A compound containing triazine and phenanthrene and an organic electroluminescence device thereof

Abstract

This invention discloses a compound containing triazine and phenanthrene, belonging to the field of semiconductor materials technology. The structure of the compound is shown in general formula (1). This compound has good electronic modulation ability and hole and exciton blocking ability, and also has good stability. When the compound of this invention is used as a hole blocking layer material for organic electroluminescent devices, the luminous efficiency and working life of the organic electroluminescent devices can be significantly improved. General formula (1)

Description

Technical Field

[0001] This invention relates to the field of semiconductor materials technology, and in particular to a compound containing triazine and phenanthrene and its organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) technology can be used to manufacture novel display products and lighting products, and is expected to replace existing liquid crystal displays and fluorescent lighting, with a wide range of applications. OLEDs have a sandwich-like structure, including electrode material layers and organic optoelectronic functional material layers sandwiched between different electrode material layers. Each organic optoelectronic functional material layer contains at least one light-emitting layer. Various different organic optoelectronic functional materials are stacked together according to their intended use to form the OLED. As a current-driven device, when a voltage is applied to its two electrodes, and an electric field is applied to the positive and negative charges in the organic optoelectronic functional material layer, the positive and negative charges recombine in the light-emitting layer, thus generating organic electroluminescence.

[0003] Currently, organic light-emitting diode (OLED) display technology has been applied in smartphones, tablets, televisions, and other fields. However, compared with the requirements of actual product applications, the luminous efficiency and lifespan of OLEDs still need further improvement. To continuously improve the performance of OLEDs, ongoing research and innovation in organic optoelectronic functional materials are needed to create higher-performance organic optoelectronic functional materials.

[0004] Organic optoelectronic functional materials used in organic electroluminescent devices can be broadly classified into two categories based on their applications: charge injection transport materials and luminescent materials. Further, charge injection transport materials can be categorized into electron injection transport materials, electron blocking materials, hole injection transport materials, and hole blocking materials. In organic electroluminescent devices, holes are injected from the anode, and electrons are injected from the cathode, transporting within the organic functional layer. They eventually meet in the luminescent layer to form excitons, which recombine to emit light. The hole blocking layer, located between the luminescent and electron transport layers, prevents holes from diffusing or moving into the electron transport layer and reduces exciton energy loss, thus acting as an interface modifier and assisting in electron injection / transport regulation. Currently, existing hole blocking layer materials have poor electron control and hole / exciton blocking capabilities, making it difficult to achieve efficient electron-hole balance within the luminescent layer and thus hindering the development of high-efficiency, long-lifetime devices. Therefore, it is necessary to further improve the electron injection and transport capabilities, as well as the hole / exciton blocking capabilities, of hole blocking layer materials, enhance material stability, achieve efficient exciton balance, and ultimately improve device efficiency and lifetime. Summary of the Invention

[0005] To address the aforementioned problems in the existing technology, this invention provides a compound containing triazine and phenanthrene and its organic electroluminescent device. The compound of this invention has excellent hole blocking ability and good material stability. When applied to organic electroluminescent devices, it can effectively improve the luminous efficiency and working life of the device.

[0006] This invention provides a compound containing triazine and phenanthrene, the structure of which is shown in general formula (1):

[0007]

[0008] General formula (1)

[0009] In general formula (1), Ar1 and Ar2 are each independently represented as substituted or unsubstituted C1-C. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 50 aryl, substituted or unsubstituted C3-C 50 Mixed aromatics;

[0010] Ar1 and Ar2 may be the same or different;

[0011] a and b represent the numbers 0 or 1, and a + b ≥ 1;

[0012] L1 and L2 can be independently represented as single bond, phenylene, diphenylene, terphenylene, and tetraphenylene;

[0013] L1 and L2 may be the same or different;

[0014] R represents one of phenyl, naphthyl, diphenyl, triphenyl, pyridyl, or pyrimidinyl.

[0015] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each is represented independently as a hydrogen atom, C1-C 20 Alkyl, C3-C 20 Cycloalkyl, pyridyl, phenyl, or diphenyl;

[0016] The R7, R8, R9, R 10 There is one and only one site that is connected to L2;

[0017] The R1~R 10 There is one and only one representation of C1-C. 20 One of alkyl, phenyl, or diphenyl;

[0018] The substituents of the above groups, whether substituted or unsubstituted, may be selected from deuterium, C1-C... 20Alkyl, C3-C 20 Cycloalkyl, phenyl, diphenyl, naphthyl, triphenyl, pyridyl, pyrimidinyl;

[0019] * Indicates a connection site;

[0020] In general formula (1), any hydrogen atom can be optionally replaced by a deuterium atom.

[0021] Furthermore, the structure of the compound is shown in any one of general formulas (2-1) to (2-19):

[0022]

[0023] General formula (2-1) General formula (2-2)

[0024]

[0025] General formula (2-3) General formula (2-4)

[0026]

[0027] General formula (2-5) General formula (2-6)

[0028]

[0029] General formula (2-7) General formula (2-8) General formula (2-9)

[0030]

[0031] General formula (2-10) General formula (2-11) General formula (2-12)

[0032]

[0033] General formula (2-13) General formula (2-14)

[0034]

[0035] General formula (2-15) General formula (2-16)

[0036]

[0037] General formula (2-17) General formula (2-18)

[0038]

[0039] General formula (2-19)

[0040] In general formulas (2-1) to (2-19), Ar1, Ar2, L1, L2, R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The meaning is the same as the limitation in the general formula (1) above.

[0041] Furthermore, the structure of the compound is shown in any one of general formulas (3-1) to (3-30):

[0042]

[0043] General formula (3-1) General formula (3-2)

[0044]

[0045] General formula (3-3) General formula (3-4)

[0046]

[0047] General formula (3-5) General formula (3-6)

[0048]

[0049] General formula (3-7) General formula (3-8)

[0050]

[0051] General formula (3-9) General formula (3-10)

[0052]

[0053] General formula (3-11) General formula (3-12)

[0054]

[0055] General formula (3-13) General formula (3-14)

[0056]

[0057] General formula (3-15) General formula (3-16)

[0058]

[0059] General formula (3-17) General formula (3-18)

[0060]

[0061] General formula (3-19) General formula (3-20)

[0062]

[0063] General formula (3-21) General formula (3-22)

[0064]

[0065] General formula (3-23) General formula (3-24)

[0066]

[0067] General formula (3-25) General formula (3-26)

[0068]

[0069] General formula (3-27) General formula (3-28)

[0070]

[0071] General formula (3-29) General formula (3-30)

[0072] In general formulas (3-1) to (3-30), Ar1, Ar2, R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The meanings of a and b are the same as those in the general formula (1) above.

[0073] Furthermore, the structure of the compound is shown in any one of general formulas (4-1) to (4-17):

[0074]

[0075] General formula (4-1) General formula (4-2) General formula (4-3)

[0076]

[0077] General formula (4-4) General formula (4-5) General formula (4-6)

[0078]

[0079] General formula (4-7) General formula (4-8) General formula (4-9)

[0080]

[0081] General formula (4-10) General formula (4-11) General formula (4-12)

[0082]

[0083] General formula (4-13) General formula (4-14) General formula (4-15)

[0084]

[0085] General formula (4-16) General formula (4-17)

[0086] In general formulas (4-1) to (4-17), Ar1, Ar2, L1, L2, R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The meaning is the same as the limitation in general formula (1) above;

[0087] R' represents one of the following: hydrogen atom, phenyl, naphthyl, diphenyl, terphenyl, pyridyl, or pyrimidinyl.

