CN117945984A

CN117945984A - Organic compound containing polyfluoro-substituted glutarimide or succinimide and organic electroluminescent device containing same

Info

Publication number: CN117945984A
Application number: CN202211298881.0A
Authority: CN
Inventors: 张钊; 张汝岳; 唐丹丹
Original assignee: Jiangsu Sunera Technology Co Ltd
Current assignee: Jiangsu Sunera Technology Co Ltd
Priority date: 2022-10-21
Filing date: 2022-10-21
Publication date: 2024-04-30

Abstract

The invention discloses an organic compound containing polyfluoro substituted glutarimide or succinimide and an organic electroluminescent device containing the same. The compound is an organic compound containing polyfluoro-substituted glutarimide or succinimide, has lower refractive index of visible light in the visible light field, and has refractive index of less than 1.60 in the blue light region. The invention is a low refractive index material, and is matched with a high refractive index material to form a low-high double-layer covering layer, and after the low-high double-layer covering layer is applied to an OLED device, the light extraction efficiency of the OLED device can be effectively improved, the angle dependence can be greatly reduced, and therefore the luminous efficiency of the device can be improved, and the viewing bias performance can be optimized.

Description

Organic compound containing polyfluoro-substituted glutarimide or succinimide and organic electroluminescent device containing same

Technical Field

The invention relates to the technical field of semiconductors, in particular to a multi-fluorine substituted glutarimide or succinimide-containing organic compound and application thereof as a coating layer in an organic electroluminescent device.

Background

Organic electroluminescent diodes (OrganicLightEmittingDiode, OLED), also known as organic electroluminescent devices, are a technology in which an organic material emits light by carrier injection and recombination under the action of an electric field, and are capable of converting electric energy into light energy through the organic luminescent material, including passive-driving OLEDs (PMOLEDs) and active-driving OLEDs (AMOLEDs). OLEDs are a new generation of display technology following cathode ray tubes (CathodeRayTube, CRT) and liquid crystal displays (LiquidCrystalDisplay, LCD), known as fantasy display technology. The nature of an OLED is a thin film stack device. In theory, in the case where both the anode and the cathode are transparent electrodes, light emitted from the light-emitting layer can propagate from the anode to the outside of the device or from the cathode to the outside of the device. Accordingly, the devices may be classified into bottom emission devices and top emission devices according to paths through which light passes.

Light from the bottom-emitting device propagates from the anode through the substrate to the outside of the device, and light from the top-emitting device propagates through the cathode to the outside of the device. The two devices have different application modes due to different light emitting modes. If a bottom emission device is used in the active matrix structure, the light emitting path is an organic layer-anode-TFT-substrate, the TFT is a mesh array switch deposited on the substrate, the aperture ratio of the device is further reduced due to the existence of the TFT, reflection, scattering and the like can occur when emergent light propagates to the position and can not propagate to the outside of the device, and the display effect of the device is seriously affected. The light-emitting direction of the top emission device is at one side of the cathode, and the substrate is not needed, so that the TFT structure is avoided, the problem of reduced aperture opening ratio in the bottom emission device is successfully avoided, the image is finer and clearer, and the color vividness is higher.

In the top-emitting organic electroluminescent device structure, there is constructive and destructive interference because the metal cathode layer and the bottom metal reflective layer form a resonant cavity (also called microcavity). With the change of the visual angle, the distance between the metal cathode layer and the metal reflecting layer at the bottom (i.e. the cavity length of the microcavity) is changed, so that great difference of brightness and color observed under different visual angles can occur, and the product performance is seriously affected.

In such a light-emitting element, when light emitted from the light-emitting layer enters another film, if the light enters at a certain angle or more, total reflection occurs at an interface between the light-emitting layer and the other film. Therefore, only a part of the emitted light can be utilized. In recent years, in order to improve light extraction efficiency and color shift, a light-emitting element provided with a "cover layer" having a high refractive index outside a translucent electrode having a low refractive index has been proposed.

However, since it is very difficult to increase the refractive index of the organic compound used for the cladding layer, a double cladding structure comprising a low refractive index cladding layer and a high refractive index cladding layer has been sought in order to further increase the luminous efficiency of the organic light emitting device without increasing the number of excessive materials. Although the samsung US20210159427A1 patent also adopts a double-layer covering layer formed by matching a low refractive index material with a high refractive index material, the low refractive index material adopts a coordination compound, the stability of coordination bonds is poor, and the patent only describes that the luminous efficiency of the device can be improved, and does not describe the influence on the visual deviation of the device. In the soil conservation valley WO2022075396A1 patent, although a double-layer covering layer is formed by matching a low-refractive-index material and a high-refractive-index material, the low-refractive-index material is formed by taking adamantane as a core, and two sides are connected with aryl or heteroaryl through bridging groups of amino, amido, ester and ether groups, so that the molecular weight of the structure is low, the evaporation temperature is low, the evaporation rate in the evaporation process is unstable and is easy to spray, evaporation equipment is polluted, crystallization is easy to occur after the film is coated, the stability of a device, especially the stability of a high-temperature device is influenced, and the patent only describes that the luminous efficiency of the device can be improved, and does not describe the influence on the visual deviation of the device.

On the double cover layer, due to the refractive index difference between the high refractive index CPL and the low refractive index CPL, a part of the light emitted from the light-emitting layer is transmitted through the cover layer, and another part of the emitted light is reflected by the cover layer. Particularly at the interface of the high refractive CPL and the low refractive CPL and at the interface of the high refractive CPL and the package structure, light is reflected. The light reflected by the cover layer is reflected again at the electrode and is enhanced upon repeated reflection. Therefore, the reflection can be repeatedly performed between the interface of the high refraction CPL and the low refraction CPL and the interface of the high refraction CPL and the packaging structure, so that the light lost by reflection on the surface facing away from the OLED is recovered.

Although it is proposed to use a metal mask having high definition in the formation of the cover layer, there are problems with this metal mask as follows: if the coating layer deposition temperature is too high, the alignment accuracy is deteriorated due to deformation caused by heat. If the mask is a high-definition mask, vapor deposition cannot be performed at a correct position. Many inorganic materials have a high vapor deposition temperature, and are not suitable for use as a mask having high definition, and may damage the light-emitting element itself. Further, since the film formation by the sputtering method damages the light-emitting element, a coating layer made of an inorganic material cannot be used.

For high energy plasmas or uv light that are contacted in subsequent packages of the device, a more stable class of materials is needed to avoid damaging the internal materials of the electroluminescent device, more LiF being currently used. The chemical activity of the protective layer LiF is high, while the TFE encapsulation layer is generally prepared by CVD process, and a large amount of high-energy plasma is generated during the preparation process, so that larger energy and electrons are released to the internal layer structure of the device. The energy released by the high energy plasma can cause the organic material of the cap layer to interact with the LiF of the adjacent layers, resulting in black specks in the device. In addition, the layer closest to the protective layer in the encapsulation layer may also participate in interactions to create black specks.

The current use of a capping layer to improve the performance of an OLED device has mainly the following problems:

1. The vapor deposition temperature is too high, and the CPL material is vapor deposited for a long time to generate serious decomposition.

2. The refractive index of the organic CPL material cannot be infinitely increased under control of low evaporation temperatures.

3. The light extraction efficiency is low, and after the light extraction efficiency is applied to an OLED device, the luminous efficiency of the device is improved only to a limited extent.

4. After the light source is applied to an OLED device, the color cast of the device is not obviously improved, the angle dependence of emergent light is strong, the brightness is attenuated along with the change of the angle, and the luminescence color is changed.

In order to realize the continuous improvement of the performance of the OLED device, not only is the innovation of the structure and the manufacturing process of the OLED device needed, but also the continuous research and innovation of the OLED photoelectric functional material are needed, and the OLED functional material with higher performance is created. Accordingly, there is a long felt need in the art to find suitable low refractive index materials in combination with high refractive index materials as bilayer cap layers for OLED devices to address the above-mentioned problems.

Disclosure of Invention

In view of the above problems of the prior art, the present application provides an organic compound containing polyfluoro-substituted glutarimide or succinimide. The blue light region of the compound has a lower refractive index. The low refractive index compound can be used as a first coating layer and matched with a second coating layer with high refractive index to improve light extraction efficiency and angle dependence.

