Compound containing triazine and spiroanthracene fluorene structures and organic electroluminescent device thereof

Abstract

The invention discloses a compound containing triazine and spiroanthracene fluorene structures and an organic electroluminescent device thereof, and belongs to the technical field of semiconductor materials. The compound containing the triazine and spiroanthracene fluorene structure is shown as a general formula (1): # imgabs0. The compound containing the triazine and spiroanthracene fluorene structure is applied to an organic thin film layer of an organic electroluminescent device, and is particularly applied to a hole blocking layer in an electron transmission region thin film layer of the organic thin film layer. The compound containing the triazine and spiroanthracene fluorene structure has good stability and good hole blocking capability, and when the compound containing the triazine and spiroanthracene fluorene structure is used as a material of an organic electroluminescent device, the efficiency of the device is remarkably improved, and the service life of the device is remarkably prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of semiconductor materials, in particular to a compound containing triazine and spiroanthracene structures and an organic electroluminescent device thereof. Background Art

[0002] Organic light-emitting diode (OLED) technology can be used to manufacture new display products as well as new lighting products. It is expected to replace existing liquid crystal displays and fluorescent lighting, and has a wide range of applications. Organic light-emitting diodes have a sandwich-like structure, including electrode material films and organic photoelectric functional materials sandwiched between different electrode material films. Various organic functional materials are superimposed on each other according to their uses to form organic light-emitting diodes. As a current device, when voltage is applied to the electrodes at both ends of the organic light-emitting diode and the electric field acts on the positive and negative charges in the organic photoelectric functional material film layer, the positive and negative charges further recombine in the light-emitting layer, generating organic electroluminescence.

[0003] Currently, organic electroluminescent device display technology has been applied in smart phones, tablet computers, TVs and other fields. However, compared with the actual product application requirements, the performance of organic electroluminescent devices such as luminous efficiency and service life needs to be further improved. In order to continuously improve the performance of organic electroluminescent devices, it is necessary to continuously research and innovate organic optoelectronic functional materials to create higher performance organic optoelectronic functional materials.

[0004] Organic optoelectronic functional materials used in organic electroluminescent devices can be divided into two categories based on their uses, namely charge injection and transport materials and luminescent materials. Furthermore, charge injection and transport materials can be divided into electron injection and transport materials, electron blocking materials, hole injection and transport materials, and hole blocking materials. For organic electroluminescent devices, holes are injected from the anode, electrons are injected from the cathode, and are transported in the organic functional layer, and finally meet in the luminescent layer to form excitons, which recombine and emit light. The hole blocking layer is located between the luminescent layer and the electron transport layer, which can block the diffusion or movement of holes to the electron transport layer, and can also reduce the energy loss of excitons, playing a role in interface modification and auxiliary regulation of electron injection / transport. Due to the poor electron regulation ability and hole and exciton blocking ability of the existing hole blocking layer materials, it is difficult to obtain an efficient electron-hole balance inside the light-emitting layer, and it is difficult to obtain low-voltage, high-efficiency, and long-life devices. At the same time, the existing hole blocking layer materials also have a narrow heat resistance window and poor electron tolerance. Therefore, it is necessary to further improve the electron injection and transmission capabilities of the hole blocking layer materials, the hole and exciton blocking ability, enhance the stability of the material, reduce the device's turn-on voltage and driving voltage, achieve an efficient balance of excitons, and improve the device's efficiency and device life. Summary of the invention

[0005] In view of the above problems existing in the prior art, the present invention provides a compound containing triazine and spiroanthraquinone structures and an organic electroluminescent device thereof. In the compound of the present invention, the triazine and spiroanthraquinone derivatives are bridged by a specific site phenyl group with a substituent, so that the compound has excellent hole blocking ability and good material stability. When applied to an organic electroluminescent device, the device operating voltage can be effectively reduced, and the device luminous efficiency and service life can be improved.

[0006] The technical solution of the present invention is as follows: a compound containing triazine and spiroanthraquinone structures, wherein the compound containing triazine and spiroanthraquinone structures is as shown in the general formula (1):

[0007]

[0008] In the general formula (1), Ar 1 ,Ar 2 Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted carbazolyl group;

[0009] Y 1 , Y 2 , Y 3 , Y 4 Each independently represents CH or N; Y 1 , Y 2 , Y 3 , Y 4 Can be the same or different; Y 2 , Y 3 At least one of them is represented by CH;

[0010] * indicates the connection position;

[0011] L 1 , L 2 , L 3 Each independently represents a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted pyridylene group; L 1 , L 2 , L 3 Can be the same or different;

[0012] R 1 , R 2Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group or a structure represented by the general formula (2); R 1 , R 2 There is only one that can be represented by the general formula (2); Ar 1 ,Ar 2 , R 1 Can be the same or different; Ar 1 ,Ar 2 , R 2 Can be the same or different;

[0013]

[0014] In the general formula (2), X represents any one of an oxygen atom, a sulfur atom, and a dimethyl-substituted methylene group; any unsubstituted carbon on the benzene ring or naphthalene ring in the general formula (2) can serve as a connection site with the general formula (1);

[0015] Ring A and Ring B are each independently a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group;

[0016] The substituent of the substituted group is selected from a deuterium atom, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a phenanthryl group, a pyrimidyl group or a halogen atom.

[0017] Furthermore, the compound containing triazine and spiroanthracene structures is represented by any one of the general formulas (3) and (4):

[0018]

[0019] In the general formula (3) and the general formula (4), Ar 1 ,Ar 2 , R 1 , R 2 , L 1 , L 2 , Y 1 , Y 2 , Y 3 , Y 4 has the same meaning as defined above.

[0020] Furthermore, the compound containing triazine and spiroanthracene structures is any one of the general formulas (5) to (10):

[0021]

[0022] In the general formula (5) to the general formula (10), Ar 1 ,Ar 2 , R 1 , R 2 , L 1, L 2 , Y 1 , Y 2 , Y 3 , Y 4 has the same meaning as defined above.

[0023] Furthermore, the compound containing triazine and spiroanthracene structures is any one of the general formulas (11) to (41):

[0024]

[0025]

[0026] In the general formula (11) to the general formula (41), Ar 1 ,Ar 2 , R 1 , R 2 has the same meaning as defined above.

