necked round-bottom flask with nitrogen and fill it with 1.0 equivalent (8.6 g) of 2-(3-chlorophenyl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,5-triazine (CAS waiver), 1.6 equivalent (2.6 g) of (3,5-dimethylphenyl)boric acid (CAS 172975-69-8), 0.02 equivalent (0.2 g) of crotonyl(2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl)palladium(II) (CAS 1798781-99-3), and 2.0 equivalent (4.6 g) of potassium phosphate (CAS 7778-53-2). Add a degassed mixture of 40 ml dialkylene and 10 ml water. The reaction was carried out overnight at 55 °C under a nitrogen atmosphere. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was dissolved in 150 mL of DCM, washed with water, dried over MgSO4, and filtered through a silica pad. The solution was slowly added to 300 mL of methanol. The precipitate was filtered and dried under vacuum. Final purification was performed by sublimation. White powder. Yield: 7.4 g (79%). (LC-MS: 870.4)

[0327] (E-10) - 2-(3',5'-dimethyl-[1,1'-biphenyl]-3-yl)-4-(2',6'-diphenyl-[1,1':4',1''-terphenyl]-4-yl)-6-phenyl-1,3,5-triazine

[0328] Rinse a three-necked round-bottom flask with nitrogen and fill it with 1.8 equivalents (9.4 g) of 3,5-dimethylphenylboronic acid (CAS172975-69-8), 1.0 equivalents (22.6 g) of 2-(3-chlorophenyl)-4-(2',6'-diphenyl-[1,1':4',1''-terphenyl]-4-yl)-6-phenyl-1,3,5-triazine (CAS 2437303-47-2), 0.03 equivalents (0.9 g) of tris(diphenylmethyleneacetone)dipalladium(0) (CAS 51364-51-3), 0.06 equivalents (0.9 g) of 2-dicyclohexylphosphine-2',4',6'-tri-isopropyl-1,1'-biphenyl (CAS 564483-18-7), and 2.0 equivalents (3.9 g) of... Potassium hydroxide (CAS 1310-58-3) g was added. A degassed mixture of 175 ml dialkylene, 175 ml toluene, and 35 ml water was added. The reaction was carried out overnight at 85 °C under a nitrogen atmosphere. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was dissolved in 500 ml DCM, washed with water, dried over MgSO4, and filtered through a silica pad. Part of the solvent was then removed, and hexane was added. The precipitate was filtered, dried under vacuum, and finally purified by sublimation. Yield: 23.9 g (95%). (LC-MS: 718.3)

[0329] (E-7)-2-(3'-methyl-4'-(3,5,6-triphenylpyrazin-2-yl)-[1,1'-biphenyl]-4-yl)-4,6-diphenyl-1,3,5-triazine

[0330] Step 1. 2-(4'-bromo-3'-methyl-[1,1'-biphenyl]-4-yl)-4,6-diphenyl-1,3,5-triazine

[0331] A three-necked round-bottom flask was rinsed with nitrogen and filled with 1 equivalent (30.0 g) of 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)phenyl)-1,3,5-triazine (CAS 1219956-23-6), 2.8 equivalents (45.0 g) of 1-bromo-4-iodo-2-toluene (CAS 202865-85-8), 0.06 equivalents (4.8 g) of tetra(triphenylphosphine)palladium(0) (CAS 14221-01-3), and 3 equivalents (28.5 g) of potassium carbonate (CAS 584-08-7). A degassed mixture of 400 ml toluene, 100 ml ethanol, and 100 ml water was added. The reaction was carried out at 75°C for 2 days under an inert atmosphere. The flask was then cooled and the solvent was evaporated. The original product was extracted in chloroform, washed with water, dried over MgSO4, and filtered through a silica pad. The solvent was then evaporated. The obtained solid was soaked in toluene at room temperature for 2 hours, then filtered and dried. White powder. Yield: 11.1 g (80%). (LC-MS: 478.1).