An organic compound containing a polyfluoro-substituted glutarimide or succinimide, which has a structure represented by the general formula (1):

in the general formula (1), Z is identical or different and each independently represents C-R or N; z at the junction with other groups is denoted C;

in the general formula (1), L represents a single bond, a substituted or unsubstituted C6-C50 arylene group, a substituted or unsubstituted C2-C50 heteroarylene group containing one or more hetero atoms; f represents the number 0 or 1; e represents the number 1 or 2;

In the general formula (1), L ₁、L₂、L₃ independently represents a single bond, substituted or unsubstituted C6-C50 arylene, and substituted or unsubstituted C2-C50 heteroarylene containing one or more hetero atoms;

In the general formula (1), a represents a number of 1,2,3,4, 5 or 6; b. c represents the number 0,1,2, 3,4 or 5;

when e represents a number 1, a+b+c is not less than 3; when e represents a number 2, a+b+c is not less than 1;

In the general formula (1), ar ₁ represents the general formula (2); ar ₂、Ar₃ independently represents a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C2-C50 heteroaryl group containing one or more hetero atoms, a structure represented by the general formula (2) or the general formula (3);

In the general formula (2), X represents a single bond, -C (R ₁₀)(R₁₁)

In the general formula (2), R ₁ to R ₄ each represent the same or different hydrogen atom, fluorine atom and trifluoromethyl independently; r ₁ to R ₄ cannot be simultaneously represented as a hydrogen atom;

Each of said R, R ₅ to R ₁₁, which are identical or different, independently of one another, represents cyano, halogen, hydrogen, deuterium, tritium, fluorine, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, fluoromethyl, fluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy; r ₅ to R ₉ can also be represented by formula (2), substituted or unsubstituted C6-30 aryl, C2-C30 heteroaryl containing one or more heteroatoms substituted or unsubstituted;

The substituents of the "substituted or unsubstituted" groups are optionally selected from one or more of protium atom, deuterium atom, tritium atom, halogen atom, cyano trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, fluoromethyl, fluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, C6-C20 aryl, C2-C20 heteroaryl containing one or more heteroatoms;

the heteroatoms in the C2-C50 heteroaryl, C2-C50 heteroarylene, C2-C30 heteroaryl, C2-C20 heteroaryl are selected from nitrogen, oxygen, phosphorus, sulfur, or fluorine.

Preferably, the structure of the organic compound containing the polyfluoro-substituted glutarimide or succinimide is shown as the general formula (4) to the general formula (9):

The definitions of Z, L, L ₁、L₂、L₃、X、R₁ to R ₁₁ are as defined in claim 1;

In the general formulas (4) to (6), a+b+c is more than or equal to 3;

In the general formulae (7) to (9), a+b+c is not less than 1.

It is further preferred that each of said R ₁ to R ₄, which are identical or different, independently represents a hydrogen atom, a fluorine atom, a trifluoromethyl group; and R ₁ to R ₄ cannot be hydrogen atoms at the same time;

the X is represented by a single bond 、-C(H)₂-、-C(H)(F)-、-C(F)(CF₃)-、-C(F)₂-、-C(F)(CF₃)-、-C(CF₃)₂-;

Each of the radicals R5 to R9, which are identical or different and each independently of one another, represents cyano, halogen, hydrogen, deuterium, tritium, fluorine, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, fluoromethyl, fluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy,Substituted or unsubstituted phenyl, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted pyridylene, substituted or unsubstituted pyrimidylene, substituted or unsubstituted phenanthryl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted triazinyl, substituted or unsubstituted furyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted dibenzooxazolyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl,

Each occurrence of Z is the same or different and each independently represents C-R or N;

Each occurrence of said R is the same or different and each independently represents cyano, halogen, hydrogen, deuterium, tritium, fluorine, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, fluoromethyl, fluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or t-butoxy;

L, L ₁、L₂、L₃ each independently represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted pyrimidinylene group;

The substituent of the "substituted or unsubstituted" is optionally selected from protium atom, deuterium atom, tritium atom, halogen atom, cyano group, trifluoromethyl group, trifluoromethoxy group, difluoromethyl group, difluoromethoxy group, fluoromethyl group, fluoromethoxy group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, benzophenanthryl group, pyridyl group, pyrimidinyl group, oxadiazolyl group, triazinyl group, furyl group, dibenzofuryl group, dibenzothienyl group, benzoxazolyl group, substituted or unsubstituted dibenzooxazolyl group, carbazolyl group, N-phenylcarbazolyl group, quinolyl group, isoquinolyl group, etc.

It is further preferred that said R ₁ to R4 represent fluorine atoms; x is a single bond or-C (F) ₂ -;

At least one of said R5 to R9 is represented by trifluoromethyl, preferably at least two are represented by trifluoromethyl.

Preferably, the structure of the organic compound containing the polyfluoro-substituted glutarimide or succinimide is shown as a general formula (1-1) or a general formula (1-2):

in the general formula (1-1) and the general formula (1-2), Z is the same or different and each independently represents C-R or N; z at the junction with other groups is denoted C;

L ₁、L₂、L₃ each independently represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted pyrimidinylene group;

Ar ₁ represents a structure shown in the general formula (2); ar ₂、Ar₃ has a structure shown in a general formula (2) or a general formula (3) which are independent from each other;

In the general formula (2), X represents a single bond, -C (R ₁₀)(R₁₁)

Each of said R, R ₅ to R ₁₁, which are identical or different, independently of one another, represents cyano, halogen, hydrogen, deuterium, tritium, fluorine, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, fluoromethyl, fluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy;

Preferably, the structure of the organic compound containing polyfluoro-substituted glutarimide or succinimide is shown as the general formulas (1-3) to (1-6):

Z, L ₁、L₂、L₃、Ar₁、Ar₂、Ar₃ in the general formulae (1-3) to (1-6) are as defined for them in the general formula (1-2).

Preferably, ar ₁ is represented as:

ar ₂、Ar₃ is represented by any one of the following structures:

the L ₁、L₂、L₃ is represented as

A single bond,

It is further preferred that the specific structural formula of the organic compound is any one of the following structures:

Preferably, the refractive index of the organic compound at blue light having a wavelength of 460nm is in the range of 1.4 to 1.7, preferably 1.4 to 1.6.

The organic electroluminescent device of the present invention includes:

A substrate layer;

a first electrode over the substrate layer;

an organic light emitting functional layer over the first electrode;

a second electrode over the organic light emitting functional layer; and

A cover layer over the second electrode;

The cover layer comprises one or more of the polyfluoro-substituted glutarimide or succinimide-containing organic compounds.

Preferably, the organic electroluminescent device, the cover layer comprises a first cover layer and a second cover layer,

The first cover layer is above the second electrode;

the second cover layer is over the first cover layer;

The first cover layer comprises one or more of the polyfluoro-substituted glutarimide or succinimide-containing organic compounds.

Preferably, the refractive index of the first cover layer material is smaller than the refractive index of the second cover layer material, the refractive index of the first cover layer material at 460nm is smaller than or equal to 1.60, the refractive index of the second cover layer material at 460nm is larger than or equal to 1.85, and the refractive index difference between the second cover layer material and the first cover layer material at 460nm is larger than or equal to 0.3.

It is further preferred that the first cover layer material has a band gap Eg of greater than 3.0ev, preferably greater than 3.5ev, and that the first cover layer material has a refractive index difference of 0.3 or less at wavelengths of 460nm and 620 nm.

The total film thickness of the cover layer is 15 to 300nm, more preferably 30 to 200nm, still more preferably 40 to 100nm, most preferably 50 to 80nm; the film thickness of the first cover layer is 1-150nm, preferably 5-100nm, more preferably 10-50nm; the film thickness of the second cover layer is 1 to 150nm, preferably 10 to 100nm, more preferably 20 to 80nm.

The term "aryl" as used herein denotes in each case optionally substituted mono-, bi-or polycyclic aromatic systems having the indicated number of ring carbon atoms, preferably from 6 to 50, in particular from 6 to 30, such as "C6-C50 aryl", examples of which include, but are not limited to, phenyl, benzyl, biphenyl, naphthyl, anthryl, phenanthryl, 9, 10-benzophenanthryl, fused tetraphenyl, pyrenyl, biphenyl, p-biphenyl, m-biphenyl,A group, a biphenylene group, a perylene group, an indenyl group, a triphenylene group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, and the like. "arylene" means an optionally substituted divalent radical of a monocyclic, bicyclic or polycyclic aromatic system having the indicated number of ring carbon atoms (preferably 6 to 50, especially 6 to 30) in each case, examples of which include, but are not limited to, the divalent radicals of the radicals mentioned above.