[0027] Furthermore, the general formula (2) is represented by any one of the general formula a, general formula b, and general formula c:

[0028]

[0029] R in formula a, formula b, and formula c 3 , R 4 Each independently represents a hydrogen atom, a deuterium atom, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a phenanthryl group, a pyrimidyl group or a halogen atom; R 3 , R 4 Can be the same or different;

[0030] Any unsubstituted carbon on the benzene ring or naphthalene ring in general formula a, general formula b, and general formula c can serve as a connection site with general formula (1);

[0031] In general formula a, general formula b and general formula c, X has the same meaning as defined above.

[0032] Further, the general formula (2) is represented by any one of the general formula a-1, general formula b-1, general formula b-2, general formula b-3, general formula c-1, general formula c-2 or general formula c-3:

[0033]

[0034]

[0035] In the general formula a-1, the connection site with the general formula (1) is any one of sites 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16; R 3 The connection site of R is any one of sites 9, 10, 11 or 12;4 The connection site is any one of sites 13, 14, 15 or 16;

[0036] In the general formula b-1, the connection site with the general formula (1) is any one of 1', 2', 3', 4', 5', 6', 7', 8', 9', 10', 11', 12', 13', 14', 15', 16', 17' or 18'; R 3 The connection site is any one of 9', 10', 11', 12', 13' or 14'; 4 The connection site is any one of 15', 16', 17' or 18';

[0037] In the general formula b-2, the connection site with the general formula (1) is any one of 19', 20', 21', 22', 23', 24', 25', 26', 27', 28', 29', 30', 31', 32', 33', 34', 35' or 36'; R 3 The connection site is any one of 27', 28', 29', 30', 31' or 32'; R 4 The connection site is any one of 33', 34', 35' or 36';

[0038] In the general formula b-3, the connection site with the general formula (1) is any one of 37', 38', 39', 40', 41', 42', 43', 44', 45', 46', 47', 48', 49', 50', 51', 52', 53' or 54'; R 3 The connection site is any one of 45', 46', 47', 48', 49' or 50'; 4 The connection site is any one of 51', 52', 53' or 54';

[0039] In the general formula c-1, the connection site with the general formula (1) is any one of 1", 2", 3", 4", 5", 6", 7", 8", 9", 10", 11", 12", 13", 14", 15", 16", 17" or 18"; R 3 The connection site is any one of 9", 10", 11" or 12"; R 4 The connection site is any one of 13", 14", 15", 16", 17" or 18";

[0040] In the general formula c-2, the connection site with the general formula (1) is any one of sites 19", 20", 21", 22", 23", 24", 25", 26", 27", 28", 29", 30", 31", 32", 33", 34", 35" or 36"; R 3 The connection site is any one of 27", 28", 29" or 30"; R 4 The connection site is any one of 31", 32", 33", 34", 35" or 36";

[0041] In the general formula c-3, the connection site with the general formula (1) is any one of sites 37", 38", 39", 40", 41", 42", 43", 44", 45", 46", 47", 48", 49", 50", 51", 52", 53" or 54"; R 3 The connection site is any one of 45", 46", 47" or 48"; R 4 The connection site is any one of sites 49", 50", 51", 52", 53" or 54";

[0042] In the general formula a-1, general formula b-1, general formula b-2, general formula b-3, general formula c-1, general formula c-2, and general formula c-3, X, R 3 , R 4 has the same meaning as defined above.

[0043] Furthermore, in the general formula (1), Y 1 , Y 2 , Y 3 , Y 4 At least one of them is represented by N.

[0044] Furthermore, the Ar 1 ,Ar 2 Selected from the following structures:

[0045] Any one of.

[0046] Furthermore, the structure of general formula (2) is as follows:

[0047]

[0048] Any of the following:

[0049] X has the same meaning as defined above.

[0050] Furthermore, the structure of general formula (2) is as follows:

[0051]

[0052] Any one of the following is shown.

[0053] Furthermore, the R 1 It is represented by the structure shown in general formula (2), wherein R 2 Selected from the following structures: Any one of.

[0054] Furthermore, the R 2 It is represented by the structure shown in general formula (2), wherein R 1 Selected from the following structures: Any one of.

[0055] Furthermore, the specific structure of the compound containing triazine and spiroanthraquinone structures is any one of the following structures:

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073] The invention also discloses an organic electroluminescent device, which comprises a substrate, a first electrode and a second electrode, wherein a multilayer organic film layer is provided between the first electrode and the second electrode, and the organic film layer contains the compound containing triazine and spiroanthracene structures of the invention.

[0074] Furthermore, 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, and the electron transport region thin film layer contains the triazine and spiroanthracene structure-containing compound of the present invention.

[0075] Furthermore, the electron transport region thin film layer comprises a hole blocking layer, and the hole blocking layer contains the compound containing triazine and spiroanthracene structures of the present invention.

[0076] Furthermore, 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 compound containing triazine and spiroanthracene structures described in the present invention.

[0077] The beneficial technical effects of the present invention are:

[0078] In the compound containing triazine and spiroanthracene structures of the present invention, the triazine structure and the spiroanthracene derivative are connected by a special bridging method, so that the compound containing triazine and spiroanthracene structures has more excellent hole blocking and exciton blocking capabilities, can effectively block holes from diffusing or moving to the electron transport layer, so that the holes are better confined in the light-emitting area, ensuring that more excitons are formed by holes and electrons in the light-emitting layer, increasing the exciton concentration, and thus improving the light-emitting efficiency and device life.

[0079] The triazine structure and the spiroanthraquinone derivative structure in the compound containing triazine and spiroanthraquinone structures of the present invention are bridged by a substituted phenyl or pyridyl group, and the ortho position of the phenyl or pyridyl group as the bridging group must be connected to the triazine to form this twisted special spatial stereo configuration molecule. Therefore, the compound containing triazine and spiroanthraquinone structures of the present invention has a more excellent electron regulation ability, supplements the electron transport layer, improves or delays electron injection and transport according to the electron-hole balance in the light-emitting layer, and improves the luminous efficiency and device life of the organic electroluminescent device.

[0080] The compound containing triazine and spiroanthracene structures of the present invention has a lower evaporation temperature and chemical stability, so that the evaporation film thereof has good film phase stability and a wider heat resistance window, thereby ensuring the stability in device manufacturing and product use. BRIEF DESCRIPTION OF THE DRAWINGS

[0081] Figure 1 It is a schematic diagram of the structure of the organic electroluminescent device described in the application example.