[0088] Furthermore, the structure of the compound is shown in any one of general formulas (5-1) to (5-7):

[0089]

[0090] General formula (5-1) General formula (5-2)

[0091]

[0092] General formula (5-3) General formula (5-4)

[0093]

[0094] General formula (5-5) General formula (5-6)

[0095]

[0096] General formula (5-7)

[0097] In general formulas (5-1) to (5-7), Ar1, Ar2, L1, L2, R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The meanings of a and b are the same as those in the general formula (1) above.

[0098] Furthermore, in the general formula (1) It can be represented as the structure shown below:

[0099] , , , , , , Any one of them;

[0100] The R1, R2, R 10 Each independently is represented as C1-C 20 Alkyl, C3-C 20 Cycloalkyl, phenyl, or diphenyl.

[0101] Furthermore, Ar1 and Ar2 are each independently represented as substituted or unsubstituted C1-C. 20 Alkyl, substituted or unsubstituted C3-C 20 The cycloalkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted diphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted carbazole group; Ar1 ​​and Ar2 may be the same or different;

[0102] The R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each can be represented independently as a hydrogen atom, methyl, tert-butyl, isopropyl, adamantyl, phenyl, or diphenyl.

[0103] The substituents may be selected from deuterium, methyl, ethyl, propyl, isopropyl, tert-amyl, tert-butyl, butyl, adamantyl, cyclopentyl, cyclohexyl, phenyl, diphenyl, naphthyl, terphenyl, pyridyl, or pyrimidinyl.

[0104] Preferably, L1 and L2 are each independently represented by any of the following structures;

[0105] , , , , , , , , , , , , , , , , , ;

[0106] Preferably, Ar1 and Ar2 are each independently represented as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-hexyl, etc. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or Any one of them;

[0107] Preferably, the substituents of the above-mentioned groups, whether substituted or unsubstituted, are selected from deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-hexyl, etc. , , , , , , , , , , , , , , , , , or Any one of them.

[0108] Furthermore, the specific structure of the compound is any one of the following structures:

[0109] (1) (2) (3)

[0110] (4) (5) (6)

[0111] (7) (8) (9) (10)

[0112] (11) (12) (13) (14)

[0113] (15) (16) (17)

[0114] (18) (19) (20)

[0115] (twenty one) (twenty two) (twenty three)

[0116] (twenty four) (25) (26)

[0117] (27) (28) (29)

[0118] (30) (31) (32)

[0119] (33) (34) (35)

[0120] (36) (37) (38)

[0121] (39) (40) (41)

[0122] (42) (43) (44)

[0123] (45) (46) (47)

[0124] (48) (49) (50)

[0125] (51) (52) (53)

[0126] (54) (55) (56)

[0127] (57) (58) (59)

[0128] (60) (61) (62)

[0129] (63) (64) (65)

[0130] (66) (67) (68)

[0131] (69) (70) (71)

[0132] (72) (73) (74)

[0133] (75) (76) (77)

[0134] (78) (79) (80)

[0135] (81) (82) (83)

[0136] (84) (85) (86)

[0137] (87) (88) (89)

[0138] (90) (91) (92)

[0139] (93) (94) (95)

[0140] (96) (97) (98)

[0141] (99) (100) (101)

[0142] (102) (103) (104)

[0143] (105) (106) (107)

[0144] (108) (109) (110)

[0145] (111) (112) (113)

[0146] (114) (115) (116)

[0147] (117) (118) (119)

[0148] (120) (121) (122)

[0149] (123) (124) (125)

[0150] (126) (127) (128)

[0151] (129) (130) (131)

[0152] (132) (133) (134)

[0153] (135) (136) (137)

[0154] (138) (139) (140)

[0155] (141) (142) (143)

[0156] (144) (145) (146)

[0157] (147) (148) (149) (150)

[0158] (151) (152) (153)

[0159] (154) (155) (156)

[0160] (157) (158) (159)

[0161] (160) (161) (162)

[0162] (163) (164) (165)

[0163] (166) (167) (168)

[0164] (169) (170) (171)

[0165] (172) (173) (174)

[0166] (175) (176) (177)

[0167] (178) (179) (180)

[0168] (181) (182) (183)

[0169] (184) (185) (186)

[0170] (187) (188) (189)

[0171] (190) (191) (192)

[0172] (193) (194) (195)

[0173] (196) (197) (198)

[0174] (199) (200) (201)

[0175] (202) (203) (204)

[0176] (205) (206) (207)

[0177] (208) (209) (210)

[0178] (211) (212) (213)

[0179] (214) (215) (216)

[0180] (217) (218) (219)

[0181] (220) (221) (222)

[0182] (223) (224) (225)

[0183] (226) (227) (228)

[0184] (229) (230) (231)

[0185] (232) (233) (234)

[0186] (235) (236) (237)

[0187] (238) (239) (240)

[0188] (241) (242) (243)

[0189] (244) (245) (246)

[0190] (247) (248) (249)

[0191] (250) (251) (252)

[0192] (253) (254) (255)

[0193] (256) (257) (258)

[0194] (259) (260) (261)

[0195] (262) (263) (264)

[0196] (265) (266) (267)

[0197] (268) (269) (270)

[0198] (271) (272) (273)

[0199] (274) (275) (276)

[0200] (277) (278) (279)

[0201] (280) (281) (282)

[0202] (283) (284) (285)

[0203] (286) (287) (288) (289)

[0204] (290) (291) (292)

[0205] (293) (294) (295)

[0206] (296) (297) (298)

[0207] (299) (300) (301)

[0208] (302) (303) (304)

[0209] (305) (306) (307)

[0210] (308) (309) (310)

[0211] (311) (312) (313)

[0212] (314) (315) (316)

[0213] (317) (318) (319)

[0214] (320) (321) (322)

[0215] (323) (324) (325)

[0216] (326) (327) (328)

[0217] (329) (330) (331)

[0218] (332) (333) (334)

[0219] (335) (336) (337)

[0220] (338) (339) (340)

[0221] (341) (342) (343)

[0222] (344) (345) (346)

[0223] (347) (348) (349)

[0224] (350) (351) (352)

[0225] (353) (354) (355)

[0226] (356) (357) (358)

[0227] (359) (360) (361)

[0228] (362) (363) (364)

[0229] (365) (366) (367)

[0230] (368) (369) (370)

[0231] (371) (372) (373)

[0232] (374) (375) (376)

[0233] (377) (378) (379)

[0234] (380) (381) (382)

[0235] (383) (384) (385)

[0236] (386) (387) (388)

[0237] (389) (390) (391)

[0238] (392) (393) (394)

[0239] (395) (396) (397) (398)

[0240] (399) (400) (401)

[0241] (402) (403) (404)

[0242] (405) (406) (407)

[0243] (408) (409) (410)

[0244] (411) (412) (413)

[0245] (414) (415) (416)

[0246] (417) (418) (419)

[0247] (420) (421) (422)

[0248] (423) (424) (425)

[0249] (426) (427) (428) (429)

[0250] (430) (431) (432) (433)

[0251] (434) (435) (436)

[0252] (437) (438) (439)

[0253] (440) (441) (442)

[0254] (443) (444) (445)

[0255] (446) (447) (448)

[0256] (449) (450) (451)

[0257] (452) (453) (454)

[0258] (455) (456) (457)

[0259] (458) (459) (460)

[0260] (461) (462) (463)

[0261] (464) (465) (466)

[0262] (467) (468) (469)

[0263] (470) (471) (472)

[0264] (473) (474) (475)

[0265] (476) (477) (478)

[0266] (479) (480) (481)

[0267] (482) (483) (484)

[0268] (485) (486) (487)

[0269] (488) (489) (490)

[0270] (491) (492) (493)

[0271] (494) (495) (496)

[0272] (497) (498) (499)