[0332] Step 2. 2-(3'-methyl-4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)-[1,1'-biphenyl]-4-yl)-4,6-diphenyl-1,3,5-triazine

[0333] Rinse a three-necked round-bottom flask with argon gas and add 1 equivalent (10.5 g) of 2-(4'-bromo-3'-methyl-[1,1'-biphenyl]-4-yl)-4,6-diphenyl-1,3,5-triazine (CAS 0), 1.1 equivalent (5.6 g) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborane) (CAS 73183-34-3), 0.03 equivalent (0.5 g) of [1,1'-bis(diphenylphosphine)ferrocene]dichloropalladium(II) (CAS 72287-26-4), and 3 equivalent (6.5 g) of potassium acetate (CAS 127-08-2). Add 120 ml of a degassed mixture of DMF. Initiate the reaction overnight at 100 °C under argon atmosphere. The next day, the reaction was cooled and the solvent was evaporated. The original product was extracted in chloroform, washed with water, dried over MgSO4, and filtered through a silica pad. The solvent was then evaporated to give a white powder. Yield: 8.5 g (74%). (LC-MS: 526.2).

[0334] Step 3. 2-(3'-methyl-4'-(3,5,6-triphenylpyrazin-2-yl)-[1,1'-biphenyl]-4-yl)-4,6-diphenyl-1,3,5-triazine

[0335] Rinse a three-necked round-bottom flask with nitrogen and fill it with 1 equivalent (8.4 g) of 2-(3'-methyl-4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)-[1,1'-biphenyl]-4-yl)-4,6-diphenyl-1,3,5-triazine (CAS 0), 1 equivalent (5.5 g) of 2-chloro-3,5,6-triphenylpyrazine (CAS 243472-78-8), 0.02 equivalent (0.2 g) of chloro(crotonyl)(2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl)palladium(II) (CAS 1798781-99-3), and 2 equivalents (6.8 g) of potassium phosphate (CAS 7778-53-2). Add a degassed mixture of 100 ml dialkylene and 20 ml water. The reaction was carried out overnight at 45°C under a nitrogen atmosphere. The next day, a brown suspension formed, and the reaction was cooled. The precipitate was filtered, washed with water and methanol, and dried under low pressure. The original product was dissolved in 500 ml of chloroform and filtered through a silica pad. The solvent was then evaporated. Next, the product was recrystallized from chlorobenzene. Final purification was performed by sublimation. White powder. Yield: 4.3 g (37.6%). (LC-MS: 706.3).

[0336] (E-9) - 2-(2',3'-dimethyl-[1,1'-biphenyl]-3-yl)-4-(2',6'-diphenyl-[1,1':4',1''-terphenyl]-4-yl)-6-phenyl-1,3,5-triazine

[0337] Rinse a three-necked round-bottom flask with nitrogen and fill it with 1 equivalent (22.6 g) of 2-(3-chlorophenyl)-4-(2',6'-diphenyl-[1,1':4',1''-terphenyl]-4-yl)-6-phenyl-1,3,5-triazine (CAS 2437303-47-2), 1.8 equivalent (9.4 g) of (2,3-dimethylphenyl)boric acid (CAS 183158-34-1), 0.03 equivalent (1.0 g) of tris(diphenylmethyleneacetone)dipalladium(0) (CAS 51364-51-3), 0.06 equivalent (1.0 g) of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (CAS 564483-18-7), and 2 equivalent (3.9 g) of potassium hydroxide (CAS 2437303-47-2). 1310-58-3). A degassed mixture of 175 ml dialkylene, 175 ml toluene, and 35 ml water was added. The reaction was carried out overnight at 90 °C under a nitrogen atmosphere. After cooling to room temperature, a brown solution was formed. The solvent was evaporated, the solid was extracted in DCM, washed with water, dried over MgSO4, and filtered through a silica pad. The DCM was then partially evaporated and hexane was added to give a white precipitate. The product was then filtered, washed with hexane and methanol, and dried. Final purification was performed by sublimation. White powder. Yield: 24.2 g (94%). (ESI-MS: 718.3).

[0338] (E-5)-2-(3,5-dimethylphenyl)-4-phenyl-6-(3'-(3,5,6-triphenylpyrazin-2-yl)-[1,1'-biphenyl]-4-yl)-1,3,5-triazine

[0339] Step 1. Synthesis of 2-(4-chlorophenyl)-4-(3,5-dimethylphenyl)-6-phenyl-1,3,5-triazine