[0082] In the figure, 1, transparent substrate layer; 2, anode layer; 3, hole injection layer; 4, hole transport layer; 5, electron blocking layer; 6, light-emitting layer; 7, hole blocking layer; 8, electron transport layer; 9, electron injection layer; 10, cathode layer; 11, light extraction layer. DETAILED DESCRIPTION

[0083] The technical solution of the present invention will be described in detail below in conjunction with the accompanying drawings and implementation plans.

[0084] In this application, unless otherwise specified, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule. In addition, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and the comparison between energy levels is also a comparison of the magnitude of their absolute values. Those skilled in the art know that the greater the absolute value of an energy level, the lower the energy of the energy level.

[0085] In the accompanying drawings, the sizes 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 "on" another layer or substrate, the layer or element may be directly on the other layer or substrate, or there may be intervening layers. In addition, 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 intervening layers. The same reference numerals throughout the text represent the same elements.

[0086] In this application, when describing electrodes and organic electroluminescent devices, as well as other structures, the words "upper" and "lower" used to indicate orientation only indicate orientation in a certain state, and do not mean that the related structure can only exist in the described orientation; on the contrary, if the structure can change its position, such as being inverted, the orientation of the structure will be changed accordingly. Specifically, in the present invention, the "lower" side of the electrode refers to the side of the electrode close to the substrate during the preparation process, and the opposite side away from the substrate is the "upper" side.

[0087] Organic electroluminescent devices

[0088] The organic electroluminescent device of the present invention may be a bottom-emitting organic electroluminescent device, a top-emitting organic electroluminescent device or a stacked organic electroluminescent device, and there is no particular limitation on this.

[0089] The organic electroluminescent device of the present invention comprises a substrate, a first electrode, a multi-layer organic thin film layer and a second electrode. The multi-layer organic thin film layer comprises a hole transport region, a light-emitting layer and an electron transport region, the hole transport region comprises a hole injection layer, a hole transport layer and an electron blocking layer, the electron transport region comprises a hole blocking layer, an electron transport layer and an electron injection layer, and a covering layer may be provided on the second electrode.

[0090] The organic electroluminescent device of the present invention may include layers and the positional relationship of each layer is as follows: 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 covering layer. If the above layers exist, the first electrode is above the substrate, the hole injection layer is above the first electrode, the hole transport layer is above the hole injection layer, the electron blocking layer is above the hole transport layer, the light-emitting layer is above the electron blocking layer, the hole blocking layer is above the light-emitting layer, the electron transport layer is above the hole blocking layer, the electron injection layer is above the electron transport layer, the second electrode is above the electron injection layer, and the covering layer is above the second electrode.

[0091] As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be used. Examples are transparent substrates, such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; flexible PI film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, its use direction is different. In the present invention, a transparent glass substrate is preferably used, and the thickness of the substrate is not particularly limited.

[0092] A first electrode is formed on the substrate, and the first electrode and the second electrode may be opposite to each other. The first electrode may be an anode or a cathode. In the present invention, the first electrode serves as an 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 (SnO 2 ), 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 including two or more layers. In addition, the thickness of the anode depends on the material used, and is generally 50-500nm, preferably 70-300nm, and more preferably 100-200nm.

[0093] A hole injection layer, a hole transport layer, and an electron blocking layer may be disposed between the first electrode and the light emitting layer.

[0094] The hole injection layer may include a main material and a P-type doping material, wherein the main material may be selected from conventional hole transport materials in the prior art, preferably the same organic material as the hole transport layer, and the P-type doping material is selected from compounds with charge conductivity 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 are not limited thereto.

[0095] For example, the compound shown below:

[0096]

[0097] According to the present invention, P1 is preferably used as the P-type doping material.

[0098] The thickness of the hole injection layer of the present invention may be 1-100 nm, preferably 2-50 nm, and more preferably 5-20 nm.

[0099] The material of the hole transport layer is preferably a material having high hole mobility, which enables holes to be transferred from the anode or the hole injection layer to the light emitting layer.

[0100] Preferably, the hole transport layer material of the present invention may be selected from the following compounds disclosed in the prior art:

[0101]

[0102]

[0103] The thickness of the hole transport layer of the present invention may be 5-200 nm, preferably 10-180 nm, and more preferably 20-150 nm.

[0104] The electron blocking layer requires that the triplet state (T1) energy level of the material is higher than the T1 energy level of the main material in the light-emitting layer, which can play a role in blocking the energy loss of the light-emitting layer material; the HOMO energy level of the electron blocking layer material is between the HOMO energy level of the hole transport layer material and the HOMO energy level of the main material of the light-emitting layer, which is conducive to the injection of holes from the positive electrode into the light-emitting layer. At the same time, the electron blocking layer material is required to have a high hole mobility, which is conducive to hole transport and reduces the power of the device; the LUMO energy level of the electron blocking layer material is higher than the LUMO energy level of the main material of the light-emitting layer, which plays a role in electron blocking, that is, the electron blocking layer material is required to have a wide bandgap width (Eg). The electron blocking layer materials that meet the above conditions can be triarylamine derivatives, fluorene derivatives, spirofluorene derivatives, dibenzofuran derivatives, carbazole derivatives, etc.

[0105] In one embodiment of the present invention, the electron blocking layer material of the present invention may be selected from the following compounds disclosed in the prior art:

[0106]

[0107] 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.

[0108] According to the present invention, the light-emitting layer is located between the electron blocking layer and the hole blocking layer, and the material of the light-emitting layer is a material that can emit visible light by receiving holes from the hole transport region and electrons from the electron transport region respectively, and combining the received holes and electrons. The light-emitting layer may include a host material and a doping material. 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 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 chrysene derivative, a spirofluorene derivative, an iridium complex or a platinum complex.

[0109] The thickness of the light-emitting layer of the present invention may be 5-60 nm, preferably 10-50 nm, and more preferably 20-45 nm.

[0110] The hole blocking layer can be arranged on the light-emitting layer, which can block the energy loss of the light-emitting layer material and play a role in hole blocking. At the same time, the hole blocking layer material is required to have a high electron mobility, which is conducive to electron transmission and reduces the application power of the device. The hole blocking layer material that meets the above conditions is the compound with the bipyrimidine structure described above in the present invention.

[0111] The thickness of the hole blocking layer of the present invention may be 2-200 nm, preferably 5-150 nm, and more preferably 5-50 nm, but the thickness is not limited to this range.