The term "heteroaryl" denotes here an aromatic radical having in each case the indicated number of ring carbon atoms (preferably from 2 to 50, in particular from 2 to 30) and at least one heteroatom selected from N, O, s and P. For example, "C2-C50 heteroaryl", examples of which include, but are not limited to, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2, 3-triazinyl, 1,2, 4-triazinyl, 1,3, 5-triazinyl, benzofuranyl, benzisofuranyl, benzothienyl, benzisothiophene, indolyl, isoindolyl, indazolyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzidinyl, benzisoxazolyl, and the like benzothiazolyl, 2,1, 3-benzoxadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinolyl, naphthyridinyl, benzotriazinyl, benzoxazinyl, purinyl, pteridinyl, indolizinyl, benzothiazinyl, acridinyl, oxazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, naphtofuranyl, quinolinyl, isoquinolinyl, indolo [1,2-f ] phenanthridinyl, imidazo [2,1-a ] isoquinolinyl, imidazo [1,2-a ] quinolinyl, benzo [4,5] imidazo [1,2-a ] pyridinyl, benzofuran [3,2-C ] quinolinyl, naphtho [1,2-b ] benzofuranyl, naphtho [2,3-b ] benzofuranyl, aromatic combination groups having heteroatoms, and the like. "heteroarylene" means a divalent radical of an aromatic group having the indicated number of ring carbon atoms (preferably 2 to 50, especially 2 to 30) and at least one heteroatom selected from N, O, s and P, examples of which include, but are not limited to, the divalent radicals of the foregoing groups.

The invention has the technical effects that:

The refractive index of the compound is lower than 1.60 in the blue light region. The fluorine-containing compound belongs to a low-refractive-index organic material, has stable vapor deposition process, and can not form material clusters in the film making process, thereby being beneficial to improving the yield of the display screen preparation.

Drawings

FIG. 1 is a schematic cross-sectional structure of an example of application of the compound of the present invention (top-emitting organic electroluminescent device)

Wherein 100 is a substrate, 200 is a first electrode, 300 is an organic light emitting functional layer, 400 is a second electrode, and 500 is a cover layer.

FIG. 2 is a schematic cross-sectional view of an organic light-emitting functional layer 300 of the top-emitting organic electroluminescent device of FIG. 1

Wherein 310 (HIL) is a hole injection layer, 320 (HTL) is a hole transport layer, 330 (EBL) is an electron blocking layer, 340 (EML) is a light emitting layer, 350 (HBL) is a hole blocking layer, 360 (ETL) is an electron transport layer, and 370 (EIL) is an electron injection layer.

FIG. 3 is a schematic cross-sectional view of the cover layer of FIG. 1

Wherein 510 is a low refractive index first cladding layer, 520 is a high refractive index second cladding layer

Detailed Description

Throughout this specification, unless explicitly stated to the contrary, the word "comprise" or variations such as "comprises" or "comprising", will be understood to imply the inclusion of other elements but not the exclusion of any other element. Furthermore, it will be understood that throughout the specification, when an element such as a layer, film, region or substrate is referred to as being "on" or "over" another element, it can be "directly on" the other element or intervening elements may also be present. In addition, "on … …" or "above … …" means above the target portion, and not necessarily above in the direction of gravity.

As used herein, "n@460nm" refers to the refractive index of the material relative to vacuum for blue light of 460nm wavelength; "n@525nm" refers to the refractive index of the material relative to vacuum for green light of wavelength 525 nm; "n@620nm" refers to the refractive index of the material relative to vacuum for red light of 620nm wavelength; "k@380nm" refers to the extinction coefficient of a material with respect to vacuum for a wavelength of 380 nm.

As used herein, a C6-C50 aryl group refers to a monovalent group comprising a carbocyclic aromatic system having from 6 to 50 carbon atoms as ring-forming atoms. Non-limiting examples of C6-C50 aryl groups can include phenyl, biphenyl, phenanthryl, terphenyl, naphthyl, phenanthryl, benzophenanthryl, benzyl, anthracenyl, 9, 10-benzophenanthryl, fused tetraphenyl, pyrenyl, biphenyl, p-biphenylyl, m-biphenylyl, p-triphenylyl, m-triphenylyl,A group, a biphenylene group, a perylene group, an indenyl group, a triphenylene group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a benzodimethylfluorenyl group, and the like. When the C6-C50 aryl group comprises two or more rings, these rings may be fused to each other.

In the present context, the term "a" is used, non-limiting examples of C2-C50 heteroaryl groups may include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2, 3-triazinyl, 1,2, 4-triazinyl, 1,3, 5-triazinyl, benzofuranyl, benzisothiophene, indolyl, isoindolyl, indazolyl, benzimidazolyl, benzoxazolyl benzoisoxazolyl, benzothiazolyl, 2,1, 3-benzoxadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinolyl, naphthyridinyl, benzotriazinyl, benzoxazinyl, purinyl, pteridinyl, indolizinyl, benzothiazinyl, acridinyl, oxazinyl, phenothiazinyl, oxazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, naphthofuranyl, quinolinyl, isoquinolinyl, indolo [1,2-f ] phenanthridinyl, imidazo [2,1-a ] isoquinolinyl, imidazo [1,2-a ] quinolinyl, benzo [4,5] imidazo [1,2-a ] pyridinyl, benzofuran [3,2-C ] quinolinyl, naphtho [1,2-b ] benzofuranyl, naphtho [2,3-b ] benzofuranyl, and the like, and aromatic groups having hetero atoms and the like are also included. When the C ₂-C₅₀ heteroaryl group includes two or more rings, these rings may be fused to each other.

As used herein, C ₆-C₂₀ aryl refers to a monovalent group comprising a carbocyclic aromatic system having from 6 to 20 carbon atoms as ring-forming atoms. Non-limiting examples of C ₆-C₂₀ aryl groups can include phenyl, biphenyl, phenanthryl, biphenyl, naphthyl, phenanthryl, benzophenanthryl, benzyl, anthracyl, 9, 10-benzophenanthryl, fused tetraphenyl, pyrenyl, biphenyl, p-biphenylyl, m-biphenylyl,A group, a biphenylene group, a perylene group, an indenyl group, a triphenylene group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a benzodimethylfluorenyl group, and the like.

As used herein, C ₂-C₂₀ heteroaryl refers to a monovalent group comprising a carbocyclic aromatic system having at least one heteroatom selected from N, O, P and S and 2 to 20 carbon atoms as ring forming atoms. Non-limiting examples of C ₂-C₂₀ heteroaryl groups can include pyridyl, oxadiazolyl, triazinyl, pyrimidinyl, furyl, dibenzofuranyl, dibenzothienyl, benzoxazolyl, dibenzooxazolyl, carbazolyl, N-phenylcarbazolyl, quinolinyl, isoquinolinyl, naphthofuryl, phenyl-substituted naphthofuryl.

As used herein, C ₆-C₅₀ arylene means phenylene, naphthylene, anthrylene, fluorenylene, dimethylfluorenylene, diphenylfluorenylene, spirofluorenylene, phenanthrylene, fused tetraphenyl, pyrenylene, biphenylene, p-biphenylene, m-biphenylene, andA group, a biphenylene, a perylene group, an indenylene group, but is not limited thereto.

As used herein, C ₂-C₅₀ heteroarylene refers to furanylene, thienyl, pyrrolylene, pyrazolylene, imidazolylene, triazolylene, oxazolylene, thiazolylene, oxadiazolylene, thiadiazolylene, pyridyl, pyrimidinylene, pyrazinylene, triazinylene, benzofuranylene, benzothienyl, benzimidazolylene, indolylene, quinolinylene, isoquinolylene, quinazolinylene, quinodown, naphthyridinyl, benzoxazolylene, benzothiazinylene, acridinylene, oxazinylene, dibenzofuranylene, dibenzothiophenylene, carbazolylene, combinations thereof, or fused rings of combinations of the foregoing, but is not limited thereto.

