CN117229192A

CN117229192A - Diphthalimide organic compound containing trifluoromethyl or perfluoro isopropyl and organic electroluminescent device containing the same

Info

Publication number: CN117229192A
Application number: CN202211028950.6A
Authority: CN
Inventors: 蔡啸; 唐丹丹; 张兆超
Original assignee: Jiangsu Sunera Technology Co Ltd
Current assignee: Jiangsu Sunera Technology Co Ltd
Priority date: 2022-08-25
Filing date: 2022-08-25
Publication date: 2023-12-15

Abstract

The invention discloses an organic compound containing trifluoromethyl or perfluoro isopropyl diphthalimide and an organic electroluminescent device containing the same. The compound is a bisphenol phthalimide organic compound containing trifluoromethyl or perfluoro isopropyl, has lower refractive index of visible light in the visible light field, and has refractive index of less than 1.65 in the blue light field. 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

Diphthalimide organic compound containing trifluoromethyl or perfluoro isopropyl and organic electroluminescent device containing the same

Technical Field

The invention relates to the technical field of semiconductors, in particular to a diphthalimide organic compound containing trifluoromethyl or perfluoro isopropyl and application thereof as a coating layer in an organic electroluminescent device.

Background

An organic electroluminescent diode (OrganicLightEmittingDiode, OLED), also known as an organic electroluminescent device, is a technology in which an organic material emits light by carrier injection and recombination under the action of an electric field, and it is 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, it is very difficult to increase the refractive index of the organic compound used for the coating layer, and thus, in order to further increase the luminous efficiency of the organic light emitting device without increasing the excessive material, a double coating structure comprising a low refractive index coating layer and a high refractive index coating layer has been explored. Although the three-star US20210159427A1 patent also uses a low refractive index material and a high refractive index material to form a double-layer coating, 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. Although the soil conservation valley WO2022075396A1 patent also adopts a double-layer covering layer formed by matching a low refractive index material and a high refractive index material, the low refractive index material adopts 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, but 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 in the prior art, the present application provides an organic compound of bis-phthalimide containing trifluoromethyl or perfluoro isopropyl, which has a low refractive index, and the low refractive index compound of the present application can be used as a first coating layer and a second coating layer with a high refractive index to improve light extraction efficiency and angle dependence.

The technical scheme provided by the application is as follows: an organic compound of the diphthalimides type containing trifluoromethyl or perfluoroisopropyl groups, said organic compound having a structure according to the general formula (1):

in the general formula (1), L represents a single bond, and structures shown in the general formulas (2) to (7);

in the general formula (2), R ₁ And R is ₂ Each independently represents a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C20 alkyl group;

In the general formula (4), R ₃ To R ₆ Each independently represents a substituted or unsubstituted C1-C20 alkyl group;

in the general formula (7), X represents O or S;

z represents, independently of one another, identical or different, C-R or N;

r each occurrence, which are the same or different, independently represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, a difluoromethyl group, a difluoromethoxy group, a fluoromethyl group, a fluoromethoxy group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group or a tert-butoxy group;

the Ar is as follows ₁ Represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C2-C50 heteroaryl group containing one or more hetero atoms, a substituted or unsubstituted C6-C50 arylamino group, a substituted or unsubstituted C2-C50 heteroarylamino group containing one or more hetero atoms, or a structure represented by formula a;

the Ar is as follows ₂ Represented by formula a:

in formula a, L ₁ Represents a single bond, a substituted or unsubstituted C6-C50 arylene group, a substituted or unsubstituted C2-C50 heteroarylene group containing one or more heteroatoms, a substituted or unsubstituted C6-C50 heteroarylene amine group, or a substituted or unsubstituted C2-C50 heteroarylene amine group containing one or more heteroatoms;

p=0, 1, 2, 3, 4 or 5;

m=1, 2, 3, 4 or 5; n=0, 1, 2, 3, 4 or 5; and m+n is more than or equal to 2;

k=1, 2, 3, 4 or 5; j=0 or 1;

the "substituted or unsubstituted" substituent is optionally selected from one or more of 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, t-butyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, t-butoxy group, C6-C20 aryl group, C2-C20 heteroaryl group containing one or more hetero atoms;