[0112] The electron transport layer may be disposed on the light-emitting layer or (if present) the hole blocking layer. The electron transport layer material is a material that easily receives electrons from the cathode and transfers the received electrons to the light-emitting layer. A material having a high electron mobility is preferred. As the electron transport layer of the organic electroluminescent device of the present invention, the following compounds disclosed in the prior art can be used as electron transport layer materials for organic electroluminescent devices:

[0113]

[0114] In a preferred embodiment of the present invention, the electron transport layer further comprises other compounds conventionally used in electron transport layers, for example, Alq3, LiQ, preferably LiQ.

[0115] The thickness of the electron transport layer of the present invention may be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm.

[0116] According to the present invention, the electron injection layer can be arranged between the electron transport layer and the cathode. The electron injection layer material is generally preferably a material with a low work function, so that electrons are easily injected into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material of the organic electroluminescent device of the present invention, the electron injection layer materials for organic electroluminescent devices disclosed in the following prior art can be used: LiF, Cs 2 CO 3 、CsF、Csq、NaF、MgF 2 , CaF 2 、Al 2 O 3 , Yb.

[0117] The thickness of the electron injection layer of the present invention may 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.

[0118] According to the present invention, as mentioned above, the second electrode can be a cathode or an anode. In the present invention, the second electrode is used as a cathode. The material used to form the cathode can be a material with a low work function, such as a metal, an alloy, a conductive compound or a mixture thereof. Non-limiting examples of cathode materials can include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), and aluminum-lithium (Al-Li), magnesium-indium (Mg-In) and magnesium-silver (Mg-Ag). The thickness of the cathode depends on the material used, typically 5-100nm, preferably 7-50nm, and more preferably 10-25nm.

[0119] Optionally, in order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (ie, CPL layer) may be added on the second electrode (ie, cathode) of the device. The following compounds disclosed in the prior art may be used as CPL layer materials.

[0120]

[0121] The thickness of the CPL layer is generally 5-300 nm, preferably 20-100 nm, and more preferably 40-80 nm.

[0122] The organic electroluminescent device may further include an encapsulation structure, which may be a protective structure for preventing foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.

[0123] Organic electroluminescent device preparation method:

[0124] The present invention also relates to a method for preparing the above-mentioned organic electroluminescent device, which comprises laminating a first electrode, a multi-layer organic thin film layer and a second electrode on a substrate in sequence. The multi-layer organic thin film layer is formed by laminating a hole transport region, a light-emitting layer and a hole blocking region on the first electrode from bottom to top, and the hole transport region is formed by laminating a hole injection layer, a hole transport layer and an electron blocking layer on the first electrode in sequence from bottom to top, and the hole blocking region is formed by laminating a hole blocking layer, an electron transport layer and an electron injection layer on the light-emitting layer in sequence from bottom to top. In addition, optionally, a CPL layer can also be laminated on the second electrode to improve the light extraction efficiency of the organic electroluminescent device.

[0125] For lamination, vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing or LITI methods may be used, but are not limited thereto. Vacuum evaporation means heating and coating a material onto a substrate in a vacuum environment.

[0126] In the present invention, the various layers are preferably formed by vacuum evaporation, wherein the layers can be formed at a temperature of about 100-500° C. and at a temperature of about 10 -8 -10 -2 Torr vacuum and approx. The vacuum evaporation is carried out at a rate of 10 -6 -10 -2 Torr, preferably 10 -5 -10 -3 Torr. The rate is about More preferably, about

[0127] In addition, it should be noted that the materials used to form each layer described in the present invention can be formed into a film alone and used as a single layer, or can be mixed with other materials to form a film and used as a single layer. It can also be a stacked structure between layers formed into films alone, a stacked structure between layers formed into films after mixing, or a stacked structure of layers formed into films alone and layers formed into films after mixing.

[0128] Display components

[0129] The present invention also relates to a display device including the above-mentioned organic electroluminescent device, in particular a flat panel display device. In a preferred embodiment, the display device may include one or more of the above-mentioned organic electroluminescent devices, and in the case of including a plurality of devices, the devices are stacked and combined laterally or longitudinally. 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 the first electrode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor or an oxide semiconductor, but is not limited thereto.

[0130] The following examples are intended to better explain the present invention, but the scope of the present invention is not limited thereto.

[0131] Example

[0132] I. Compound Preparation Examples

[0133] The raw materials involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art;

[0134] Preparation of intermediate B5 and intermediate M7:

[0135]

[0136] Under nitrogen protection, in a 500 ml round-bottom flask, raw material C1 (6.35 g, 20 mmol), raw material D1 (4.13 g, 24 mmol), K2 CO 3 (8.29 g, 60 mmol), ethylene glycol dimethyl ether (150 mL), water (25 mL), nitrogen was passed through for 30 min to replace the air, and bis(triphenylphosphine)palladium dichloride (PdCl) was added 2 (PPh 3 ) 2 (0.42g, 0.6mmol), heated to reflux for 13h under nitrogen protection. TCL detection of the reaction solution found that the raw material C1 reacted completely. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, 150ml of dichloromethane was added to the residue to dissolve, 100ml of water was added to wash, poured into a separatory funnel and shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (50ml*3), the organic phases were combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel chromatography to obtain intermediate B5. LC-MS: Measured value: 316.88 ([M+H] + ); exact mass: 315.97.

[0137] Under nitrogen protection, in a 500 ml round-bottom flask, raw material A1 (4.16 g, 15 mmol), intermediate B5 (5.72 g, 18 mmol), K 2 CO 3 (6.22 g, 45 mmol), tetrahydrofuran (120 mL), water (40 mL), nitrogen was passed through for 40 min to replace the air, and Pd(PPh 3 ) 4 (0.35g, 0.30mmol), heated to reflux for 17h under nitrogen protection. TCL detection of the reaction solution showed that the raw material A1 reacted completely. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, 100ml of dichloromethane was added to the residue to dissolve, 100ml of water was added to wash, poured into a separatory funnel and shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (50ml*3), the organic phases were combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel chromatography to obtain intermediate M7. LC-MS: Measured value: 470.27 ([M+H] + ); exact mass: 469.13.