[0340] A three-necked round-bottom flask was rinsed with nitrogen and filled with 1 equivalent (30 g) of 2-chloro-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (CAS 30894-93-0), 1.1 equivalent (16.4 g) of (3,5-dimethylphenyl)boronic acid (CAS 172975-69-8), 0.02 equivalent (2.3 g) of tetra(triphenylphosphine)palladium(0) (CAS 14221-01-3), and 2 equivalent (27.4 g) of potassium carbonate (CAS 584-08-7). A degassed mixture of 400 ml dialkylene and 100 ml water was added. The reaction was carried out overnight at 65 °C under a nitrogen atmosphere. After cooling to room temperature, a gray suspension was formed. The original solid material was filtered, washed with dialkylene, acetone, water, and methanol, and dried under low pressure. The product was dissolved in 1 L of DCM and filtered through a silica pad. The solvent was evaporated, and the product was obtained as a white powder. Yield: 28.9 g (78%). (LC-MS: 373.1)

[0341] Step 2. Synthesis of 2-(3,5-dimethylphenyl)-4-phenyl-6-(3'-(3,5,6-triphenylpyrazin-2-yl)-[1,1'-biphenyl]-4-yl)-1,3,5-triazine

[0342] Rinse the three-necked round-bottom flask with nitrogen and fill it with 1.0 equivalent (15 g) of 2-(4-chlorophenyl)-4-(3,5-dimethylphenyl)-6-phenyl-1,3,5-triazine (CAS 0), 0.95 equivalent (19.6 g) of 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)phenyl)pyrazine (CAS 2396743-64-7), 0.01 equivalent (0.13 g) of crotonyl(2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl)palladium(II) (CAS 1798781-99-3), and 2.0 equivalent (17.1 g) of potassium phosphate (CAS 7778-53-2). A degassed mixture of 160 ml toluene, 40 ml THF, and 40 ml water was added. The reaction was carried out at 60 °C for 3 days under a nitrogen atmosphere. After cooling to room temperature, a gray suspension was formed. The original solid material was filtered, washed with THF, water, methanol, and hexane, and dried under low pressure. The residue was dissolved in 2 L of chlorobenzene and hot-filtered through a silica pad. The solvent was evaporated, and the solid material was recrystallized from DMF. Final purification was performed by sublimation. White powder. Yield: 17.9 g (62%). (LC-MS: 721.3)

[0343] (E-6)-2,4-bis(3,5-dimethylphenyl)-6-(3'-(3,5,6-triphenylpyrazin-2-yl)-[1,1'-biphenyl]-4-yl)-1,3,5-triazine

[0344] In a three-necked round-bottom flask, add 1.0 equivalent (17.8 g) of 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)phenyl)pyrazine (CAS 2396743-64-7), 1.05 equivalent (14.6 g) of 2-(4-chlorophenyl)-4,6-bis(3,5-dimethylphenyl)-1,3,5-triazine (CAS 2830402-45-2), 0.03 equivalent (0.6 g) of crotonyl(2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl)palladium(II) (CAS 1798781-99-3), and 2.0 equivalent (14.8 g) of potassium phosphate (CAS 7778-53-2). Then empty the flask and rinse it with argon. A degassed mixture of 240 mL dialkylene and 80 mL water was added, and the reaction was carried out overnight at 95 °C under an argon atmosphere. The reaction mixture was allowed to cool to room temperature, and a thick gray suspension formed. The solid material was filtered and washed with dialkylene, DCM, water, methanol, and finally with a mixture of DCM in methanol (5%). The solid was dried, adsorbed onto silica gel (100 g), and separated chromatographically using DCM / petroleum ether (1:1) as the eluent. The solvent was then removed under reduced pressure to give a white powder. Final purification was performed by sublimation. Yield: 21 g (82%). (LC-MS: 748.3).

[0345] (E-8)-2-(3',5'-dimethyl-[1,1'-biphenyl]-3-yl)-4-phenyl-6-(3-(10-phenylanthracene-9-yl)phenyl)-1,3,5-triazine