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

Preferably, the organic compound has a structure represented by the general formula (1-1) or the general formula (1-2):

in the general formula (1-1) or the general formula (1-2), L represents a single bond, and structures shown in the general formulas (2) to (7);

in the general formula (7), X represents O or S;

in the general formula (1-1) or the general formula (1-2), L ₁ Represents a single bond, a substituted or unsubstituted C6-C50 arylene group, a substituted or unsubstituted C2-C50 heteroarylene group containing one or more heteroatoms, a substituted or unsubstituted C6-C50 heteroarylene amine group, or a substituted or unsubstituted C2-C50 heteroarylene amine group containing one or more heteroatoms;

ar in the general formula (1-1) or the general formula (1-2) ₁ Represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C2-C50 heteroaryl group containing one or more heteroatoms, a substituted or unsubstituted C6-C50 arylamino group, or a substituted or unsubstituted C2-C50 heteroarylamino group containing one or more heteroatoms;

in the general formula (1-1), p=0, 1, 2, 3, 4 or 5;

in the general formula (1-1) or the general formula (1-2), m=1, 2, 3, 4 or 5; n=0, 1, 2, 3, 4 or 5; and m+n is more than or equal to 2;

in the general formula (1-1) or the general formula (1-2), k=1, 2, 3, 4 or 5; j=0 or 1;

in the general formula (1-1) or the general formula (1-2), Z is the same or different and each independently represents C-R or N;

Preferably, the R ₁ And R is ₂ Each independently represents the following group substituted or unsubstituted with 1 or more fluorine atoms: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl;

The R is ₂ To R ₆ Each independently represents the following group substituted or unsubstituted with 1 or more fluorine atoms: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl;

the L is ₁ Represented by a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted benzophenanthrylene group, a substituted or unsubstituted picolinic groupA pyridylene group, a substituted or unsubstituted carbazolylene group, a substituted or unsubstituted furanylene group, a substituted or unsubstituted naphthylofuranopylene group, a substituted or unsubstituted thienylene group, a substituted or unsubstituted pyrimidinylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted pyridazinylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted N-phenylcarbazolyl group, a substituted or unsubstituted N-diphenylcarbazolyl group, a substituted or unsubstituted N-naphthylcarbazolyl group, a substituted or unsubstituted N-dibenzofuranylcarbazolyl group, a substituted or unsubstituted quinolinylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted quinazolinylene group, a substituted or unsubstituted quinoxalinylene group, a substituted or unsubstituted cinnolinyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted carbazolylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted benzoxazolylene group, a substituted or unsubstituted naphthyridine group; l (L) ₁ Can be represented as a single bond;

the Ar is as follows ₁ Represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, a difluoromethyl group, a difluoromethoxy group, a fluoromethyl group, a fluoromethoxy group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted naphthacene group, a substituted or unsubstituted N-phenyl carbazolyl group, a substituted or unsubstituted naphthacene groupA substituted N-diphenylcarbazolyl group, a substituted or unsubstituted N-naphthylene carbazolyl group, a substituted or unsubstituted N-dibenzofuranyl carbazolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted cinnolinyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted naphthofuranyl group, a substituted or unsubstituted naphthothienyl group;

The substituent of the "substituted or unsubstituted" is optionally selected from one or more of 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, t-butyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, t-butoxy group, phenyl group, naphthyl group, biphenyl group, pyridyl group, naphthyridinyl group.

Preferably, the formula a is represented by the following structure:

preferably, the structure of the organic compound is shown in the general formulas (3-1) to (3-3):

in the general formulae (3-2) to (3-3), Y, which are identical or different for each occurrence, each independently represents C-R or N;

z, R, L, m, n, p, k, j has the same meaning as above.