Organic electroluminescent device

The compound is particularly suitable for vapor deposition and improving light extraction efficiency, and can improve the stability of a production process, improve the optimal vapor deposition film thickness range, avoid the phenomenon of black spots of devices and the like, and the obtained devices or elements have high yield and high visible light extraction efficiency. It is therefore an object of the present invention to provide an organic electroluminescent device comprising:

A substrate layer;

a first electrode over the substrate layer;

an organic light emitting functional layer over the first electrode;

a second electrode over the organic light emitting functional layer; and

A cover layer over the second electrode;

In one embodiment of the invention, the refractive index of the first cladding layer is less than the refractive index of the second cladding layer; the refractive index @460nm of the first cover layer is less than or equal to 1.65, preferably less than or equal to 1.60, preferably less than or equal to 1.55; preferably 1.50 or less; the refractive index @525nm of the first cover layer is less than or equal to 1.65, preferably less than or equal to 1.60, preferably less than or equal to 1.55; preferably 1.50 or less; the refractive index @620nm of the first cover layer is less than or equal to 1.65, preferably less than or equal to 1.60, preferably less than or equal to 1.55; preferably 1.50 or less; the second cladding layer has a refractive index @460nm of 1.85 or more, preferably 1.9 or more, preferably 2.0 or more, preferably 2.1 or more, preferably 2.2 or more; more preferably 2.3 or more; the second cover layer has a refractive index @525nm of 1.85 or more, preferably 1.9 or more, preferably 2.0 or more, preferably 2.1 or more, more preferably 2.2 or more; the second cover layer has a refractive index @620nm of 1.8 or more, preferably 1.9 or more, preferably 2.0 or more, more preferably 2.1 or more.

In one embodiment of the present invention, the difference in refractive index @460nm between the first cover layer and the second cover layer is 0.3 or more; preferably 0.4 or more; preferably 0.5 or more; preferably 0.6 or more; preferably 0.7 or more; more preferably 0.8 or more.

In a preferred embodiment of the present invention, there is provided an OLED comprising a substrate, an anode, a cathode, an organic light-emitting functional layer and a capping layer, wherein the organic light-emitting functional layer may comprise a light-emitting layer, a hole-transporting layer, a hole-injecting layer, an electron-blocking layer, an electron-transporting layer, an electron-injecting layer, etc., and may also comprise only the light-emitting layer and one or more other layers, wherein the capping layer consists of one or more of the compounds of the above general formula (1) or comprises one or more of the compounds of the general formula (1). Optionally, a protective layer and an encapsulation layer are also provided over the cover layer.

As shown in fig. 1, the substrate 100 may be any substrate used in a typical organic light emitting device. The flexible PI film can be a glass or transparent plastic substrate, a substrate made of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness and waterproofness, and the use direction is different according to the different properties of the substrates.

The first electrode 200 is formed on the substrate 100, and the first electrode 200 may be a cathode or an anode. Here, the first electrode 200 may be only a reflective film formed of a reflective electrode such as silver (Ag), magnesium (Mg), aluminum (Al), gold (Au), nickel (Ni), chromium (Cr)) or an alloy thereof, or may be an electrode formed by combining a reflective film and a transparent or semitransparent electrode, for example, a transparent or semitransparent electrode layer having a high work function and formed on the reflective film. The transparent or semitransparent electrode layer may be formed of Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), zinc oxide (ZnO), aluminum Zinc Oxide (AZO), indium Gallium Oxide (IGO), indium oxide (In ₂O₃), or tin oxide (SnO ₂); it may also be formed from a combination of metals and oxides, such as ITO/Ag/ITO, IGO/Al/IGO or AZO/Ag/AZO.

The first electrode 200 may be formed by a sputtering method, an ion plating method, a vacuum evaporation method, a spin coating method, an electron beam evaporation method, a Chemical Vapor Deposition (CVD) method, or the like, and is preferably formed by a sputtering method.

The thickness of the first electrode layer 200 depends on the material used, and is generally 5nm to 1. Mu.m, preferably 10nm to 1. Mu.m, more preferably 10nm to 500nm, particularly preferably 10nm to 300nm, and most preferably 10nm to 200nm.

As shown in fig. 2, the organic light emitting functional layer 300 may include an emitting layer 340 (EML), and if the first electrode 200 is an anode, a hole transport region may be formed between the EML and the first electrode 200, and an electron transport region may be formed between the EML and the second electrode layer 400; if the first electrode 200 is a cathode, an electron transport region may be formed between the EML and the first electrode 200, and a hole transport region may be formed between the EML and the second electrode layer 400. The hole transport region may include at least one of a hole injection layer 310 (HIL), a hole transport layer 320 (HTL), and an electron blocking layer 330 (EBL). The electron transport region may include at least one of a hole blocking layer 350 (HBL), an electron transport layer 360 (ETL), and an electron injection layer 370 (EIL). Thus, the organic light emitting functional layer 300 includes a combination of at least 2 layers of a light emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

The thickness of the organic light emitting functional layer 300 is 50nm to 1000nm.

As the material of the hole injection layer, the hole transport layer, and the electron blocking layer (HIL 310, HTL320, EBL 330), any material may be selected from known related materials for OLED devices.

At least one of the HIL310 and the HTL320 may further include a charge generation material for improving conductivity. The charge generating material may be a p-dopant. Non-limiting compounds of P-dopants are as follows: quinone derivatives such as Tetracyanoquinodimethane (TCNQ) and 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinone dimethane (F4-TCNQ); or hexaazatriphenylene derivatives such as 2,3,6,7, 10, 11-hexacyano-1,4,5,8,9, 12-hexaazatriphenylene (HAT-CN); or cyclopropane derivatives such as 4,4',4 "- ((1E, 1' E, 1" E) -cyclopropane-1, 2, 3-trimethylenetris (cyanoformylidene)) tris (2, 3,5, 6-tetrafluorobenzyl); or metal oxides such as tungsten oxide and molybdenum oxide, but not limited thereto.

The triplet (T1) level of the desired material in EBL330 is higher than the T1 level of the host material in light emitting layer 340 and can act to block energy loss from the light emitting layer material; the HOMO energy level of the EBL330 material is between the HOMO energy level of the HTL320 material and the HOMO energy level of the host material of the light-emitting layer 340, which facilitates hole injection from the positive electrode into the light-emitting layer, while requiring the EBL330 material to have high hole mobility, facilitate hole transport, and reduce the device application power; the LUMO level of the EBL330 material is higher than that of the host material of the light emitting layer 340, and functions as an electron blocking, i.e., the EBL330 material is required to have a wide forbidden bandwidth (Eg). The EBL330 material satisfying the above conditions may be a triarylamine derivative, a fluorene derivative, a spirofluorene derivative, a dibenzofuran derivative, a carbazole derivative, or the like. Among them, triarylamine derivatives such as N4, N4-bis ([ 1,1 '-biphenyl ] -4-yl) -N4' -phenyl N4'- [1,1':4',1 "-terphenyl ] -4-yl- [1,1' -biphenyl ] -4,4' -diamine; spirofluorene derivatives such as N- ([ 1,1 '-diphenyl ] -4-yl) N- (9, 9-dimethyl-9H-furan-2-yl) -9,9' -spirobifluorene-2-amine; dibenzofuran derivatives such as, but not limited to, N-di ([ 1,1' -biphenyl ] -4-yl) -3' - (dibenzo [ b, d ] furan-4-yl) - [1,1' -biphenyl ] -4-amine.

In order to obtain a high-efficiency OLED device, the light-emitting layer 340 may be made of the same doped material, or multiple doped materials, where the doped materials may be a single fluorescent material, a delayed fluorescence (TADF) material, or a phosphorescent material, or may be made of different fluorescent materials, TADF materials, or phosphorescent materials, and the light-emitting layer 340 may be made of a single light-emitting layer material, or may be made of a composite light-emitting layer material stacked together transversely or longitudinally. The light emitting layer 340 constituting the above-described OLED light emitter may be selected from a variety of configurations as follows:

(1) A single organic light emitting layer material;

(2) Any combination of blue organic light emitting layer material and green, yellow or red light emitting layer material, not in order;

(3) Any two combinations of blue organic light emitting layer material and green, yellow or red light emitting layer material are not in order;

(4) The blue organic light-emitting layer material, the green organic light-emitting layer material and the red organic light-emitting layer material are transversely arranged.

In order to adjust the effective combination of carrier charges in the light-emitting layer, the film thickness of the light-emitting layer 340 constituting the OLED light-emitting body may be arbitrarily adjusted as required, or light-emitting layers which cannot be colored may be alternately stacked and combined as required, and charge blocking layers for different functional purposes may be added to the organic layers adjacent to the light-emitting layers.