[0273] (500) (501) (502)

[0274] (503) (504) (505)

[0275] (506) (507) (508)

[0276] (509) (510) (511)

[0277] (512) (513) (514)

[0278] (515) (516) (517)

[0279] (518) (519) (520)

[0280] (521) (522) (523)

[0281] (524) (525) (526)

[0282] (527) (528) (529)

[0283] (530) (531) (532)

[0284] (533) (534) (535)

[0285] (536) (537) (538)

[0286] (539) (540) (541)

[0287] (542) (543) (544)

[0288] (545) (546) (547)

[0289] (548) (549) (550)

[0290] (551) (552) (553)

[0291] (554) (555) (556)

[0292] (557) (558) (559)

[0293] (560) (561) (562)

[0294] (563) (564) (565)

[0295] (566) (567) (568)

[0296] (569) (570) (571)

[0297] (572) (573) (574)

[0298] (575) (576) (577)

[0299] (578) (579) (580)

[0300] (581) (582) (583)

[0301] (584) (585) (586)

[0302] (587) (588) (589)

[0303] (590) (591) (592)

[0304] (593) (594) (595)

[0305] (596) (597) (598)

[0306] (599) (600) (601)

[0307] (602) (603) (604)

[0308] (605) (606) (607)

[0309] (608).

[0310] The present invention also provides an organic electroluminescent device, comprising a substrate, a first electrode, an organic thin film layer, and a second electrode, wherein the organic thin film layer contains the triazine and phenanthrene compound described in the present invention.

[0311] Preferably, the organic thin film layer includes a hole transport region thin film layer, a light emission region thin film layer, and an electron transport region thin film layer, wherein the electron transport region thin film layer contains the triazine and phenanthrene compound described in this invention.

[0312] Furthermore, the electron transport region thin film layer includes a hole blocking layer containing the triazine and phenanthrene compound described in this invention.

[0313] Preferably, the electron transport region thin film layer comprises a hole blocking layer, an electron transport layer, and an electron injection layer, wherein the hole blocking layer contains the triazine and phenanthrene compound described in this invention.

[0314] Preferably, the hole transport region thin film layer comprises a hole injection layer, a hole transport layer, and an electron blocking layer; the electron transport region thin film layer comprises a hole blocking layer, an electron transport layer, and an electron injection layer; and the hole blocking layer contains the triazine and phenanthrene compound of the present invention.

[0315] The beneficial technical effects of this invention are as follows:

[0316] In the triazine and phenanthrene compounds of the present invention, the substituted triazine is linked to the substituted phenanthrene group through a specific bridging group, thereby giving the compounds of the present invention superior hole blocking and exciton blocking capabilities. This enables them to efficiently block the diffusion or movement of holes into the electron transport layer, thus better confining holes to the light-emitting region. This ensures that more holes and electrons in the light-emitting layer form excitons, increasing the exciton concentration and thereby improving the luminous efficiency and operating life of the device.

[0317] The structural features of the compounds in this invention enable them to have superior electronic control capabilities, supplement the electron transport layer, and possess suitable electron injection and transport performance. They can better adapt to the electron-hole balance within the luminescent layer, thereby improving the device's luminous efficiency and lifespan. Attached Figure Description

[0318] Figure 1 This is a schematic diagram of the structure of an organic electroluminescent device using the materials listed in this invention. In the figure, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, 10 is a cathode layer, and 11 is a light extraction layer.

[0319] Figure 2 The 1H NMR spectrum of compound 75 of this invention;

[0320] Figure 3 The image shows the 1H NMR spectrum of compound 187 of this invention in deuterated chloroform. Detailed Implementation

[0321] The technical solution of the present invention will be described in detail below with reference to the implementation scheme.

[0322] In this invention, unless otherwise stated, HOMO refers to the highest occupied orbital of a molecule, and LUMO refers to the lowest empty orbital of a molecule.

[0323] In the accompanying drawings, the dimensions of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "above" another layer or substrate, the layer or element may be located directly above that other layer or substrate, or there may be intermediate layers. Furthermore, it will be understood that when a layer is referred to as being "between" two layers, the layer may be the only layer between the two layers, or there may be one or more intermediate layers.

[0324] In this invention, the terms "upper" and "lower," used to describe electrodes, organic electroluminescent devices, and other structures, indicate orientation only in a specific state and do not imply that the structure can only exist in that orientation. Conversely, if the structure can be repositioned, such as by inverting it, the orientation of the structure changes accordingly. Specifically, in this invention, the "lower" side of an electrode refers to the side of the electrode closer to the substrate during fabrication, while the opposite side farther from the substrate is the "upper" side.

[0325] The substituted or unsubstituted C6-C of this invention 50 Aryl group, preferably substituted or unsubstituted C6-C 30 Aryl group, preferably substituted or unsubstituted C6-C 20Aryl group, preferably substituted or unsubstituted C6-C 10 The aryl group is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthraquinone group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted tetraphenyl group, a substituted or unsubstituted pyrene group, a substituted or unsubstituted diphenyl group, a substituted or unsubstituted triphenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted indene group, a substituted or unsubstituted triphenylene group, a combination thereof, or a fused ring of the foregoing groups, but is not limited thereto.

[0326] The substituted or unsubstituted C3-C described in this invention 50 Heteroaryl groups, preferably substituted or unsubstituted C3-C 30 Heteroaryl groups, preferably substituted or unsubstituted C3-C 20 Heteroaryl groups, preferably substituted or unsubstituted C3-C 10 Heteroaryl groups, preferably substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrrole, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted The substituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted naphridyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzothiazinyl group, substituted or unsubstituted acridineyl group, substituted or unsubstituted benzazinyl group, substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted fumonyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted carbazoleyl group, combinations thereof, or fused rings of the foregoing groups, but not limited thereto.

[0327] The substituted or unsubstituted C1-C of this invention 20 Alkyl groups (including straight-chain alkyl and branched-chain alkyl) are preferably substituted or unsubstituted C1-C. 10Alkyl groups, preferably substituted or unsubstituted C1-C4 alkyl groups, preferably substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted neopentyl, substituted or unsubstituted n-pentyl, substituted or unsubstituted isopentyl, substituted or unsubstituted octyl, substituted or unsubstituted heptyl, substituted or unsubstituted n-decyl, substituted or unsubstituted 1-methylpentyl, substituted or unsubstituted 2-methylpentyl, substituted or unsubstituted 3-methylpentyl, substituted or unsubstituted 1-butylpentyl, etc., but not limited thereto.

[0328] The substituted or unsubstituted C3-C described in this invention 20 Cycloalkyl groups are preferably substituted or unsubstituted C5-C. 10 Cycloalkyl, non-limiting examples of which may include substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted 4-methylcyclohexyl, substituted or unsubstituted 4,4-dimethylcyclohexyl, substituted or unsubstituted adamantyl and substituted or unsubstituted cycloheptyl.

[0329] The C1-C of this invention 20 Alkyl groups (including straight-chain alkyl and branched-chain alkyl) refer to methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl, etc., but are not limited to these.

[0330] The C3-C of this invention 20 Cycloalkyl groups are preferably C5-C. 10 Cycloalkyl, more preferably C5-C8 cycloalkyl, non-limiting examples of which may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl and cycloheptyl.

[0331] Organic electroluminescent devices

[0332] The organic electroluminescent device of the present invention can be a bottom-emitting organic electroluminescent device, a top-emitting organic electroluminescent device, or a multilayer organic electroluminescent device, and there is no specific limitation thereto.