Preferably, the structure of the organic compound is shown in the general formulas (4-1) to (4-7):

in the general formula (4-3) and the general formula (4-7), Y, which are identical or different at each occurrence, each independently represents C-R or N;

z, R, L, m, n, p, k, j has the same meaning as above.

Preferably, in the general formula (1)p is independently represented by the structure:

Preferably, the specific structural formula of the organic compound is any one of the following structures:

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the present invention also provides 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 capping layer over the second electrode;

the cover layer comprises one or more of the organic compounds of the diphthalimides containing trifluoromethyl or perfluoroisopropyl groups.

Preferably, 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 above the first cover layer;

the first cover layer comprises one or more of the organic compounds of the diphthalimides containing trifluoromethyl or perfluoroisopropyl groups.

Preferably, the refractive index of the first cover layer material is smaller than that of the second cover layer material;

preferably, the refractive index of the first cover layer material at a wavelength of 460nm is 1.65 or less;

Preferably, the refractive index of the second cover layer material at a wavelength of 460nm is 1.85 or more;

preferably, the difference in refractive index between the second cover layer material and the first cover layer material at 460nm wavelength is 0.3 or more;

preferably, the first capping layer material has a bandgap Eg greater than 3.0ev, preferably greater than 3.5ev;

preferably, the refractive index difference of the first cover layer material at the wavelengths of 460nm and 620nm is less than or equal to 0.3.

Preferably, the total film thickness of the cover layer is 15-300nm, more preferably 30-200nm, more preferably 40-100 nm, and most preferably 50-80nm; 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.

Preferably, the refractive index of the bisphenol phthalimide organic compound containing trifluoromethyl or perfluoro isopropyl is in the range of 1.4-1.7, preferably 1.4-1.65 under the blue light with the wavelength of 460 nm.

The invention has the technical effects that:

the refractive index of the compound in the blue light area is lower than 1.65, the fluorine-containing compound belongs to a low refractive index organic material, the vapor deposition temperature is low, the vapor deposition process is stable, material clusters are not formed in the film making process, and therefore the method is favorable for improving the preparation yield of the display screen.

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 structure of an organic light-emitting functional layer 300 of the top-emission 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 structure of the cover layer 500 in fig. 1, wherein 510 is a low refractive index first cover layer, and 520 is a high refractive index second cover layer.

FIG. 4 is an ultraviolet-visible absorption spectrum of Compound 1 of the synthesis example, the intersection point of the tangential lines corresponds to the obtained wavelength being 321nm, eg=1240/321=3.86 eV.

FIG. 5 is an ultraviolet-visible absorption spectrum of a compound 99 of the synthesis example, the intersection point of the tangent lines corresponding to the obtained wavelength 314nm, eg=1240/314=3.95 eV.

FIG. 6 is a graph showing refractive index at different wavelengths for Compound 1 and Compound 99 of the Synthesis example.

FIG. 7 is a nuclear magnetic resonance spectrum of compound 1 of the synthesis example, using deuterated chloroform (CDCl) ₃ )。

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, triphenylyl, naphthyl, phenanthryl, benzophenanthryl, and the like. When the C6-C50 aryl group comprises two or more rings, these rings may be fused to each other.

In this context, C is used ₂ -C ₅₀ Heteroaryl is meant to include those having as ring-forming atoms at least one heteroatom selected from N, O, P and S and from 2 toMonovalent radicals of a 50 carbon carbocyclic aromatic system. C (C) ₂ -C ₅₀ Non-limiting examples of heteroaryl groups can include pyridyl, oxadiazolyl, triazinyl, pyrimidinyl, furyl, dibenzofuranyl, dibenzothienyl, benzoxazolyl, dibenzooxazolyl, carbazolyl, N-phenylcarbazolyl, quinolinyl, isoquinolinyl, naphthofuryl, phenyl-substituted naphthofuryl, and the like. When C ₂ -C ₅₀ Where the heteroaryl group includes two or more rings, the rings may be fused to each other.