The host material constituting the light-emitting layer of the OLED light-emitting device needs to have not only bipolar charge transport characteristics but also an appropriate energy level, and thus excitation energy generated by recombination of electrons and holes is efficiently transferred to the guest light-emitting material, i.e., the dopant material. Examples of such a material include distyrylarylene derivatives, stilbene derivatives, carbazole derivatives, triarylamine derivatives, anthracene derivatives, pyrene derivatives, triazine derivatives, xanthone derivatives, triphenylene derivatives, triazine derivatives, hexabenzobenzene derivatives, bis (2-methyl-8-quinoline) (p-phenylphenol) aluminum (BAlq), and the like.

The hole blocking layer 350 and the electron transport layer 360 constituting the OLED device may be formed of any material selected from materials for OLED having electron transport characteristics. Examples of such a material include oxadiazole derivatives such as 1, 3-bis [5'- (p-tert-butylphenyl) -1,3, 4-oxadiazol-2' -yl ] benzene, 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole, triazole derivatives such as 3- (4 '-tert-butylphenyl) -4-phenyl-5- (4' -biphenyl) -1,2, 4-triazole, triazine derivatives, quinoline derivatives, quinoxaline derivatives, dibenzoquinone derivatives, nitro substituted-pyridone derivatives, thiopyran dioxide derivatives, anthraquinone-dimethane derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic acid anhydrides such as naphthalene perylene, carbodiimide, fluorene derivatives, anthraquinone-dimethane derivatives, anthranone derivatives, diphenylpyrazine derivatives, silacyclopentadiene derivatives, diazaphenanthrene derivatives, or imidazopyridine derivatives.

The second electrode 400 is formed on the organic light emitting functional layer 300, and the second electrode layer may be a cathode, an anode, or a transparent electrode or a semitransparent electrode. The second electrode 400 may be made of lithium, calcium, lithium/calcium fluoride, lithium/aluminum fluoride, aluminum, silver, magnesium, or an alloy thereof to form a thin film having a low work function. Further, the second electrode layer 400 may be made of an alloy including silver and at least one metal including aluminum, platinum, ytterbium, chromium, or magnesium. And, the weight ratio of Ag in the alloy may be the same as that of other metals or greater or less than that of other metals. For example: the second electrode layer 400 may be formed of an ag—mg alloy, wherein a mass ratio of Ag to Mg may be 90:10 to 10:90. or the second electrode layer 400 may be formed of an alloy including at least one metal such as silver, gold, platinum, copper, nickel, or tungsten and at least one metal such as ytterbium, indium, magnesium, or chromium. These metal films can form transparent or semitransparent electrodes by adjusting the thickness of the film. Accordingly, light generated from the organic light emitting functional layer 300 may be emitted through the second electrode layer 400. And, the second electrode layer 400 may have a thickness of 5-20nm.

A capping layer 500 is formed on the second electrode layer 400, and includes a first capping layer 510 and a second capping layer 520.

The material used for the first cover layer is one or more of the compounds of the above general formula (1) constituting the compound of the general formula (1).

The second cover layer material may have the following structure:

The total film thickness of the coating layer of the present invention is 15 to 300nm, preferably 30 to 200nm, preferably 40 to 100nm, most preferably 50 to 80nm; the film thickness of the first cover layer is 1-150nm, preferably 5-100nm, more preferably 10-50nm; the film thickness of the second cover layer is 1-150nm, preferably 10-100nm, more preferably 20-80nm; the film thickness of the second cover layer may be the same as or different from the film thickness of the first cover layer.

Referring to fig. 1, the organic electroluminescent device of the present invention includes a substrate layer 100, a first electrode layer 200, an organic light emitting functional layer 300, a second electrode layer 400, and a capping layer 500.

Barrier layers (which may be composed of inorganic materials or/and organic materials for preventing foreign materials from penetrating the substrate and the device) and wiring layers (which may include driving TFTs, capacitors, wires, and low temperature polysilicon LTPS) may be formed on the substrate layer using well-known methods.

In a specific embodiment, the first electrode 200 may be a reflective electrode and the second electrode 400 is a transparent or translucent electrode. Accordingly, light generated by the organic light emitting functional layer 300 may be directly emitted from the second electrode 400, or may be reflected by the first electrode 200 to be emitted after being emitted toward the second electrode 400. The first electrode 200 may be prepared by, for example, an evaporation method or a sputtering method. The second electrode 400 may be prepared by, for example, a vacuum evaporation method.

The organic light emitting functional layer 300 may include an emitting layer 340 (EML), and a hole transport region may be formed between the EML and the first electrode 200, and an electron transport region may be formed between the EML and the second electrode layer 400. The hole transport region may include at least one of a hole injection layer 310 (HIL), a hole transport layer 320 (HTL), and an electron blocking layer 330 (EBL). The electron transport region may include at least one of a hole blocking layer 350 (HBL), an electron transport layer 360 (ETL), and an electron injection layer 370 (EIL).

The organic light emitting functional layer 300 may be composed of a small molecular organic material or a high molecular material, and the organic light emitting functional layer 300 may be prepared by various methods, such as a vacuum evaporation method, a solution spin coating method, a screen printing method, an inkjet printing method.

The capping layer 500 may be composed of the organic compound based on the heteroaryl amine structure, and the capping layer 500 may be prepared using various methods, such as a vacuum evaporation method, a solution spin coating method, a screen printing method, an inkjet printing method.

A protective layer is provided on the cover layer 500. The protective layer comprises lithium fluoride (LiF). The thickness of the protective layer depends on the material used, and is generally 20 to 400nm, preferably 30 to 200nm and more preferably 40 to 100nm.

An encapsulation layer is arranged on the protection layer. The encapsulation layer is a protection structure for preventing foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device, and is a multi-layer film covering the whole surfaces of the organic layer, the cover layer and the protection layer. A first encapsulation layer on the protective layer, a second encapsulation layer on the first encapsulation layer, and a third encapsulation layer on the second encapsulation layer; the first packaging layer is an inorganic layer; the second packaging layer is an organic layer; the third packaging layer is an inorganic layer; the inorganic layer comprises at least one selected from the group consisting of Al ₂O₃、SiO_xN_y、TiO₂、SiO_x and SiN _x, wherein x and y are the same or different, x, y being independently from each other greater than 0 and less than 10, preferably greater than 0 and less than 5, most preferably greater than 0 and less than 3. The inorganic layer is prepared by Chemical Vapor Deposition (CVD).

As the encapsulating layer organic material for the organic electroluminescent device of the present invention, encapsulating layer organic materials for organic electroluminescent devices known in the art may be used. In a preferred embodiment of the present invention, the encapsulating layer organic material used is Polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), polystyrene (PS), a polymer derivative having a phenol group (phenolgroup), an acrylic polymer (acryl-basedpolymer), an imide polymer (imide-basedpolymer), an aryl ether polymer (arylether-basedpolymer), an amide polymer (amide-basedpolymer), a fluorine polymer (fluoride-basedpolymer), a p-xylene polymer (p-xylene-basedpolymer), a vinyl alcohol polymer (vinylalcohol-basedpolymer) or a mixture thereof.

The encapsulating layer organic material is sufficiently thick to cover the encapsulating inorganic layer, and is cured to a polymer by UV curing.

According to the present invention, the organic electroluminescent device is preferably a top-emission organic electroluminescent device comprising evaporating a material comprising the compound of the general formula (1) of the present invention as a capping layer on the light-emitting side after preparing an anode, a cathode and an organic light-emitting functional layer for improving light extraction efficiency and viewing bias problems.

The problem of visual bias referred to herein refers to viewing the device at different angles with a gradual change in the color of the emitted light. In this context, improvement of the visual deviation and reduction of the angle dependence are reflected in a significant reduction of the trend of the change in the emission color with the change in the angle of observation, and no change in the emission color occurs in an ideal state. The color difference can be measured by parameters JNCD (JUSTNOTICEABLECOLORDIFFERENCE), JNCD is obvious color difference which can be perceived by human eyes, and the smaller the numerical value of JNCD is, the more obvious the effect of improving the visual deviation is.

In addition, the OLED device of the present invention can be used in OLED lighting and display devices.