[0346] In a three-necked round-bottom flask, 1.0 equivalent (22.4 g) of 2-(3-chlorophenyl)-4-phenyl-6-(3-(10-phenylanthracene-9-yl)phenyl)-1,3,5-triazine (CAS 2576432-81-8), 1.8 equivalent (10.1 g) of (3,5-dimethylphenyl)boric acid (CAS 172975-69-8), 0.03 equivalent (1.0 g) of tris(diphenylmethyleneacetone)dipalladium(0) (CAS 51364-51-3), 0.06 equivalent (1.1 g) of 2-dicyclohexylphosphine-2',4',6'-tris-isopropyl-1,1'-biphenyl (CAS 564483-18-7), and 2.0 equivalent (4.2 g) of potassium hydroxide (CAS 1310-58-3) were added. The flask was then purged and rinsed with nitrogen. A degassed mixture of 200 ml dialkylene, 200 ml toluene, and 40 ml water was added, and the reaction was carried out overnight at 90 °C under an inert atmosphere. After cooling to room temperature, a gray suspension was formed. The solid raw material was filtered and washed with dialkylene, toluene, water, and methanol. The material was then dissolved in 400 ml DCM and filtered through a silica pad. The solvent was evaporated, and the solid material was first soaked in acetonitrile, then in a mixture of 200 ml DCM and 400 ml hexane. Final purification was performed by sublimation. Yield: 13.6 g (54%). (LC-MS: 666.3).

[0347] Table 1: Properties of the synthesized compounds Td5% = Temperature (10 K / min) determined by TGA with 5% weight loss.

[0348] Device Experiment

[0349] General steps in manufacturing a bottom-emitting OLED

[0350] For bottom-emitting OLED devices, the ITO / glass substrate is cut to a size of 150 mm × 150 mm × 0.7 mm, rinsed with isopropanol for about 5 minutes, then ultrasonically cleaned with pure water for about 5 minutes, and baked in an oven at 200°C for about 2 hours. Before the organic material is deposited, it is subjected to plasma treatment (usually N2 plasma) in a vacuum chamber.

[0351] The device is fabricated as follows: a hole injection layer of HT-1 doped with D-1 is deposited onto a substrate with an ITO anode, followed by the deposition of an undoped HT-1 hole transport layer. Subsequently, an electron blocking layer of HT-2 is deposited on the HTL. Then, a blue fluorescent emitting layer of HOST-1 doped with EMITTER-1 is deposited. A layer made of a comparative compound or the compound of the present invention is deposited on the emitting layer as a hole blocking layer. The electron transport layer of ET-1 is co-deposited with LiQ on the HBL. Finally, an Al cathode is deposited. All depositions are performed by vacuum thermal evaporation.

[0352] Stack: ITO, 90 nm / (HT-1): (D-1) (2 wt%), 10 nm / (HT-1), 128 nm / (HT-2), 5 nm / H09(HOST-1): BD200(EMITTER-1) (3 vol%), 20 nm / HBL (100% of the present invention or comparative compound), 5 nm / (ET-1): LiQ (50 vol%), 31 nm / Al, 100 nm

[0353] The compound tested: E-1 E-2 E-3 E-4 E-5 E-6 E-7 E-8 E-9 E-10.

[0354] Comparison of compound CE-1

[0355] 2,4-Diphenyl-6-(4'-(3,5,6-triphenylpyrazin-2-yl)-[1,1'-biphenyl]-4-yl)-1,3,5-triazine

[0356] CAS 2397584-94-8 CE-1.

[0357] Comparison of compound CE-2

[0358] 2-([1,1'-biphenyl]-3-yl)-4-phenyl-6-(3-(10-phenylanthracene-9-yl)phenyl)-1,3,5-triazine

[0359] CAS 2437303-42-7

[0360] Comparison of compound CE-3

[0361] 2-([1,1'-biphenyl]-3-yl)-4-phenyl-6-(4',5',6'-triphenyl-[1,1':2',1'':3'',1'''-tetraphenyl]-3'''-yl)-1,3,5-triazine

[0362] CAS 2032364-68-2

[0363] Table 2: Other compounds used:

[0364] Table 3: Performance of OLED devices, Comparative example CE-1

[0365] Table 4. Performance of OLED devices, comparative example CE-2

[0366] Table 5. Performance of OLED devices, comparative example CE-3

[0367] As can be seen from Tables 3 to 5, the organic light-emitting devices according to the present invention, which contain a compound of formula (I) in their hole blocking layer but do not contain an electro-doped agent, have improved efficiency and driving voltage.

[0368] Preferred substitute R 1 and R 2 LUMO value of the group

[0369] Table 6:

[0370] As can be seen from Table 6, compared with such groups having only a meta-substituent, R groups having at least one substituent at the ortho or para position... 1 and R 3 Groups can be advantageous. Specifically, as can be seen from Table 6, IIa-1 has the lowest calculated LUMO of -0.58 eV. For this low LUMO, the lowest OLED device efficiency C can be expected. eff On the other hand, higher LUMO can be expected to result in higher OLED device efficiency C. eff .