Herein, C is used ₆ -C ₂₀ Aryl refers to a monovalent group comprising a carbocyclic aromatic system having from 6 to 20 carbon atoms as ring-forming atoms. C (C) ₆ -C ₃₀ Non-limiting examples of aryl groups may include phenyl, biphenyl, phenanthryl, triphenylyl, naphthyl, phenanthryl, benzophenanthryl, phenanthryl, and the like benzyl, anthryl, 9, 10-benzophenanthryl, fused tetraphenyl, pyrenyl, and a biphenyl group, a p-triphenyl group m-biphenyl triphenyl radical,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.

In this context, C is used ₂ -C ₂₀ 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. C (C) ₂ -C ₂₀ Non-limiting examples of 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, benzisothiofuranyl, benzothienyl, benzisothiophene, indolyl, isoindolyl, indazolyl Benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, 2,1, 3-benzoxadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinolyl, naphthyridinyl, benzotriazinyl, benzoxazinyl, purinyl, pteridinyl, indolizinyl, benzothiazinyl, acridinyl, oxazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, naphthofuranyl, quinolinyl, isoquinolinyl, indole [1,2-f]Phenanthridinyl, imidazo [2,1-a]Isoquinolinyl, imidazo [1,2-a ]]Quinolinyl, benzo [4,5 ]]Imidazo [1,2-a]Pyridinyl, imidazo [1,2-a]Pyridyl, benzofurane [3,2-c ]]Quinolinyl, naphtho [1,2-b]Benzofuranyl, naphtho [2,3-b ]]Benzofuranyl, and the like, also include aromatic combination groups bearing heteroatoms.

Herein, C ₆ -C ₅₀ Arylene means phenylene, naphthylene, anthracenylene, fluorenylene, dimethylfluorenylene, diphenylfluorenylene, spirofluorenylene, phenanthrylene, fused tetraphenylene, pyrenylene, biphenylene, p-biphenylene, m-biphenylene, and m-biphenyleneA group, a biphenylene, a perylene group, an indenylene group, but is not limited thereto.

Herein, C ₂ -C ₅₀ Heteroarylene refers to a furanylene, a thienyl, a pyrrolylene, a pyrazolylene, an imidazolylene, a triazolylene, an oxazolylene, a thiazolylene, an oxadiazolylene, a thiadiazolylene, a pyridyl, a pyrimidylene, a pyrazinylene, a triazinylene, a benzofuranylene, a benzothienyl, a benzimidazolylene, an indolylene, a quinolinylene, an isoquinolylene, a quinazolinylene, a quinolizinylene, a naphthyridinyl, a benzoxazinylene, a benzothiazinylene, an acridinylene, a oxazinylene, a fluorenylene, a dibenzofuranylene, a dibenzothiophenylene, a carbazolylene, a combination thereof, or a fused ring of a combination of the foregoing, but is not limited thereto.

C of the invention ₁ -C ₂₀ Alkyl (containing straightChain alkyl and branched alkyl) means methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, hexyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl and the like, but is not limited thereto.

The halogen atom in the present invention means fluorine atom, chlorine atom, bromine atom and iodine atom.

Herein, the term "amine group" refers to a primary, secondary or tertiary amine group having the indicated number of carbon atoms (e.g., 1 to 100, preferably 1 to 50, preferably 1 to 30, preferably 1 to 20, still preferably 1 to 12, more preferably 1 to 6) in each case.

Herein, the term "arylamino" refers to a primary, secondary, or tertiary amino group substituted with an aryl group. The term "heteroarylamino" refers to a primary, secondary, or tertiary amino group substituted with a heteroaryl group.

"Arylamino" refers to a divalent group of an arylamino system and "heteroaryleneamino" refers to a divalent group of a heteroarylamino system.