Preferably, the OLED device prepared by the method is used in the fields of smart phones, tablet computers and the like, the fields of intelligent wearable equipment, the fields of large-size application such as televisions and the like, the VR (virtual reality) and micro-display fields, and an automobile central control screen or an automobile tail lamp.

Preparation of the Compounds of the invention

Examples

The present invention will be described in detail below with reference to the drawings and examples.

I. synthesis of intermediate 1:

To a 200mL two-necked round bottom flask were added 3-bromo-5-iodoaminobenzene (5 g,16.8 mmol), 3, 5-bis (trifluoromethyl) phenylboronic acid (3.87 g,15.0 mmol), pd (OAc) ₂(101mg,0.450mmol)、PPh₃ (239 mg,0.911 mmol) and K ₂CO₃ (6.23 g,45.1 mmol), respectively. Toluene (40 mL) and water (40 mL) were added via syringe and the mixture was refluxed for 24 hours at 100deg.C. The resulting mixture was extracted with ethyl acetate (30 mL. Times.3). The combined organic layers were dried over Na ₂SO₄ and concentrated in vacuo. The residue was subjected to silica gel column chromatography (eluent: hexane) to give intermediate 1.LC-MS: measurement value: 383.72 ([ M+H ] ⁺), precise mass: 382.97.

II, synthesis of intermediate 2:

Intermediate 1 (1.15 g,3 mmol), pinacol biborate (1.52 g,6 mmol), naOAc (1 g,12 mmol), pd (PPh) ₂Cl₂ (10.5 g,1.5 mmol) were added to 5mL of DMF in sequence under nitrogen protection, reacted for 8h in an oil bath at 90 ℃ with hexane and ethyl acetate as eluent, and the progress of the reaction was checked by thin layer chromatography. After the completion of the reaction, the reaction system was cooled to room temperature, extracted with diethyl ether (10 mL. Times.3), and the diethyl ether layer was washed 3 times with brine, dried over anhydrous magnesium sulfate, distilled under reduced pressure, and purified by silica gel column chromatography using hexane and ethyl acetate (9:1) as eluent to give intermediate 2.LC-MS: measurement value: 432.19 ([ M+H ] ⁺), precise mass: 431.15.

III, synthesis of intermediate 3:

Into an oven dried round bottom flask was added hexafluoroglutaric anhydride (0.67 g,3.0 mmol) solution, intermediate 2 (1.29 g,3.0 mmol) to 30ml toluene solution at room temperature and heated to reflux for 6 hours. The reaction mixture was cooled to room temperature and diluted with hexane (15 mL). The precipitated solid was filtered, washed with hexane and dried under vacuum to give the crude product. The crude product was dissolved in 30ml Ac ₂ O, naOAc (3.69 g,4.5 mmol) was added and the resulting mixture was stirred in an oil bath at 120℃for 6 hours. After completion of the reaction, quench with cold water (30 mL) and extract with dichloromethane (15 mL x 3), the combined organic layers were washed with saturated NaHCO ₃ solution (30 mL x 2) and brine (20 mL). The organic layer was dried over anhydrous MgSO ₄, filtered and concentrated in vacuo. The crude product was purified by column chromatography (hexane/EtOAc, 7/3, silica gel) to give intermediate 3.LC-MS: measurement value: 636.31 ([ M+H ] ⁺), precise mass: 635.11.

Synthesis of intermediate 4:

Intermediate 4 was prepared following the procedure of intermediate 3, except intermediate 2 was replaced with intermediate 1.LC-MS: measurement value: 587.75 ([ M+H ] ⁺), precise mass: 586.94.

V. synthesis of intermediate 5:

To a dry flask were added 1,3, 5-tribromobenzene (9.6 g,31 mmol) and Pd (PPh ₃)₄ (1.0 g,0.9 mmol) under Ar, a solution of 3, 5-bis (trifluoromethyl) phenylboronic acid (17 g,66 mmol) in toluene (120 mL) and a solution of 1M Na ₂CO₃ (100 mL) were added to the reaction vessel and the mixture was refluxed under Ar for 48H.

Synthesis of intermediate 6:

Intermediate 6 was prepared as in intermediate 1 except that 3-bromo-5-iodoaminobenzene was replaced with 2-bromo-4-iodoaniline (5 g,16.8 mmol) and the reaction conditions were adjusted from 100℃for 24 hours to 80℃for 3d. LC-MS: measurement value: 383.52 ([ M+H ] ⁺), precise mass: 382.97.

Synthesis of intermediate 7:

In a three-necked flask, intermediate 6 (0.19 g,0.5 mmol), pinacol biborate (3.81 g,15 mmol) in dioxane (50 ml), et ₃N(2.2ml,15mmol),PdCl₂ (dppf) (0.22 g,0.25 mmol) were added sequentially under nitrogen and the mixture was stirred in an oil bath at 100deg.C for 3h. After the completion of the reaction, the reaction system was cooled to room temperature, and quenched by addition of 50ml of H ₂ O. The aqueous layer was extracted with EtOAc (50 ml×3) and the combined organic layers were dried over anhydrous magnesium sulfate and concentrated in vacuo. Purification by column chromatography on silica gel using petroleum ether/EtOAc (20/1) as eluent afforded intermediate 7.LC-MS: measurement value: 432.19 ([ M+H ] ⁺), precise mass: 431.15.

Synthesis of intermediate 8:

Intermediate 8 was prepared following the procedure for intermediate 3, except intermediate 2 was replaced with intermediate 7 (1.29 g,3.0 mmol). LC-MS: measurement value: 636.34 ([ M+H ] ⁺), precise mass: 635.11.

IX. Synthesis of intermediate 9:

intermediate 9 was prepared following the procedure for intermediate 3, except intermediate 2 was replaced with intermediate 6 (1.15 g,3.0 mmol). LC-MS: measurement value: 587.82 ([ M+H ] ⁺), precise mass: 586.94.

Synthesis of intermediate 10:

1, 2-diiodo-4-bromobenzene (12.67 g,31 mmol) and Pd (PPh ₃)₄ (1.0 g,0.9 mmol) were added to a dry flask under Ar, a solution of 3, 5-bis (trifluoromethyl) phenylboronic acid (17 g,66 mmol) in toluene (120 mL) and a solution of 1M Na ₂CO₃ (100 mL) were added to the reaction vessel, and the mixture was refluxed under Ar for 48H.

XI. Synthesis of intermediate 11:

In a three-necked flask, 1,3, 5-benzenetricarbonate trippinacol ester (1.46 g,3.2 mmol), 2-bromo-3, 5-bistrifluoromethylaniline (3.08 g,10.0 mmol), pd (dppf) Cl ₂(130mg,0.1mmol)、Na₂CO₃ (3.30 g,31.5 mmol) were dissolved in a mixture of THF/water (50 mL/20 mL) under nitrogen. The mixture was heated to 70 ℃ and stirred overnight. After cooling to room temperature, a saturated solution of ammonium chloride (100 mL) was added and the organic layer was extracted with dichloromethane (4×50 mL). The combined organic extracts were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate 9/1) to give intermediate 11. Measurement value: 760.44 ([ M+H ] ⁺), precise mass: 759.10.

Synthesis of intermediate 12:

Intermediate 12 was prepared following the procedure of intermediate 11, except that the starting material 2-bromo-3, 5-bistrifluoromethylaniline was replaced by 3-amino-5-bromobenzotrifluoride (2.40 g,10.0 mmol). LC-MS: measurement value: 556.45 ([ M+H ] ⁺), precise mass: 555.14.

Xiii. synthesis of intermediate 13:

3,3', 5' -tetrabromo-1, 1' -biphenyl (0.5 g,1.1 mmol), 4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -3- (trifluoromethyl) aniline (1.52 g,5.3 mmol), pd (PPh ₃)₄ (0.1 g,0.1 mmol) and Cs ₂CO₃ (2.8 g,8.5 mmol) were added to a flask containing 1, 4-dioxane/water (30 mL/3 mL.) the mixture was heated at 90 ℃ nitrogen for 3 days after cooling to room temperature, the solvent was removed under reduced pressure, the residue was then dissolved in CH ₂Cl₂, washed with water and brine, and dried over anhydrous Na ₂SO₄ after which the solvent was evaporated under reduced pressure and the crude product was purified by column chromatography with eluent CH ₂Cl₂/ethyl acetate=1/1, giving intermediate 13.ms-MS: 535629 m+6257 by mass.