[0371] The features disclosed in the foregoing specification and dependent claims may be used individually and in any combination thereof, thereby fulfilling the aspects of this disclosure set forth in the independent claims as material in various forms.

Claims

1. An organic light-emitting device, the organic light-emitting device comprising an anode, a cathode, a light-emitting layer, a hole-blocking layer, and an electron transport layer, in - The light-emitting layer, the hole-blocking layer, and the electron transport layer are disposed between the anode and the cathode; - The hole blocking layer and the electron transport layer are disposed between the light-emitting layer and the cathode; - The hole blocking layer is disposed between the light-emitting layer and the electron transport layer; - The hole blocking layer is in direct contact with the electron transport layer; - The hole blocking layer does not contain electrical dopants; - The hole-blocking layer comprises a compound of formula (I). (I) In equation (I) - m and n are 0 or 1 independently; - p is 0 or 1; - m+n+p≥1; - R 1 and R 3 Independently, C6 to C6 are substituted or unsubstituted. 18 Aryl; - R 2 and R 4 Independently, C6 to C6 are substituted or unsubstituted. 18 Aranediol; - R 5 It is substituted or unsubstituted C6 to C 18 Aranediol; - R 6 Selected from benzene, pyrazine, and anthracene groups; - R 7 It is unreplaced C6 to C 18 Aryl; - R 8 To R 11 Independently selected from H and unsubstituted C6 to C 18 Aryl; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

2. The organic light-emitting device according to claim 1, wherein R 1 and R 3 It is either a substituted or unsubstituted phenyl group.

3. The organic light-emitting device according to claim 1 or 2, wherein R 2 and R 4 It is either a substituted or unsubstituted phenylene group.

4. The organic light-emitting device according to any one of the preceding claims, wherein R 5 It is substituted or unsubstituted C6 to C 12 Fangyaji.

5. The organic light-emitting device according to any one of the preceding claims, wherein R 6 Selected from phenylene group and pyrazine group.

6. The organic light-emitting device according to any one of the preceding claims, wherein R 7 It is an unsubstituted phenyl group.

7. The organic light-emitting device according to any one of the preceding claims, wherein R 8 To R 11 It is independently selected from H and phenyl.

8. The organic light-emitting device according to any one of the preceding claims, wherein R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 5 It is substituted with at least one C1 to C6 alkyl substituent.

9. The organic light-emitting device according to any one of the preceding claims, wherein in R 1 To R 5 In the case where one or more of the components are substituted, each of the one or more substituents is a methyl group.

10. The organic light-emitting device according to any one of the preceding claims, wherein the compound of formula (I) is selected from E-1 to E-10. E-1、 E-2、 E-3、 E-4、 E-5、 E-6、 E-7、 E-8、 E-9、 E-10。 11. An apparatus comprising an organic light-emitting device according to any one of the preceding claims, wherein the apparatus is a display device or a lighting device.

12. Compounds of formula (II) (II) In equation (II) - m and n are 0 or 1 independently; - p is 0, 1, or 2; - m+n+p≥1; - R 1 and R 3 It is either a substituted or unsubstituted phenyl group; - R 2 and R 4 It is either a substituted or unsubstituted phenylene group; - Each R 5 It is either a substituted or unsubstituted phenylene group; - R 6 Selected from benzene, pyrazine, and anthracene groups; - R 7 It is an unsubstituted phenyl group; - R 8 To R 11 Independently selected from H and unsubstituted phenyl groups; - In R 1 To R 5 In the case where one or more of the components are substituted, the one or more substituents are independently C1 to C6 alkyl groups; and - R 1 and R 3 At least one of them is substituted with at least one C1 to C6 alkyl substituent; and / or R 2 R 4 and R 5 At least one of them is substituted by at least one C1 to C6 alkyl substituent.

13. The compound according to claim 12, wherein R 1 and R 3 At least one of them is substituted by at least two C1 to C6 alkyl substituents; and / or R 5 It is substituted with at least one C1 to C6 alkyl substituent.

14. The compound according to claim 12 or 13, wherein in R 1 To R 5 In the case where one or more of the components are substituted, each of the one or more substituents is a methyl group.

15. The compound according to claims 12 to 14, wherein the compound is selected from E-2 to E-10. E-2、 E-3、 E-4、 E-5、 E-6、 E-7、 E-8、 E-9、 E-10。

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