[0333] The organic electroluminescent device of the present invention comprises, in sequence, a substrate, a first electrode, an organic thin film layer, and a second electrode. The organic thin film layer includes a hole transport region thin film layer, a light-emitting region thin film layer, and an electron transport region thin film layer. The hole transport region thin film layer includes a hole injection layer, a hole transport layer, and an electron blocking layer. The electron transport region thin film layer includes a hole blocking layer, an electron transport layer, and an electron injection layer. Additionally, a light extraction layer may be disposed on the second electrode.

[0334] The organic electroluminescent device of the present invention may include the following layers and their positional relationships: it may include a substrate, a first electrode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a second electrode, and a light extraction layer. If the above layers are present, the first electrode is on the substrate, the hole injection layer is on the first electrode, the hole transport layer is on the hole injection layer, the electron blocking layer is on the hole transport layer, the light-emitting layer is on the electron blocking layer, the hole blocking layer is on the light-emitting layer, the electron transport layer is on the hole blocking layer, the electron injection layer is on the electron transport layer, the second electrode is on the electron injection layer, and the light extraction layer is on the second electrode.

[0335] As the substrate for the organic electroluminescent device of this invention, any substrate commonly used in organic electroluminescent devices can be used. Examples include transparent substrates, such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; and flexible PI film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Their application varies depending on their properties. In this invention, a transparent glass substrate is preferred, and the thickness of the substrate is not particularly limited.

[0336] A first electrode is formed on a substrate, and the first electrode and a second electrode may be opposite each other. The first electrode can be an anode or a cathode. In this invention, the first electrode serves as the anode, and the anode material is preferably a material with a high work function so that holes can be easily injected into the organic functional material layer. Non-limiting examples of anode materials include, but are not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The first electrode may have a single-layer structure or a multilayer structure comprising two or more layers. In addition, the thickness of the anode depends on the material used, typically 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

[0337] The hole injection layer, hole transport layer, and electron blocking layer can be disposed between the first electrode and the light-emitting layer.

[0338] The hole injection layer may comprise a host material and a p-type doped material. The host material may be selected from conventional hole transport materials in the prior art, preferably the same organic material as the hole transport layer. The p-type doped material is selected from charge-conducting compounds disclosed in the prior art, and may be selected from compounds disclosed in the following patent documents: WO2011073149A, EP1968131A1, EP2276085A1, EP2213662A1, EP1722602A1, EP2 045848A1, DE102007031220A1, US20100181555A1, US20100102709A1, WO2009003455A1, WO2010094378A1, WO2011120709A1, US20100096600A1, DE102012209523A1, CN101728485A and WO2012095143A1, but not limited to these.

[0339] For example, the compounds shown below:

[0340] P-1, P-2, P-3.

[0341] According to the present invention, P-1 is preferably used as the P-type doped material.

[0342] The thickness of the hole injection layer of the present invention can be 1-100 nm, preferably 2-50 nm and more preferably 5-20 nm.

[0343] The material of the hole transport layer is preferably a material with high hole mobility, which enables holes to be transferred from the anode or hole injection layer to the light-emitting layer.

[0344] Preferably, the hole transport layer material of the present invention may be selected from the compounds disclosed in the prior art:

[0345]

[0346] The thickness of the hole transport layer of the present invention can be 5-200 nm, preferably 10-180 nm, and more preferably 20-150 nm.

[0347] The electron blocking layer requires that its triplet (T1) energy level be higher than that of the host material in the emissive layer, thus blocking energy loss from the emissive layer material. The HOMO energy level of the electron blocking layer material should be between that of the hole transport layer material and the host material of the emissive layer, facilitating hole injection from the positive electrode into the emissive layer. Simultaneously, the electron blocking layer material should possess high hole mobility to promote hole transport and reduce the power consumption of the device. The LUMO energy level of the electron blocking layer material should be higher than that of the host material of the emissive layer, serving as an electron blocker; that is, the electron blocking layer material should have a wide bandgap (Eg). Electron blocking layer materials meeting these conditions can be triarylamine derivatives, fluorene derivatives, spirofluorene derivatives, dibenzofuran derivatives, carbazole derivatives, etc.

[0348] In one embodiment of the present invention, the electron blocking layer material may be selected from the compounds disclosed in the prior art:

[0349]

[0350] According to the present invention, the thickness of the electron blocking layer may be 1-200 nm, preferably 5-150 nm, and more preferably 5-50 nm.

[0351] According to the present invention, the light-emitting layer is located between the electron blocking layer and the hole blocking layer. The material of the light-emitting layer is a material that emits visible light by respectively receiving holes from the hole transport region and electrons from the electron transport region, and combining the received holes and electrons. The light-emitting layer may include a host material and a dopant material. The host material may be classified as a red light host material, a green light host material, a blue light host material, etc., and the dopant material may be classified as a red light dopant material, a green light dopant material, a blue light dopant material, etc. The present invention takes a blue light device as an example, using it as the host material and guest material of the light-emitting layer of the organic electroluminescent device of the present invention. The host material may be one or a combination of two of the following: anthracene derivatives, quinoxaline derivatives, triazine derivatives, xanthone derivatives, diphenyl ketone derivatives, carbazole derivatives, pyridine derivatives, or pyrimidine derivatives. The guest material may be a pyrene derivative, a boron derivative, a quinolone derivative, a spirofluorene derivative, an iridium complex, or a platinum complex.

[0352] The thickness of the light-emitting layer of the present invention can be 5-60 nm, preferably 10-50 nm, and more preferably 20-45 nm.

[0353] A hole-blocking layer can be disposed above the light-emitting layer. The triplet (T1) energy level of the hole-blocking layer material is higher than the T1 energy level of the main material of the light-emitting layer, which can block the energy loss of the light-emitting layer material; the HOMO energy level of the material is lower than the HOMO energy level of the main material of the light-emitting layer, which can block holes. At the same time, the hole-blocking layer material is required to have a suitable electron mobility to facilitate electron transport and reduce the power consumption of the device. The hole-blocking layer material that meets the above conditions is the triazine and phenanthrene compound described above in this invention.

[0354] The thickness of the hole blocking layer of the present invention can be 2-200 nm, preferably 5-150 nm and more preferably 5-50 nm, but the thickness is not limited to this range.

[0355] An electron transport layer can be disposed above a hole blocking layer. The electron transport layer material is one that readily receives electrons from the cathode and transfers them to the light-emitting layer. Preferably, a material with high electron mobility is used. As the electron transport layer of the organic electroluminescent device of the present invention, compounds disclosed in the prior art can be used as the electron transport layer material for the organic electroluminescent device:

[0356]

[0357] In a preferred embodiment of the invention, the electron transport layer further includes other compounds conventionally used in electron transport layers, such as Alq3, Liq, preferably Liq.

[0358] The thickness of the electron transport layer of the present invention can be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm.

[0359] According to the present invention, an electron injection layer may be disposed between the electron transport layer and the cathode. The electron injection layer material is generally preferably a material with a low work function, which facilitates electron injection into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material for the organic electroluminescent device of the present invention, the following electron injection layer materials for organic electroluminescent devices disclosed in the prior art can be used: LiF, Cs₂CO₃, CsF₂, Csq, NaF, MgF₂, CaF₂, Al₂O₃, and Yb.

[0360] The thickness of the electron injection layer of the present invention can be 0.1-5 nm, preferably 0.5-3 nm and more preferably 0.8-1.5 nm, but the thickness is not limited to this range.

[0361] According to the present invention, as previously described, the second electrode can be either a cathode or an anode. In this invention, the second electrode is used as the cathode. The material used to form the cathode can be a material with low work function, such as a metal, alloy, conductive compound, or a mixture thereof. Non-limiting examples of cathode materials may include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), as well as aluminum-lithium (Al-Li), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The thickness of the cathode depends on the material used, typically 5-100 nm, preferably 7-50 nm, and more preferably 10-25 nm.