[0138] Intermediate B was prepared by the synthesis method of intermediate B5, except that different raw materials were replaced, and the raw materials C and D used were shown in Table 1; Intermediate M was prepared by the synthesis method of intermediate M7, except that different raw materials were replaced, and the raw materials A, raw materials B or intermediate B used were shown in Table 1;

[0139] Table 1

[0140]

[0141]

[0142] Preparation of intermediate N5:

[0143]

[0144] Under nitrogen protection, in a round-bottom flask, raw material E1 (11.32 g, 40 mmol), raw material F1 (7.22 g, 42 mmol), K 2 CO 3 (16.58 g, 120 mmol), tetrahydrofuran (270 mL), water (90 mL), nitrogen was passed through for 30 min to replace the air, and Pd(PPh 3 ) 4 (0.462g, 0.4mmol), heated to reflux for 10h under nitrogen protection. The reaction liquid was taken for TCL detection to find that the raw material E1 reacted completely. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, 100ml of dichloromethane was added to the residue to dissolve, 100ml of water was added to wash, poured into a separatory funnel and shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (50ml*3), the organic phases were combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel chromatography to obtain intermediate G1. LC-MS: Measured value: 283.05 ([M+H] + ), exact mass: 282.00.

[0145] Under nitrogen protection, in a round-bottom flask, add intermediate G1 (8.50 g, 30 mmol) and tetrahydrofuran (200 mL) in sequence, stir and pass nitrogen for 30 min to replace the air, cool the reaction solution system to -78 ° C, and keep it at -78 ° C for 20 min, slowly add 1.6 mol / L tetrahydrofuran solution of n-butyl lithium (20.6 ml, 33 mmol) dropwise, stir and react the resulting mixture at -78 ° C for 3 h, then add a mixture of raw material H1 (6.92 g, 30 mmol) dissolved in tetrahydrofuran (300 mL), react at -78 ° C for 2 h, and then gradually heat up to room temperature for 10 h. Finally, 20 mL of water was added to the reaction solution system, and the solvent was removed by rotary evaporation. The residue was dissolved by adding 100 ml of dichloromethane, washed with 100 ml of water, poured into a separatory funnel, shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (50 ml*3), the organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was subjected to rotary evaporation to remove dichloromethane to obtain intermediate I1. LC-MS: Measured value: 435.40 ([M+H] + ), exact mass: 434.11.

[0146] Under nitrogen protection, in a round-bottom flask, add intermediate I1 (8.70g, 20mmol), acetic acid (90mL), nitrogen was passed for 30min to replace the air, 3mL hydrochloric acid (36%) was added, and the reaction was heated to 110°C for 4h. The reactants were cooled to room temperature, ice water (100ml) was added, and filtered. The filter cake was dissolved in 100ml dichloromethane in a 500ml flask, washed with 100ml water, poured into a separatory funnel, shaken, and allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (50ml*3), the organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel chromatography to obtain intermediate J1. LC-MS: Measured value: 417.24 ([M+H] + ), exact mass: 416.10.

[0147] Under nitrogen protection, in a round-bottom flask, intermediate J1 (6.25 g, 15 mmol), bipyralidone (4.57 g, 18 mmol), KOAC (50 mmol), and dioxane (120 ml) were added in sequence, and nitrogen was passed through for 30 min to replace the air. Pd(PPh 3 ) 4 (0.347g, 0.3mmol), heated to reflux for 10h under nitrogen protection. The reaction solution was taken for TCL detection to find that the intermediate J1 reacted completely. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, 100ml of dichloromethane was added to the residue to dissolve, 100ml of water was added to wash, poured into a separatory funnel and shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (50ml*3), the organic phases were combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was subjected to rotary evaporation to remove dichloromethane to obtain the intermediate N5. LC-MS: Measured value: 509.17 ([M+H] + ); exact mass: 508.22.

[0148] Intermediate G was prepared by a synthetic method similar to that of intermediate G1, and the raw materials E and F used were shown in Table 2;

[0149] Intermediate I was prepared by a synthetic method similar to that of intermediate I1, and the intermediate G and raw material H used were shown in Table 2;

[0150] Intermediate J was prepared by a synthetic method similar to that of intermediate J1, and the intermediate I used was shown in Table 2;

[0151] Intermediate N was prepared by a synthetic method similar to that of intermediate N5, and the intermediate J used is shown in Table 2.

[0152] Table 2

[0153]

[0154]

[0155] Example 1: Synthesis of Compound 2

[0156]

[0157] Under nitrogen protection, in a 250 ml round-bottom flask, intermediate M1 (4.20 g, 10 mmol), raw material N1 (5.50 g, 12 mmol), K 2 CO 3 (4.15g, 30mmol), tetrahydrofuran (90mL), water (45mL), nitrogen was passed for 30min to replace the air, palladium acetate (0.067g, 0.30mmol,), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.43g, 0.90mmol,) was added, and the mixture was heated under reflux for 21h under nitrogen protection. The reaction solution was taken for TCL detection and it was found that the intermediate M1 reacted completely. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, 100ml of dichloromethane was added to the residue to dissolve, 100ml of water was added to wash, poured into a separating funnel and shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (75ml*3), the organic phases were combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel column chromatography to obtain compound 2. Elemental analysis: C 52 H 33 N 3 O; theoretical value: C, 87.25; H, 4.65; N, 5.87; test value: C, 87.44; H, 4.47; N, 5.80. LC-MS: Found: 716.05 ([M+H] + ), exact mass: 715.26.

[0158] Example 2: Synthesis of Compound 10

[0159]

[0160] Compound 10 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M2 was used to replace intermediate M1. Elemental analysis: C 52 H 33 N 3 O; theoretical value: C, 87.25; H, 4.65; N, 5.87; test value: C, 87.06; H, 4.78; N, 5.93. LC-MS: Found: 716.39 ([M+H] + ), exact mass: 715.26.

[0161] Example 3: Synthesis of Compound 23

[0162]

[0163] Compound 23 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate M3 was used to replace intermediate M1, and raw material N2 was used to replace raw material N1. Elemental analysis: C 52 H 33 N 3 O; theoretical value: C, 87.25; H, 4.65; N, 5.87; test value: C, 87.37; H, 4.81; N, 5.62. LC-MS: Found: 716.45 ([M+H] + ), exact mass: 715.26.