Synthesis of intermediate 14:

Intermediate 14 was prepared following the procedure of intermediate 13, except that starting material 4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -3- (trifluoromethyl) aniline was replaced with 3- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -4- (trifluoromethyl) aniline. LC-MS: measurement value: 791.36 ([ M+H ] ⁺), precise mass: 790.20.

XV. Synthesis of intermediate 15:

intermediate 15 was prepared following the procedure of intermediate 11, except that 1,3, 5-benzenetricarbonic acid trippinacol ester, 2-bromo-3, 5-bistrifluoromethylaniline was replaced with 2,4, 6-trifluoro-1, 3, 5-tribromobenzene (1.18 g,3.2 mmol), and [ 3-amino-5- (trifluoromethyl) phenyl ] boronic acid (2.03 g,10.0 mmol). LC-MS: measurement value: 610.18 ([ M+H ] ⁺), precise mass: 609.11.

Synthesis of intermediate 16:

Intermediate 16 was prepared following the procedure of intermediate 11, except that the starting 1,3, 5-benzenetricarbonate, trippinacol ester, 2-bromo-3, 5-bistrifluoromethylaniline was replaced by 2,4, 6-tribromo-1, 3, 5-trimethylbenzene (1.14 g,3.2 mmol), and [ 3-amino-5- (trifluoromethyl) phenyl ] boronic acid (2.03 g,10.0 mmol). LC-MS: measurement value: 598.24 ([ M+H ] ⁺), precise mass: 597.18.

Synthesis of intermediate 17:

Intermediate 17 was prepared following the procedure of intermediate 11, except that the starting material 2-bromo-3, 5-bistrifluoromethylaniline was replaced by 3-bromo-4-trifluoromethylaniline (2.40 g,10.0 mmol). LC-MS: measurement value: 556.31 ([ M+H ] ⁺), precise mass: 555.14.

Preparation of the Compounds of the invention

Example 1: synthesis of Compound 4:

In a three-necked flask, under the protection of nitrogen, intermediate 3 (1.9 g,3 mmol) and intermediate 4 (1.76 g,3 mmol) were sequentially added, 15ml of 2M Na ₂CO₃,Pd(PPh₃)₄ (3.47 g,3 mmol) was added to a 2:1 mixed solution of 100ml toluene and ethanol, and the mixture was refluxed in an oil bath for 10 hours. After the completion of the reaction, the reaction system was cooled to room temperature, water (30 ml) and dichloro (30 ml) were added to separate the organic layer, the organic layer was washed 3 times with water, dried over anhydrous magnesium sulfate, distilled under reduced pressure, and purified by silica gel column chromatography using hexane and dichloro (5:1) as eluent to give compound 4.LC-MS: measurement value: 1017.19 ([ M+H ] ⁺), precise mass: 1016.04.

The following synthesis examples 2 to 4 were prepared using the same method as synthesis example 1, and the following synthesis examples 5 to 12 were prepared using the same method as synthesis intermediate 3, except that different raw materials M, raw materials N, intermediate a, intermediate C were used, and raw materials and intermediates used in the synthesis are shown in table 1 below.

TABLE 1

IV determination of physical Properties of Compounds determination method: refractive index n and extinction coefficient k (glass substrate isotropy) were measured by ellipsometry (model j.a. woollam co. ALPHA-SE, usa) (tested as atmospheric environment); all test result data by the above assay methods are shown in table 2 below.

TABLE 2

As can be seen from the data in table 2 above, the refractive index of the compounds of the present invention in the blue region is lower than 1.6; even less than 1.5;

V device embodiment

The beneficial technical effects of the compounds of the present invention as a capping layer in an OLED device are further illustrated by the following device examples.

1. Materials, apparatus and test methods used in the examples

The material sources are as follows: commercial purchase or reference to literature self-synthesis in the prior art.

The molecular structural formula of the related material is shown as follows:

The device comprises:

Vacuum evaporation device: 200 x 200mm vapor deposition equipment for Japanese Changzhou industry

The testing method comprises the following steps:

Determination of current efficiency, CIEx, CIEy, perceived color difference (JNCD):

The OLED devices in the device examples and device comparative examples described below were tested using an IVL (Current-Voltage-Brightness) test system (Freund's scientific instruments, st.., su.) with software EILV20060707 selected, while data concerning the IVL characteristics, efficiency versus Current density, color coordinate position, etc. of the devices were obtained, and the test was performed in a dark environment under a masking device. The data under the condition of @10mA/cm ² are subject to (namely, the corresponding performance values when the test current density reaches 10mA/cm ²).

Structure and fabrication method of device example 1: :

structure of device example 1: substrate layer 100/first electrode (anode) layer 200 (Ag (100 nm))/hole injection layer 310 (HT-1: P-1=97:3 mass ratio, thickness 10 nm)/hole transport layer 320 (HT-1, thickness 117 nm)/electron blocking layer 330 (EB-1, thickness 10 nm)/light emitting layer 340 (BH-1: BD-1=97:3 mass ratio, thickness 20 nm)/hole blocking layer 350 (HB-1, thickness 8 nm)/electron transport layer 360 (ET-1: liq=1:1 mass ratio, thickness 30 nm)/electron injection layer 370 (LiF, thickness 1 nm)/second electrode (cathode) layer 400 (Mg: ag=1:9 mass ratio, thickness 16 nm)/first capping layer 510 (inventive compound 4, thickness 15 nm)/second capping layer 520 (CP-H1, thickness 50 nm).

Method for manufacturing device example 1: the transparent substrate layer 100 is transparent glass, the first electrode (anode) layer 200 is Ag (100 nm), and the first electrode (anode) layer 200 is washed, i.e., alkali washing, pure water washing, drying are sequentially performed, and then ultraviolet-ozone washing is performed to remove organic residues on the surface of the anode layer. On the anode layer 2 after the above washing, HT-1 and P-1 having film thicknesses of 10nm were vapor deposited as hole injection layers 310 by a vacuum vapor deposition apparatus, and the mass ratio of HT-1 and P-1 was 97:3. Next, HT-1 was evaporated to a thickness of 117nm as a hole transport layer 320. EB-1 was then evaporated to a thickness of 10nm as electron blocking layer 330. After the evaporation of the electron blocking material is completed, the light emitting layer 340 of the OLED light emitting device is fabricated, and the structure of the light emitting layer includes BH-1 used for the OLED light emitting layer 340 as a main material, BD-1 as a doping material, the doping material doping ratio is 3% by weight, and the film thickness of the light emitting layer is 20nm. After the light-emitting layer 340 was deposited, HB-1 was further deposited to a thickness of 8nm as a hole blocking layer 350. And continuously evaporating ET-1 and Liq on the hole blocking layer 350, wherein the mass ratio of the ET-1 to the Liq is 1:1. The vacuum deposition film thickness of the material is 30nm, and the layer is an electron transport layer 360. On the electron transport layer 360, a LiF layer having a film thickness of 1nm, which is an electron injection layer 370, was formed by a vacuum vapor deposition apparatus. On the electron injection layer 370, mg having a film thickness of 16nm was produced by a vacuum vapor deposition apparatus: the Ag electrode layer, mg and Ag in a mass ratio of 1:9, is the second electrode (cathode) layer 400. Vacuum evaporating the compound 4 of the present invention having a film thickness of 15m as a first coating layer on the cathode layer; on the first coating layer, a CP-H1 film having a thickness of 50nm was further vacuum deposited as a second coating layer.

Blue light device examples 2 to 12

The device structure and fabrication method are similar to device embodiment 1, except that the materials of the first cover layer, the second cover layer are changed; specific cover layer materials are described in table 3 below.

Blue light device comparative examples 1 to 3 and 8

The device structures and manufacturing methods of blue light devices of comparative examples 1 to 3 and 8 are similar to those of device example 1, except that a double-layer cover layer is not used and only a single-layer cover layer is used; the specific coating materials and film thicknesses are described in Table 3 below.

Blue light device comparative examples 4 to 7

The device structures and fabrication methods of blue light devices of comparative examples 4-7 are similar to device example 1, except that a comparative compound is used as the first capping layer material, and the specific capping layer materials are described in table 3 below.

The test data for the material of the cap layer in the OLED device, the current efficiency of the device, CIEy, and perceived color difference are presented in table 3.