[0362] Optionally, to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., a CPL layer) may be added above the second electrode (i.e., the cathode) of the device. The following compounds disclosed in the art in the prior art can be used as light extraction layer materials.

[0363]

[0364] The thickness of the light extraction layer is typically 5-300 nm, preferably 20-100 nm, and more preferably 40-80 nm.

[0365] Organic electroluminescent devices may also include an encapsulation structure. The encapsulation structure may be a protective structure that prevents external substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass or metal can; or a thin film covering the entire surface of the organic layer.

[0366] Methods for fabricating organic electroluminescent devices

[0367] The present invention also relates to a method for fabricating the above-mentioned organic electroluminescent device, comprising sequentially laminating a first electrode, an organic thin film layer, and a second electrode on a substrate. The organic thin film layer is formed by sequentially laminating a hole transport region thin film layer, a light-emitting region thin film layer, and an electron transport region thin film layer on the first electrode from bottom to top. The hole transport region thin film layer is formed by sequentially laminating a hole injection layer, a hole transport layer, and an electron blocking layer on the first electrode from bottom to top. The electron transport region thin film layer is formed by sequentially laminating a hole blocking layer, an electron transport layer, and an electron injection layer on the light-emitting layer from bottom to top. Optionally, a light extraction layer may also be laminated on the second electrode to improve the light extraction efficiency of the organic electroluminescent device.

[0368] Regarding lamination, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI can be used, but are not limited to these. Among them, vacuum evaporation refers to heating the material and depositing it onto the substrate in a vacuum environment.

[0369] In this invention, vacuum evaporation is preferably used to form the various layers, wherein the vapor deposition process can be carried out at a temperature of about 100-500°C for about 10... -8 -10 -2 Vacuum deposition is performed at a vacuum level of approximately 0.01-50 Å / s. The vacuum level is preferably 10 Å. -6 -10 -2 Torr, more preferably 10 -5 -10 -3 Torr. The rate is about 0.05-20 Å / s, more preferably about 0.1-10 Å / s.

[0370] In addition, it should be noted that the materials used to form each layer described in this invention can be used as a single layer by forming a film on their own, or they can be used as a single layer by mixing with other materials to form a film. They can also be a stacked structure between layers that are formed on their own, a stacked structure between layers that are formed by mixing, or a stacked structure between layers that are formed on their own and layers that are formed by mixing.

[0371] Display device

[0372] The present invention also relates to a display device including the aforementioned organic electroluminescent devices, particularly a flat panel display device. In a preferred embodiment, the display device may include one or more of the aforementioned organic electroluminescent devices, and in the case of multiple devices, the devices are stacked laterally or vertically. The display device may also include at least one thin-film transistor. The thin-film transistor may include a gate electrode, a source electrode and a drain electrode, a gate insulating layer and an active layer, wherein one of the source electrode and the drain electrode may be electrically connected to a first electrode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, organic semiconductor or oxide semiconductor, but is not limited thereto.

[0373] The following examples are intended to better explain the present invention, but the scope of the invention is not limited thereto.

[0374] Example

[0375] I. Compound Preparation Examples

[0376] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0377] All raw materials involved in the synthesis embodiments of the present invention can be purchased from the market or obtained by conventional preparation methods in the art;

[0378] Synthesis of intermediate b-1:

[0379]

[0380] Preparation of intermediate b-1: In a flask equipped with a magnetic stir bar, add starting material a-4 (14.44 g, 50 mmol), starting material a-5 (13.33 g, 52.5 mmol), xylene (200 ml), palladium acetate (112 mg, 0.5 mmol), (oxo-2,1-phenylene)bis(diphenylphosphine) (DPEPhos, 269 mg, 0.5 mmol), and anhydrous NaOAc (4.92 g, 60 mmol). Transfer the resulting mixture to a preheated oil bath (110°C) and stir for 22 hours. Evacuate the reaction mixture until all volatiles are distilled off, then distill off the product and transfer it to a liquid nitrogen trap to obtain intermediate b-1. LC-MS: Measured value: 381.26 ([M+H]+), exact mass: 380.19.

[0381] The synthesis methods of intermediates b-2 to b-7 are similar to those of intermediate b-1, with the same reaction conditions. The difference lies in the starting materials used, as shown in Table 1.

[0382] Table 1

[0383]

[0384] Example 1: Synthesis of compound 49:

[0385]

[0386] Preparation of intermediate O-1: Starting materials a-2 (5.74 g, 16 mmol), a-1 (4.16 g, 15.0 mmol), Pd(OAc)2 (101 mg, 0.450 mmol), PPh3 (239 mg, 0.911 mmol), and K2CO3 (6.23 g, 45.1 mmol) were added to a 200 mL double-necked round-bottom flask. Toluene (50 mL) and water (50 mL) were added via syringe, and the mixture was refluxed and reacted at 100 °C for 24 hours. The resulting mixture was extracted with ethyl acetate (30 mL × 3). The combined organic layers were dried over Na2SO4 and concentrated under vacuum. The residue was subjected to silica gel column chromatography (eluent: hexane) to give intermediate O-1. LC-MS: Measured value: 464.29 ([M+H]). + Precision quality: 463.07.

[0387] Preparation of compound 49: Under a nitrogen atmosphere, intermediate O-1 (23.22 g, 50 mmol) was added to a three-necked flask and dissolved in a mixed solvent (100 ml toluene, 50 ml ethanol, 50 ml H2O). The mixture was stirred under nitrogen for 1 hour. Then, intermediate b-1 (22.82 g, 60 mmol), K2CO3 (9.95 g, 72 mmol), and Pd(PPh3)4 (0.462 g, 0.4 mmol) were slowly added. The mixture was heated to 75 °C and reacted for 8 hours. The reaction was observed by thin-layer chromatography (TLC) until complete. After natural cooling, the mixture was filtered, and the filtrate was rotary evaporated and passed through a silica gel column to obtain compound 49.

[0388] The synthesis methods of Examples 2 to 8 are similar to those of Example 1, and the reaction conditions are the same. The difference lies in the raw materials and intermediates used, which are shown in Table 2.

[0389] Table 2

[0390]

[0391] Example 9: Synthesis of Compound 66

[0392]

[0393] Preparation of intermediate O-9: Under nitrogen protection, intermediate O-1 (9.29 g, 20 mmol), raw material a-3 (3.44 g, 22 mmol), K2CO3 (8.29 g, 60 mmol), tetrahydrofuran (250 mL), and water (100 mL) were added sequentially to a round-bottom flask. Nitrogen gas was purged for 40 min to replace the air. Pd(PPh3)4 (0.46 g, 0.4 mmol) was added, and the mixture was heated under nitrogen protection and refluxed for 24 h. TLC analysis of the reaction solution showed that intermediate O-1 reacted completely. After the reaction was complete, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, the residue was dissolved in 200 ml of dichloromethane, washed with 200 ml of water, poured into a separatory funnel, shaken, and allowed to stand for separation. The aqueous phase was extracted with dichloromethane (100 ml × 4). The organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was rotary evaporated to remove dichloromethane to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain intermediate O-9. LC-MS: Measured value: 496.34 ([M+H]+), theoretical value: 495.15.

[0394] Preparation of Compound 66: Under a nitrogen atmosphere, intermediate O-9 (24.8 g, 50 mmol) was added to a three-necked flask and dissolved in a mixed solvent (100 ml toluene, 60 ml ethanol, 50 ml H2O). The mixture was stirred under nitrogen for 1 hour. Then, intermediate b-1 (22.82 g, 60 mmol), K2CO3 (10.37 g, 75 mmol), palladium acetate (0.057 g, 0.25 mmol), and Xphos (0.238 g, 0.5 mmol) were slowly added. The mixture was heated to 75 °C and reacted for 10 hours. The reaction was observed by thin-layer chromatography (TLC) until complete. After natural cooling, the mixture was filtered, and the filtrate was rotary evaporated and passed through a silica gel column to obtain compound 66.