[0164] Example 4: Synthesis of Compound 30

[0165]

[0166] Compound 30 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate M4 was used to replace intermediate M1, and raw material N3 was used to replace raw material N1. Elemental analysis: C 52 H 33 N 3 O; theoretical value: C, 87.25; H, 4.65; N, 5.87; test value: C, 87.36; H, 4.62; N, 5.71. LC-MS: Found: 716.20 ([M+H] + ), exact mass: 715.26.

[0167] Example 5: Synthesis of Compound 34

[0168]

[0169] Compound 34 was prepared according to the synthesis method of compound 2 in Example 1, except that raw material N4 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.60; H, 4.75; N, 5.41. LC-MS: Found: 766.22 ([M+H] + ), exact mass: 765.28.

[0170] Example 6: Synthesis of Compound 35

[0171]

[0172] Compound 35 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate N5 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.97; H, 4.43; N, 5.55. LC-MS: Found: 766.25 ([M+H] + ), exact mass: 765.28.

[0173] Example 7: Synthesis of Compound 37

[0174]

[0175] Compound 37 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate N6 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.86; H, 4.60; N, 5.60. LC-MS: Found: 766.13 ([M+H] + ), exact mass: 765.28.

[0176] Example 8: Synthesis of Compound 47

[0177]

[0178] Compound 47 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M2 was used to replace intermediate M1, and intermediate N7 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.66; H, 4.45; N, 5.74. LC-MS: Found: 766.41 ([M+H] + ), exact mass: 765.28.

[0179] Example 9: Synthesis of Compound 48

[0180]

[0181] Compound 48 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate M2 was used to replace intermediate M1, and raw material N4 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.57; H, 4.71; N, 5.66. LC-MS: Found: 766.19 ([M+H] + ), exact mass: 765.28.

[0182] Example 10: Synthesis of Compound 52

[0183]

[0184] Compound 52 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M2 was used to replace intermediate M1, and raw material N8 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.53; H, 4.54; N, 5.72. LC-MS: found value: 766.35 ([M+H] + ), exact mass: 765.28.

[0185] Example 11: Synthesis of Compound 73

[0186]

[0187] Compound 73 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M4 was used to replace intermediate M1, and intermediate N9 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.89; H, 4.63; N, 5.44. LC-MS: Found: 766.02 ([M+H] + ), exact mass: 765.28.

[0188] Example 12: Synthesis of Compound 94

[0189]

[0190] Compound 94 was prepared according to the synthesis method of compound 2 in Example 1, except that raw material N10 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.94; H, 4.50; N, 5.53. LC-MS: Found: 766.09 ([M+H]+ ), exact mass: 765.28.

[0191] Example 13: Synthesis of Compound 187

[0192]

[0193] Compound 187 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate M4 was used to replace intermediate M1, and intermediate N11 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.71; H, 4.84; N, 5.32. LC-MS: Found: 766.37 ([M+H] + ), exact mass: 765.28.

[0194] Example 14: Synthesis of Compound 202

[0195]

[0196] Compound 202 was prepared according to the synthesis method of compound 2 in Example 1, except that raw material N12 was used to replace raw material N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.93; H, 4.36; N, 5.68. LC-MS: Found: 766.43 ([M+H] + ), exact mass: 765.28.

[0197] Example 15: Synthesis of Compound 263

[0198]

[0199] Compound 263 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M5 was used to replace intermediate M1, and intermediate N13 was used to replace intermediate N1. Elemental analysis: C 58 H 37 N 3 O; theoretical value: C, 87.96; H, 4.71; N, 5.31; test value: C, 87.88; H, 4.53; N, 5.55. LC-MS: Found: 792.04 ([M+H] + ), exact mass: 791.29.

[0200] Example 16: Synthesis of Compound 286

[0201]

[0202] Compound 286 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate M7 was used to replace intermediate M1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.64; H, 4.86; N, 5.25. LC-MS: Found: 766.16 ([M+H] + ), exact mass: 765.28.

[0203] Example 17: Synthesis of Compound 303

[0204]

[0205] Compound 303 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M6 was used to replace intermediate M1, and raw material N14 was used to replace intermediate N1. Elemental analysis: C 56 H 35 N 3 O; theoretical value: C, 87.82; H, 4.61; N, 5.49; test value: C, 87.99; H, 4.58; N, 5.44. LC-MS: Found: 766.30 ([M+H] + ), exact mass: 765.28.

[0206] Example 18: Synthesis of Compound 357

[0207]

[0208] Compound 357 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M8 was used to replace intermediate M1. Elemental analysis: C 58 H 37 N 3 O; theoretical value: C, 87.96; H, 4.71; N, 5.31; test value: C, 87.72; H, 4.77; N, 5.42. LC-MS: Found: 792.16 ([M+H] + ), exact mass: 791.29.

[0209] Example 19: Synthesis of Compound 360

[0210]

[0211] Compound 360 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M9 was used to replace intermediate M1. Elemental analysis: C 51 H 32 N 4 O; theoretical value: C, 85.45; H, 4.50; N, 7.82; test value: C, 85.64; H, 4.36; N, 7.77. LC-MS: Found: 717.31 ([M+H] + ), exact mass: 716.26. .

[0212] Example 20: Synthesis of Compound 428

[0213]

[0214] Compound 428 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M2 was used to replace intermediate M1, and intermediate N15 was used to replace raw material N1. Elemental analysis: C 58 H 37 N 3 O; theoretical value: C, 87.96; H, 4.71; N, 5.31; test value: C, 87.99; H, 4.80; N, 5.23. LC-MS: Found: 792.43 ([M+H] + ), exact mass: 791.29.

[0215] Example 21: Synthesis of Compound 435

[0216]

[0217] Compound 435 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M2 was used to replace intermediate M1, and intermediate N16 was used to replace raw material N1. Elemental analysis: C 58 H 37 N 3 O; theoretical value: C, 87.96; H, 4.71; N, 5.31; test value: C, 88.03; H, 4.86; N, 5.18. LC-MS: Found: 792.11 ([M+H] + ), exact mass: 791.29.

[0218] Example 22: Synthesis of Compound 445

[0219]

[0220] Intermediate N17 was prepared according to the synthetic method of intermediate N5, except that raw material K1 was used to replace biboric acid pinacol ester, and raw material J20 was used to replace raw material J1. LC-MS: Measured value: 535.15 ([M+H] + ), exact mass: 534.24.