TABLE 3 Table 3

Note that: index = current efficiency/CIEy and applies only to blue devices, the quality of blue device efficiency is generally not referenced to current efficiency, but to Index (industry standard); perceived chromatic aberration, unit: JNCD;1JNCD = 0.004.

From the data in table 3, it is shown that blue OLED device Index using the inventive compounds as a bilayer cap for a low refractive Index first cap in combination with a high refractive Index second cap is improved by 7% to 12% compared to comparative example 1 for a blue device having only a high refractive Index cap; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 51 percent@30 degrees are reduced (device example 11), so that the angle variation is smaller, and the color cast effect is obviously improved.

Compared with the blue light device comparative example 2 with only the low refractive Index coating, the blue light OLED device Index applied by the double-layer coating using the compound of the invention as the low refractive Index first coating and the high refractive Index second coating is improved by 56% to 65%; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and is even reduced by 37 percent@30 degrees (device example 11), so that the angle variation is smaller, and the color cast effect is obviously improved.

The blue OLED device Index using the inventive compound as a bilayer cap for the low Index first cap in combination with the high Index second cap was increased by 72% to 82% compared to comparative example 3 for a blue device having only the low Index cap of comparative compound CP-R1; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even the perceived color difference is reduced by 35 percent@45 degrees (device example 10), so that the angle variation is smaller, and the color cast effect is obviously improved.

Compared with comparative example 4 of a blue light device with a double-layer coating matched with a comparative compound CP-R1, the Index of the blue light OLED device applied by the double-layer coating matched with a high-refractive-Index second coating and using the compound of the invention as a low-refractive-Index first coating is improved by 5 to 10 percent; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and is even reduced by 37 percent@30 degrees (device example 11), so that the angle variation is smaller, and the color cast effect is obviously improved.

Compared with comparative example 5 of the blue light device of the double-layer coating matched with the comparative compound CP-R2, the Index of the blue light OLED device applied by the double-layer coating matched with the high-refractive-Index second coating and using the compound of the invention as the low-refractive-Index first coating is improved by 4 to 10 percent; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 40 percent@30 degrees are reduced (device example 11), so that the angle variation is smaller, and the color cast effect is obviously improved.

Compared with comparative example 6 of the blue light device with the double-layer coating matched with the comparative compound CP-R3, the Index of the blue light OLED device applied by the double-layer coating matched with the high-refractive-Index second coating and using the compound of the invention as the low-refractive-Index first coating is improved by 4 to 10 percent; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even the perceived color difference is reduced by 35 percent@60 degrees (device example 11), so that the angle variation is smaller, and the color cast effect is obviously improved.

Compared with comparative example 7 of a blue light device with a double-layer coating matched with a comparative compound CP-R4, the Index of the blue light OLED device applied by the double-layer coating matched with a high-refractive-Index second coating by using the compound of the invention as a low-refractive-Index first coating is improved by 7% -9%; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 30 percent@60 degrees are reduced (device example 3, the second cover layer is CP-H12), so that the angle change amount is smaller, and the color cast effect is obviously improved.

Compared with the blue light device comparative example 8 with only the high refractive Index coating, the blue light OLED device Index of the double-layer coating application of the compound of the invention as the low refractive Index first coating and the high refractive Index second coating is improved by 8% -10%; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 53 percent@60 degrees are reduced (device example 3, the second cover layer is CP-H12), so that the angle change amount is smaller, and the color cast effect is obviously improved.

It will be appreciated that the smaller the perceived color difference, the smaller the amount of chromaticity change, meaning that the better the angular dependence of the wavelength of the emitted light of the organic electroluminescent device is suppressed.

In a word, the compound provided by the invention is used as a double-layer coating prepared by matching a first coating material with a high-refractive-index second coating to be applied to an OLED device, so that the light extraction efficiency is greatly improved, the current efficiency is remarkably improved, the angle dependence is improved, and meanwhile, the excellent light extraction efficiency and the visual deflection performance of the device are maintained at a high temperature.

In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention, but any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. An organic compound containing polyfluoro-substituted glutarimide or succinimide, characterized in that the organic compound containing polyfluoro-substituted glutarimide or succinimide has a structure as shown in the general formula (1):

In the general formula (2), X represents a single bond, -C (R ₁₀)(R₁₁) -;

In the general formula (2), R ₁ to R4 are the same or different and each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group;

R ₁ to R ₄ cannot be simultaneously represented as a hydrogen atom;

Each occurrence of R, R to R ₁₁ is the same or different and each represents independently cyano, halogen, hydrogen, deuterium, tritium, fluorine, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, fluoromethyl, fluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy; r ₅ to R ₉ can also be represented by formula (2), substituted or unsubstituted C6-30 aryl, C2-C30 heteroaryl containing one or more heteroatoms substituted or unsubstituted;

2. The organic compound containing polyfluoro-substituted glutarimide or succinimide according to claim 1, wherein the structure of the organic compound containing polyfluoro-substituted glutarimide or succinimide is shown as the general formula (4) to the general formula (9):

In the general formulas (4) to (6), a+b+c is more than or equal to 3;

In the general formulae (7) to (9), a+b+c is not less than 1.

3. The organic compound containing polyfluoro-substituted glutarimide or succinimide according to claim 1 or 2, wherein R ₁ to R ₄ each occurrence of which is the same or different, each independently represents a hydrogen atom, a fluorine atom, a trifluoromethyl group; and R ₁ to R ₄ cannot be hydrogen atoms at the same time; the X is represented by a single bond 、-C(H)₂-、-C(H)(F)-、-C(F)(CF₃)-、-C(F)₂-、-C(F)(CF₃)-、-C(CF₃)₂-;

Each occurrence of R ₅ to R ₉, which are identical or different, independently of one another, represents cyano, halogen, hydrogen, deuterium, tritium, fluorine, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, fluoromethyl, fluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy,Substituted or unsubstituted phenyl, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted pyridylene, substituted or unsubstituted pyrimidylene, substituted or unsubstituted phenanthryl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted triazinyl, substituted or unsubstituted furyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted dibenzooxazolyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl,

Each of said L, L ₁、L₂、L₃ independently represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted pyrimidinylene group;

4. The organic compound containing polyfluoro-substituted glutarimide or succinimide according to claim 1, wherein the structure of the organic compound containing polyfluoro-substituted glutarimide or succinimide is represented by general formula (1-1) or general formula (1-2):

In the general formula (2), X represents a single bond, -C (R ₁₀)(R₁₁)

In the general formula (2), R ₁ to R ₄ each represent the same or different hydrogen atom, fluorine atom and trifluoromethyl independently;

R ₁ to R ₄ cannot be simultaneously represented as a hydrogen atom;

5. The organic compound containing polyfluoro-substituted glutarimide or succinimide according to claim 1, wherein the specific structural formula of the organic compound is any one of the following structures:

6. The organic compound according to any one of claims 1 to 5, comprising a polyfluoro-substituted glutarimide or succinimide, wherein the refractive index of the organic compound is in the range of 1.4 to 1.7, preferably 1.4 to 1.6, at a wavelength of 460nm blue light.

7. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises:

A substrate layer;

a first electrode over the substrate layer;

an organic light emitting functional layer over the first electrode;

a second electrode over the organic light emitting functional layer; and

A cover layer over the second electrode;

The coating layer is characterized in that the coating layer comprises one or more of the organic compounds containing polyfluoro-substituted glutarimide or succinimide according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, wherein the cover layer comprises a first cover layer and a second cover layer,

The first cover layer is above the second electrode;

the second cover layer is over the first cover layer;

The first cover layer is characterized in that the first cover layer comprises one or more of the organic compounds containing polyfluoro-substituted glutarimide or succinimide according to any one of claims 1 to 6.

9. The organic electroluminescent device according to claim 8, wherein a refractive index of the first cover layer material is smaller than a refractive index of the second cover layer material, the refractive index of the first cover layer material at a wavelength of 460nm is 1.60 or less, the refractive index of the second cover layer material at a wavelength of 460nm is 1.85 or more, and a refractive index difference between the second cover layer material and the first cover layer material at a wavelength of 460nm is 0.3 or more.

10. An organic electroluminescent device according to any of claims 7-9, characterized in that the band gap Eg of the first cover material is larger than 3.0ev, preferably larger than 3.5ev, and the difference in refractive index of the first cover material at wavelengths of 460nm and 620nm is smaller than or equal to 0.3.