[0395] The synthesis methods of Examples 10 to 13 are similar to those of Example 9, and the reaction conditions are the same. The difference lies in the raw materials and intermediates used, which are shown in Table 3.

[0396] Table 3

[0397]

[0398] Example 14: Synthesis of Compound 187

[0399]

[0400] Preparation of intermediate O-14: Under a nitrogen atmosphere, starting material a-17 (17.95 g, 50 mmol) was added to a three-necked flask and dissolved in a mixed solvent (100 ml toluene, 50 ml ethanol, 50 ml H2O). The mixture was stirred under nitrogen for 1 hour. Then, starting material a-3 (9.38 g, 60 mmol), K2CO3 (9.95 g, 72 mmol), and Pd(PPh3)4 (0.462 g, 0.4 mmol) were slowly added. The mixture was heated to 75 °C and reacted for 6 hours. The reaction was observed using thin-layer chromatography (TLC) until complete. After natural cooling, the mixture was filtered, and the filtrate was rotary evaporated and passed through a silica gel column to obtain intermediate O-14. LC-MS: Measured value: 342.87 ([M+H]+), theoretical value: 341.98.

[0401] Preparation of intermediate P-14: Refer to the preparation of intermediate O-9, except that intermediate O-1 is replaced by intermediate O-14 and raw material a-3 is replaced by raw material a-16. LC-MS: Test value: 572.39 ([M+H]+), theoretical value: 571.18.

[0402] Preparation of compound 187: Refer to the preparation of compound 66, except that intermediate O-9 is replaced by intermediate P-14.

[0403] Example 15: Synthesis of Compound 219

[0404]

[0405] Preparation of intermediate O-15: Refer to the preparation of intermediate O-14, except that raw material a-3 is replaced by raw material a-19. LC-MS: Test value: 342.91 ([M+H]+), theoretical value: 341.98.

[0406] Preparation of intermediate P-15: Refer to the preparation of intermediate O-9, except that intermediate O-1 is replaced by intermediate O-15 and raw material a-3 is replaced by raw material a-18. LC-MS: Test value: 572.22 ([M+H]+), theoretical value: 571.18.

[0407] Preparation of compound 219: Refer to the preparation of compound 66, except that intermediate O-9 is replaced by intermediate P-15.

[0408] Example 16: Synthesis of Compound 231

[0409]

[0410] Preparation of intermediate O-16: Refer to the preparation of intermediate O-9, except that intermediate O-1 is replaced by intermediate O-14, and raw material a-3 is replaced by raw material a-18. LC-MS: Test value: 572.36 ([M+H]+), theoretical value: 571.18.

[0411] Preparation of compound 231: Refer to the preparation of compound 66, except that intermediate O-9 is replaced by intermediate O-16 and starting material b-1 is replaced by starting material b-3.

[0412] Example 17: Synthesis of Compound 86

[0413]

[0414] Preparation of intermediate O-17: In a three-necked flask under nitrogen protection, intermediate O-1 (1.39 g, 3 mmol), starting material a-5 (0.84 g, 3.3 mmol), NaOAc (1 g, 12 mmol), and Pd(PPh3)2Cl2 (0.14 g, 0.2 mmol) were added sequentially to 20 mL of DMF. The mixture was stirred in a 90°C oil bath for 10 h. Hexane and ethyl acetate were used as eluents, and the reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the reaction system was cooled to room temperature and extracted with diethyl ether (10 mL × 3). The ether layer was washed three times with brine, dried over anhydrous magnesium sulfate, and purified by vacuum distillation using hexane and ethyl acetate (9:1) as eluents, yielding intermediate O-17. LC-MS: Measured value: 512.37 ([M+H]+), theoretical value: 511.24.

[0415] Preparation of intermediate P-17: Under a nitrogen atmosphere, starting material a-7 (17.95 g, 50 mmol) was added to a three-necked flask and dissolved in a mixed solvent (100 ml toluene, 50 ml ethanol, 50 ml H2O). The mixture was stirred under nitrogen for 1 hour. Then, intermediate O-17 (28.13 g, 55 mmol), K2CO3 (9.95 g, 72 mmol), and Pd(PPh3)4 (0.462 g, 0.4 mmol) were slowly added. The mixture was heated to 75 °C and reacted for 5 hours. The reaction was observed using thin-layer chromatography (TLC) until complete. After natural cooling, the mixture was filtered, and the filtrate was rotary evaporated and passed through a silica gel column to obtain intermediate P-17. LC-MS: Measured value: 616.07 ([M+H]+), theoretical value: 615.13.

[0416] Preparation of compound 86: Refer to the preparation of compound 49, except that intermediate O-1 is replaced by intermediate P-17.

[0417] Example 18: Synthesis of Compound 97

[0418]

[0419] Preparation of intermediate O-18: Refer to the preparation of intermediate O-14, except that raw material a-8 is used instead of raw material a-17, and raw material a-1 is used instead of raw material a-3. LC-MS: Test value: 422.04 ([M+H]+), theoretical value: 421.00.

[0420] Preparation of intermediate P-18: Refer to the preparation of intermediate O-9, except that intermediate O-1 is replaced by intermediate O-18, and raw material a-3 is replaced by raw material a-9. LC-MS: Test value: 421.18 ([M+H]+), theoretical value: 420.11.

[0421] Preparation of intermediate Q-18: Refer to the preparation of intermediate b-1, except that intermediate P-18 is used to replace the starting material a-4. LC-MS: Test value: 513.39 ([M+H]+), theoretical value: 512.24.

[0422] Preparation of intermediate R-18: Refer to the preparation of intermediate P-17, except that intermediate Q-18 is used instead of intermediate O-17. LC-MS: Test value: 617.21 ([M+H]+), theoretical value: 616.13.

[0423] Preparation of compound 86: Refer to the preparation of compound 49, except that intermediate O-1 is replaced by intermediate R-18.

[0424] Example 19: Synthesis of Compound 160

[0425]

[0426] Preparation of intermediate O-19: Refer to the preparation of intermediate P-17, except that intermediate b-3 is used instead of intermediate O-17, and starting material a-17 is used instead of starting material a-7. LC-MS: Test value: 485.11 ([M+H]+), theoretical value: 484.08.

[0427] Preparation of compound 160: Refer to the preparation of intermediate O-9, except that intermediate O-1 is replaced by intermediate O-19 and starting material a-3 is replaced by starting material a-16.

[0428] Example 20: Synthesis of Compound 211

[0429]

[0430] Preparation of intermediate O-20: Refer to the preparation of intermediate P-17, except that intermediate b-1 is used instead of intermediate O-17, and starting material a-17 is used instead of starting material a-7. LC-MS: Test value: 485.23 ([M+H]+), theoretical value: 484.08.

[0431] Preparation of intermediate P-20: Refer to the preparation of intermediate O-9, except that intermediate O-1 is replaced by intermediate O-20. LC-MS: Test value: 517.06 ([M+H]+), theoretical value: 516.16.

[0432] Preparation of compound 211: Under a nitrogen atmosphere, intermediate P-20 (25.85 g, 50 mmol) was added to a three-necked flask and dissolved in a mixed solvent (100 ml toluene, 50 ml ethanol, 50 ml H2O). The mixture was stirred under nitrogen for 1 hour. Then, starting material a-16 (21.19 g, 60 mmol), K2CO3 (9.95 g, 72 mmol), and Xphos (0.191 g, 0.4 mmol) were slowly added. The mixture was heated to 75 °C and reacted for 10 hours. The reaction was observed by thin-layer chromatography (TLC) until complete. After natural cooling, the mixture was filtered, and the filtrate was rotary evaporated and passed through a silica gel column to obtain compound 211.