[0221] Compound 445 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate N17 was used to replace raw material N1. Elemental analysis: C 58 H 37 N 3 O; theoretical value: C, 87.96; H, 4.71; N, 5.31; test value: C, 88.11; H, 4.64; N, 5.26. LC-MS: Found: 792.25 ([M+H] + ), exact mass: 791.29.

[0222] Example 23: Synthesis of Compound 484

[0223]

[0224] Compound 484 was prepared according to the synthesis method of compound 2 in Example 1, except that raw material N18 was used to replace raw material N1. Elemental analysis: C 52 H 33 N 3 S; theoretical value: C, 85.33; H, 4.54; N, 5.74; S, 4.38; measured value: C, 85.45; H, 4.62; N, 5.66; S, 4.30. LC-MS: measured value: 732.35 ([M+H] + ), exact mass: 731.24. .

[0225] Example 24: Synthesis of Compound 518

[0226]

[0227] Compound 518 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M11 was used to replace intermediate M1. Elemental analysis: C 51 H 32 N 4 O; theoretical value: C, 85.45; H, 4.50; N, 7.82; test value: C, 85.52; H, 4.68; N, 7.65. LC-MS: found value: 717.43 ([M+H] + ), exact mass: 716.26. .

[0228] Example 25: Synthesis of Compound 558

[0229]

[0230] Compound 558 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate M2 was used to replace intermediate M1, and raw material N19 was used to replace raw material N1. Elemental analysis: C 55 H 39 N 3 ; Theoretical value: C, 89.04; H, 5.30; N, 5.66; Test value: C, 88.98; H, 5.44; N, 5.61. LC-MS: Measured value: 742.37 ([M+H] + ), exact mass: 741.31. .

[0231] Example 26: Synthesis of Compound 563

[0232]

[0233] Compound 563 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate M5 was used to replace intermediate M1, and raw material N4 was used to replace raw material N1. Elemental analysis: C 62 H 39 N 3 O; theoretical value: C, 88.44; H, 4.67; N, 4.99; test value: C, 88.57; H, 4.79; N, 4.72. LC-MS: Found: 842.18 ([M+H] + ), exact mass: 841.31.

[0234] II. Device Preparation Example

[0235] The following describes in detail the application effect of the compound synthesized according to the present invention as a hole blocking layer material in the device through device examples 1-26 and device comparative examples 1-25. Compared with device comparative examples 1-25, device examples 1-26 have the same manufacturing process of the device, and use the same substrate material and electrode material, and the film thickness of the electrode material is also the same. The difference is that the hole blocking layer material in the device has changed. The device layer structure is shown in Table 3, and the performance test results of each device are shown in Table 3.

[0236] The molecular structure formula of the relevant materials is shown below:

[0237]

[0238]

[0239] The structures of comparative compounds HB-1 to HB-25 are shown above. The above materials were all purchased from the market.

[0240] Device Comparison Example 1

[0241] The specific preparation process is as follows:

[0242] like Figure 1 As shown, the transparent substrate layer 1 is transparent glass, and Ag (100nm) is evaporated as the anode layer 2. On the anode layer 2, a vacuum evaporation device is used to evaporate HT-1 and P-1 with a film thickness of 10nm as the hole injection layer 3, and the mass ratio of HT-1 and P-1 is 97:3. Then, HT-1 with a thickness of 130nm is evaporated as the hole transport layer 4. Then, EB-1 with a thickness of 5nm is evaporated as the electron blocking layer 5. After the above-mentioned electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is prepared, using BH-1 as the main material and BD-1 as the doping material. The doping ratio of the doping material is 3% by weight, and the film thickness of the light-emitting layer 6 is 20nm. After the above-mentioned light-emitting layer 6, HB-1 is continuously evaporated, and the film thickness is 5nm, as a hole blocking layer 7. On the above-mentioned hole blocking layer 7, ET-1 and LiQ are continuously evaporated, and the mass ratio of ET-1 and LiQ is 1:1. The vacuum-deposited film thickness of this material is 30nm, and this layer is the electron transport layer 8. On the electron transport layer 8, a LiF layer with a film thickness of 1nm is made by a vacuum evaporation device, and this layer is the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a film thickness of 16nm is made by a vacuum evaporation device, and the mass ratio of Mg to Ag is 1:9, and this layer is used as the cathode layer 10. On the cathode layer 10, 65nm of CP-1 is vacuum-deposited as the light extraction layer 11 (CPL layer).

[0243] Device Examples 1-26 and Device Comparative Examples 2-25 were prepared in a similar manner to Device Comparative Example 1, except that the hole blocking layer materials in Table 3 below were used.

[0244] Table 3

[0245]

[0246]

[0247]

[0248]

[0249]

[0250] III. Device Testing Example

[0251] The device prepared in II was tested for its current efficiency, CIEy and LT95 life. The current efficiency and CIEy were tested using an IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.) at a current density of 10 mA / cm 2 LT95 refers to the time it takes for the device brightness to decay to 95% of the initial brightness. The current density during the test is 30mA / cm 2 ; The life test system is the EAS-62C OLED device life tester produced by Japan System Engineering Co., Ltd.; The test results are shown in Table 4 below.

[0252] Table 4

[0253]

[0254]

[0255] It can be seen from the device test data results in Table 4 above that 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, HB-17, HB-18, HB-19, HB-20, HB-21, HB-22, HB-23, HB-24, and HB-25 as hole blocking layer materials, the current efficiency of the device prepared using the compound of the present invention as the hole blocking layer material is improved and the device life is extended. For example, its life is basically more than 1.14 times that of the device comparison examples 1-25, and some embodiments (such as device embodiment 1 prepared using compound 2 of the present invention) are even more than 1.25 times that of the device comparison examples 1-25.

[0256] The structural formulas of the comparative compounds HB-1 to HB-25 used in the device comparison examples are close to the structures of the compounds of the present invention, and only the intermediate special bridging groups, triazine substituents, and spiroanthracene derivative substituents between the structures of triazine and spiroanthracene derivatives are different; wherein the intermediate special bridging refers to the connection of triazine and spiroanthracene derivatives to phenyl groups having substituents at specific sites. However, the compounds of the present invention have achieved better technical effects as hole blocking layer materials than the comparative compounds.