[0433] Example 21: Synthesis of Compound 303

[0434]

[0435] Preparation of intermediate O-21: Refer to the preparation of compound 49, except that intermediate O-1 was replaced by intermediate O-14. LC-MS: Measured value: 517.23 ([M+H]+), theoretical value: 516.16.

[0436] Preparation of compound 303: Refer to the preparation of compound 211, except that intermediate P-20 is replaced by intermediate O-21.

[0437] The structural characterization of the compounds obtained in each example is shown in Table 4:

[0438] Table 4

[0439]

[0440]

[0441] II. Device Fabrication Examples

[0442] The following describes in detail the application effects of the compounds synthesized according to the present invention as hole blocking layer materials in devices through device Examples 1-42 and device Comparative Examples 1-17. Device Examples 1-42 and device Comparative Examples 2-17 are identical to device Comparative Example 1 in terms of fabrication process, substrate material, electrode material, and electrode film thickness; the only difference is the change in the hole blocking layer material. The device layer structures are shown in Table 5, and the performance test results of each device are shown in Table 6.

[0443] The molecular structural formulas of the relevant materials are shown below:

[0444] HT-1 EB-1

[0445] ET-1

[0446] CP-1

[0447] HB-1 HB-2 HB-3

[0448] HB-4 HB-5 HB-6

[0449] HB-7 HB-8 HB-9

[0450] HB-10 HB-11 HB-12

[0451] HB-13 HB-14 HB-15

[0452] HB-16 HB-17

[0453] The structures of compounds HB-1, HB-2, HB-3, HB-4, HB-5, HB-6, HB-7, HB-8, HB-9, HB-10, HB-11, HB-12, HB-13, HB-14, HB-15, HB-16, and HB-17 are shown above. These materials are commercially available or obtained using conventional preparation methods in this field.

[0454] Device Comparison Example 1

[0455] The specific preparation process is as follows:

[0456] like Figure 1As shown, the transparent substrate layer 1 is transparent glass. Ag (100nm) is deposited as the anode layer 2. On the anode layer 2, HT-1 and P-1 with a thickness of 10nm are deposited using a vacuum evaporation apparatus as the hole injection layer 3, with a mass ratio of HT-1 to P-1 of 97:3. Next, HT-1 with a thickness of 130nm is deposited as the hole transport layer 4. Subsequently, EB-1 with a thickness of 5nm is deposited as the electron blocking layer 5. After the electron blocking materials are deposited, the light-emitting layer 6 of the organic electroluminescent device is fabricated, using BH-1 as the host material and BD-1 as the dopant material, with a doping ratio of 3% by weight, and a light-emitting layer thickness of 20nm. After the light-emitting layer 6, HB-1 is deposited with a thickness of 5nm as the hole blocking layer 7. On the hole blocking layer 7, ET-1 and Liq are deposited with a mass ratio of ET-1 to Liq of 1:1. The vacuum-deposited film of this material is 30 nm thick, and this layer is the electron transport layer 8. On the electron transport layer 8, a 1 nm thick LiF layer is fabricated using a vacuum evaporation apparatus; this layer is the electron injection layer 9. On the electron injection layer 9, a 16 nm thick Mg:Ag electrode layer is fabricated using a vacuum evaporation apparatus, with a Mg to Ag mass ratio of 1:9; this layer is used as the cathode layer 10. On the cathode layer 10, a 65 nm thick CP-1 layer is vacuum-deposited as the light extraction layer 11.

[0457] Device Examples 1-42 and Device Comparative Examples 2-17 were prepared in a similar manner to Device Comparative Example 1, except that the hole blocking layer materials in Table 5 below were used.

[0458] Table 5

[0459]

[0460]

[0461]

[0462]

[0463] III. Device Testing Examples

[0464] The devices fabricated in Part II were tested to determine their current efficiency, CIEy, and LT95 lifetime. Current efficiency and CIEy were measured using an IVL (current-voltage-luminance) testing system (Suzhou Fushida Scientific Instruments Co., Ltd.), with a current density of 10 mA / cm². 2 LT95 refers to the time it takes for the device's brightness to decay to 95% of its initial brightness, measured at a current density of 30 mA / cm². 2The lifetime testing system was the EAS-62C OLED device lifetime tester from System Technology Inc., Japan; the test results are shown in Table 6 below.

[0465] Table 6

[0466]

[0467] As can be seen from the device test data in Table 6 above, compared with the comparative devices using HB-1, HB-2, HB-3, HB-4, HB-5, HB-6, HB-7, HB-8, HB-9, HB-10, HB-11, HB-12, HB-13, HB-14, HB-15, HB-16, and HB-17 as hole blocking layer materials, the devices prepared using the compounds of this invention as hole blocking layer materials have improved current efficiency and extended device lifetime.

[0468] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A compound containing triazine and phenanthrene, characterized in that, The structure of the compound is shown in general formula (1): General formula (1) In general formula (1), Ar1 and Ar2 are each independently represented as substituted or unsubstituted C1-C. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 50 aryl, substituted or unsubstituted C3-C 50 Mixed aromatics; Ar1 and Ar2 may be the same or different; a and b represent the numbers 0 or 1, and a + b ≥ 1; L1 and L2 can be independently represented as single bond, phenylene, diphenylene, terphenylene, and tetraphenylene; L1 and L2 may be the same or different; R represents one of phenyl, naphthyl, diphenyl, triphenyl, pyridyl, or pyrimidinyl. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each is represented independently as a hydrogen atom, C1-C 20 Alkyl, C3-C 20 Cycloalkyl, pyridyl, phenyl, or diphenyl; The R7, R8, R9, R 10 There is one and only one site that is connected to L2; The R1~R 10 There is one and only one representation of C1-C. 20 One of alkyl, phenyl, or diphenyl; The substituents of the above groups, whether substituted or unsubstituted, may be selected from deuterium, C1-C... 20 Alkyl, C3-C 20 Cycloalkyl, phenyl, diphenyl, naphthyl, triphenyl, pyridyl, pyrimidinyl; * Indicates a connection site; In general formula (1), any hydrogen atom can be optionally replaced by a deuterium atom.

2. The compound containing triazine and phenanthrene according to claim 1, characterized in that, The structure of the compound is shown in any one of general formulas (2-1) to (2-19): General formula (2-1) General formula (2-2) General formula (2-3) General formula (2-4) General formula (2-5) General formula (2-6) General formula (2-7) General formula (2-8) General formula (2-9) General formula (2-10) General formula (2-11) General formula (2-12) General formula (2-13) General formula (2-14) General formula (2-15) General formula (2-16) General formula (2-17) General formula (2-18) General formula (2-19) In general formulas (2-1) to (2-19), Ar1, Ar2, L1, L2, R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The meaning is the same as that in the general formula (1) of claim 1.

3. The compound containing triazine and phenanthrene according to claim 1, characterized in that, The structure of the compound is shown in any one of general formulas (3-1) to (3-30): General formula (3-1) General formula (3-2) General formula (3-3) General formula (3-4) General formula (3-5) General formula (3-6) General formula (3-7) General formula (3-8) General formula (3-9) General formula (3-10) General formula (3-11) General formula (3-12) General formula (3-13) General formula (3-14) General formula (3-15) General formula (3-16) General formula (3-17) General formula (3-18) General formula (3-19) General formula (3-20) General formula (3-21) General formula (3-22) General formula (3-23) General formula (3-24) General formula (3-25) General formula (3-26) General formula (3-27) General formula (3-28) General formula (3-29) General formula (3-30) In general formulas (3-1) to (3-30), Ar1, Ar2, R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The meanings of a and b are the same as those in the general formula (1) of claim 1.