[0257] 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 principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A compound containing triazine and spiroanthracene structures, characterized in that: The compound containing triazine and spiroanthraquinone structures is shown in general formula (1): In the general formula (1), Ar1 and Ar2 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group; Y1, Y2, Y3, and Y4 are each independently represented by CH or N; Y1, Y2, Y3, and Y4 may be the same or different; at least one of Y2 and Y3 is represented by CH; * indicates the connection position; L1, L2, and L3 are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted pyridylene group; L1, L2, and L3 may be the same or different; R1 and R2 are independently represented by substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl or the structure represented by the general formula (2); one and only one of R1 and R2 is represented by the general formula (2); Ar1, Ar2, and R1 may be the same or different; Ar1, Ar2, and R2 may be the same or different; In the general formula (2), X represents any one of an oxygen atom, a sulfur atom, and a dimethyl-substituted methylene group; any unsubstituted carbon on the benzene ring or naphthalene ring in the general formula (2) can serve as a connection site with the general formula (1); Ring A and Ring B are each independently a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group; The substituent of the substituted group is selected from a deuterium atom, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a phenanthryl group, a pyrimidyl group or a halogen atom.

2. A compound containing triazine and spiroanthracene structures according to claim 1, characterized in that: The compound containing triazine and spiroanthraquinone structures is represented by any one of the general formulas (3) and (4): In general formula (3) and general formula (4), Ar1, Ar2, R1, R2, L1, L2, Y1, Y2, Y3, and Y4 have the same meanings as defined in claim 1.

3. The compound containing triazine and spiroanthracene structures according to claim 1, characterized in that: The compound containing triazine and spiroanthraquinone structures is any one of general formulas (5) to (10): In general formula (5) to general formula (10), Ar1, Ar2, R1, R2, L1, L2, Y1, Y2, Y3, and Y4 have the same meanings as defined in claim 1.

4. The compound containing triazine and spiroanthracene structures according to claim 1, characterized in that: The compound containing triazine and spiroanthracene structures is any one of the general formulas (11) to (41): In general formula (11) to general formula (41), Ar1, Ar2, R1, and R2 have the same meanings as defined in claim 1.

5. The compound containing triazine and spiroanthracene structures according to claim 1, characterized in that: The general formula (2) is represented by any one of the general formulas a, b and c: In the general formula a, general formula b and general formula c, R3 and R4 are independently represented by a hydrogen atom, a deuterium atom, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a phenanthryl group, a pyrimidyl group or a halogen atom; R3 and R4 may be the same or different; Any unsubstituted carbon on the benzene ring or naphthalene ring in general formula a, general formula b, and general formula c can serve as a connection site with general formula (1); In general formula a, general formula b and general formula c, X has the same meaning as defined in claim 1.

6. The compound containing triazine and spiroanthracene structures according to claim 5, characterized in that: The general formula (2) is represented by any one of the general formula a-1, general formula b-1, general formula b-2, general formula b-3, general formula c-1, general formula c-2 or general formula c-3: In the general formula a-1, the connection site with the general formula (1) is any one of sites 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16; the connection site of R3 is any one of sites 9, 10, 11 or 12; the connection site of R4 is any one of sites 13, 14, 15 or 16; In the general formula b-1, the connection site with the general formula (1) is any one of 1', 2', 3', 4', 5', 6', 7', 8', 9', 10', 11', 12', 13', 14', 15', 16', 17' or 18'; the connection site of R3 is any one of 9', 10', 11', 12', 13' or 14'; the connection site of R4 is any one of 15', 16', 17' or 18'; In the general formula b-2, the connection site with the general formula (1) is any one of 19', 20', 21', 22', 23', 24', 25', 26', 27', 28', 29', 30', 31', 32', 33', 34', 35' or 36'; the connection site of R3 is any one of 27', 28', 29', 30', 31' or 32'; the connection site of R4 is any one of 33', 34', 35' or 36'; In the general formula b-3, the connection site with the general formula (1) is any one of 37', 38', 39', 40', 41', 42', 43', 44', 45', 46', 47', 48', 49', 50', 51', 52', 53' or 54'; the connection site of R3 is any one of 45', 46', 47', 48', 49' or 50'; the connection site of R4 is any one of 51', 52', 53' or 54'; In the general formula c-1, the connection site with the general formula (1) is any one of 1", 2", 3", 4", 5", 6", 7", 8", 9", 10", 11", 12", 13", 14", 15", 16", 17" or 18"; the connection site of R3 is any one of 9", 10", 11" or 12"; the connection site of R4 is any one of 13", 14", 15", 16", 17" or 18"; In the general formula c-2, the connection site with the general formula (1) is any one of 19", 20", 21", 22", 23", 24", 25", 26", 27", 28", 29", 30", 31", 32", 33", 34", 35" or 36"; the connection site of R3 is any one of 27", 28", 29" or 30"; the connection site of R4 is any one of 31", 32", 33", 34", 35" or 36"; In the general formula c-3, the connection site with the general formula (1) is any one of 37", 38", 39", 40", 41", 42", 43", 44", 45", 46", 47", 48", 49", 50", 51", 52", 53" or 54"; the connection site of R3 is any one of 45", 46", 47" or 48"; the connection site of R4 is any one of 49", 50", 51", 52", 53" or 54"; In the general formula a-1, general formula b-1, general formula b-2, general formula b-3, general formula c-1, general formula c-2, and general formula c-3, the meaning of X is the same as that defined in claim 1.

7. The compound containing triazine and spiroanthracene structures according to claim 1, characterized in that: In the general formula (1), at least one of Y1, Y2, Y3 and Y4 is represented by N.

8. The compound containing triazine and spiroanthracene structures according to claim 1, characterized in that: The specific structure of the compound containing triazine and spiroanthraquinone structures is any one of the following structures:

9. An organic electroluminescent device comprising a substrate, a first electrode and a second electrode, wherein a plurality of organic thin film layers are provided between the first electrode and the second electrode, wherein: The organic thin film layer contains the compound containing triazine and spiroanthracene fluorene structures according to any one of claims 1 to 8. Preferably, the organic thin film layer comprises a hole transport region thin film layer, a light emitting region thin film layer and an electron transport region thin film layer, and the electron transport region thin film layer contains the compound containing triazine and spiroanthracene structures according to any one of claims 1 to 8. Preferably, the electron transport region thin film layer comprises a hole blocking layer, and the hole blocking layer comprises the compound containing triazine and spiroanthracene fluorene structures according to any one of claims 1 to 8.

10. An organic electroluminescent device according to claim 9, characterized in that: 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 compound containing triazine and spiroanthracene structures as described in any one of claims 1 to 8.

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