4. The compound containing triazine and phenanthrene according to claim 1, characterized in that, The structure of the compound is shown in any one of general formulas (4-1) to (4-17): General formula (4-1) General formula (4-2) General formula (4-3) General formula (4-4) General formula (4-5) General formula (4-6) General formula (4-7) General formula (4-8) General formula (4-9) General formula (4-10) General formula (4-11) General formula (4-12) General formula (4-13) General formula (4-14) General formula (4-15) General formula (4-16) General formula (4-17) In general formulas (4-1) to (4-17), Ar1, Ar2, L1, L2, R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The meaning is the same as that defined in general formula (1) in claim 1; R' represents one of the following: hydrogen atom, phenyl, naphthyl, diphenyl, terphenyl, pyridyl, or pyrimidinyl.

5. The compound containing triazine and phenanthrene according to claim 1, characterized in that, The structure of the compound is shown in any one of general formulas (5-1) to (5-7): General formula (5-1) General formula (5-2) General formula (5-3) General formula (5-4) General formula (5-5) General formula (5-6) General formula (5-7) In general formulas (5-1) to (5-7), Ar1, Ar2, L1, L2, R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The meanings of a and b are the same as those in the general formula (1) of claim 1.

6. The compound containing triazine and phenanthrene according to claim 1, characterized in that, In the general formula (1) It can be represented as the structure shown below: , , , , , , Any one of them; The R1, R2, R 10 Each independently is represented as C1-C 20 Alkyl, C3-C 20 Cycloalkyl, phenyl, or diphenyl.

7. The compound containing triazine and phenanthrene according to claim 1, characterized in that, Ar1 and Ar2 are each independently represented as substituted or unsubstituted C1-C. 20 Alkyl, substituted or unsubstituted C3-C 20 The cycloalkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted diphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted carbazole group; Ar1 ​​and Ar2 may be the same or different; The R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each can be represented independently as a hydrogen atom, methyl, tert-butyl, isopropyl, adamantyl, phenyl, or diphenyl. The substituents may be selected from deuterium, methyl, ethyl, propyl, isopropyl, tert-amyl, tert-butyl, butyl, adamantyl, cyclopentyl, cyclohexyl, phenyl, diphenyl, naphthyl, terphenyl, pyridyl, or pyrimidinyl.

8. The compound containing triazine and phenanthrene according to claim 1, characterized in that, The specific structure of the compound is any one of the following structures: (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (45) (46) (47) (48) (49) (50) (51) (52) (53) (54) (55) (56) (57) (58) (59) (60) (61) (62) (63) (64) (65) (66) (67) (68) (69) (70) (71) (72) (73) (74) (75) (76) (77) (78) (79) (80) (81) (82) (83) (84) (85) (86) (87) (88) (89) (90) (91) (92) (93) (94) (95) (96) (97) (98) (99) (100) (101) (102) (103) (104) (105) (106) (107) (108) (109) (110) (111) (112) (113) (114) (115) (116) (117) (118) (119) (120) (121) (122) (123) (124) (125) (126) (127) (128) (129) (130) (131) (132) (133) (134) (135) (136) (137) (138) (139) (140) (141) (142) (143) (144) (145) (146) (147) (148) (149) (150) (151) (152) (153) (154) (155) (156) (157) (158) (159) (160) (161) (162) (163) (164) (165) (166) (167) (168) (169) (170) (171) (172) (173) (174) (175) (176) (177) (178) (179) (180) (181) (182) (183) (184) (185) (186) (187) (188) (189) (190) (191) (192) (193) (194) (195) (196) (197) (198) (199) (200) (201) (202) (203) (204) (205) (206) (207) (208) (209) (210) (211) (212) (213) (214) (215) (216) (217) (218) (219) (220) (221) (222) (223) (224) (225) (226) (227) (228) (229) (230) (231) (232) (233) (234) (235) (236) (237) (238) (239) (240) (241) (242) (243) (244) (245) (246) (247) (248) (249) (250) (251) (252) (253) (254) (255) (256) (257) (258) (259) (260) (261) (262) (263) (264) (265) (266) (267) (268) (269) (270) (271) (272) (273) (274) (275) (276) (277) (278) (279) (280) (281) (282) (283) (284) (285) (286) (287) (288) (289) (290) (291) (292) (293) (294) (295) (296) (297) (298) (299) (300) (301) (302) (303) (304) (305) (306) (307) (308) (309) (310) (311) (312) (313) (314) (315) (316) (317) (318) (319) (320) (321) (322) (323) (324) (325) (326) (327) (328) (329) (330) (331) (332) (333) (334) (335) (336) (337) (338) (339) (340) (341) (342) (343) (344) (345) (346) (347) (348) (349) (350) (351) (352) (353) (354) (355) (356) (357) (358) (359) (360) (361) (362) (363) (364) (365) (366) (367) (368) (369) (370) (371) (372) (373) (374) (375) (376) (377) (378) (379) (380) (381) (382) (383) (384) (385) (386) (387) (388) (389) (390) (391) (392) (393) (394) (395) (396) (397) (398) (399) (400) (401) (402) (403) (404) (405) (406) (407) (408) (409) (410) (411) (412) (413) (414) (415) (416) (417) (418) (419) (420) (421) (422) (423) (424) (425) (426) (427) (428) (429) (430) (431) (432) (433) (434) (435) (436) (437) (438) (439) (440) (441) (442) (443) (444) (445) (446) (447) (448) (449) (450) (451) (452) (453) (454) (455) (456) (457) (458) (459) (460) (461) (462) (463) (464) (465) (466) (467) (468) (469) (470) (471) (472) (473) (474) (475) (476) (477) (478) (479) (480) (481) (482) (483) (484) (485) (486) (487) (488) (489) (490) (491) (492) (493) (494) (495) (496) (497) (498) (499) (500) (501) (502) (503) (504) (505) (506) (507) (508) (509) (510) (511) (512) (513) (514) (515) (516) (517) (518) (519) (520) (521) (522) (523) (524) (525) (526) (527) (528) (529) (530) (531) (532) (533) (534) (535) (536) (537) (538) (539) (540) (541) (542) (543) (544) (545) (546) (547) (548) (549) (550) (551) (552) (553) (554) (555) (556) (557) (558) (559) (560) (561) (562) (563) (564) (565) (566) (567) (568) (569) (570) (571) (572) (573) (574) (575) (576) (577) (578) (579) (580) (581) (582) (583) (584) (585) (586) (587) (588) (589) (590) (591) (592) (593) (594) (595) (596) (597) (598) (599) (600) (601) (602) (603) (604) (605) (606) (607) (608)。 9. An organic electroluminescent device, comprising, in sequence, a substrate, a first electrode, an organic thin film layer, and a second electrode, characterized in that, The organic thin film layer contains the triazine and phenanthrene compound as described in any one of claims 1 to 8; Preferably, the organic thin film layer includes a hole transport region thin film layer, a light emission region thin film layer, and an electron transport region thin film layer, wherein the electron transport region thin film layer contains the triazine and phenanthrene compound as described in any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, characterized in that, The electron transport region thin film layer includes a hole blocking layer, the hole blocking layer containing a triazine and phenanthrene compound as described in any one of claims 1 to 8; Preferably, the electron transport region thin film layer comprises a hole blocking layer, an electron transport layer, and an electron injection layer, wherein the hole blocking layer contains a triazine and phenanthrene compound as described in any one of claims 1 to 8.

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