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, and the obtained device or element has high yield and high visible light extraction efficiency.

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 capping layer over the second electrode;

the first cover layer is above the second electrode;

the second cover layer is above the first cover layer;

Preferably, the refractive index of the first cover layer material is smaller than that of the second cover layer material, the refractive index of the first cover layer material at the wavelength of 460nm is smaller than or equal to 1.65, the refractive index of the second cover layer material at the wavelength of 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 the wavelength of 460nm is larger than or equal to 0.3.

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 organic electroluminescent device 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 include 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 include only the light emitting layer and one or more other layers, wherein the capping layer is composed of one or more of organic compounds containing trifluoromethyl or perfluoroisopropyl diphthalimides represented by the above general formula (1) or general formula (1-2) or general formula (3-1) to general formula (3-3) or general formula (4-1) to general formula (4-7). 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 a reflective film and a transparent filmOr a semitransparent electrode, such as a transparent or semitransparent electrode layer having a high work function and formed on the reflective film. The transparent or semitransparent electrode layer can be made of Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), zinc oxide (ZnO), aluminum Zinc Oxide (AZO), indium Gallium Oxide (IGO), indium oxide (In) ₂ O ₃ ) Or tin oxide (SnO) ₂ ) Forming; 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"- ((1 e,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, diphenoquinone derivatives, nitro substituted-pyridone derivatives, thiopyran dioxide derivatives, anthraquinone dimethane derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydride such as naphthalene groups, carbodiimide, fluorene derivatives, anthraquinone dimethane derivatives, anthranone derivatives, diphenylvinylpyrzine 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. Alternatively, 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 an organic compound of diphthalimides containing trifluoromethyl or perfluoroisopropyl groups represented by the above general formula (1) or general formula (1-2) or general formula (3-1) to general formula (3-3) or general formula (4-1) to general formula (4-7).

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 a metal selected from Al ₂ O ₃ 、SiO _x N _y 、TiO ₂ 、SiO _x And SiN _x At least one of the group consisting of x and y, which are the same or different, are independently greater than 0 and less than 10, preferably greater than 0 and less than 5, and 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 (phenyl group), an acrylic polymer (acryl-based DPOLymer), an imide-based polymer (imide-based DPOLymer), an aryl ether polymer (acryl-based DPOLymer), an amide-based polymer (amide-based DPOLymer), a fluorine-based polymer (fluoro-based DPOLymer), a p-xylene-based polymer (p-xylene-based DPOLymer), a vinyl alcohol polymer (vinyl alcohol-based DPOLymer) 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, after preparing an anode, a cathode and an organic light-emitting functional layer, evaporating a material comprising the organic compound containing a trifluoromethyl-or perfluoroisopropyl-containing diphthalimide type represented by the general formula (1-1) or the general formula (1-2) of the present invention as a cap layer on the light-emitting side 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 JNCD is an obvious color difference which can be perceived by human eyes and can be measured by a parameter JNCD (JUSTNOTICEABLECOLORDIFFERENCE), and the smaller the JNCD value 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

Preparation example 1, synthesis of compound 1:

0.01mol of raw material A1, 0.024mol of raw material B1,0.024mol of isoquinoline and 2X 10 ^-5 mol of 4- (dimethylamino) pyridine is added into 150mL of N-methyl-2-pyrrolidone solvent, and the mixture is heated to 70 ℃ to react for 2 hours under the protection of nitrogen, and then heated to 205 ℃ to reflux and react for 12 hours. Sampling point plate, after the reaction of raw material A1 is completed, naturally cooling to room temperature, adding 200mL of pure water into the mixed solution, precipitating solids, filtering the mixed solution, taking filter cake, placing the filter cake into a vacuum drying oven, drying to obtain crude product, and passing through a silica gel column to obtain compound 1; elemental analysis formula (C) ₃₅ H ₁₂ F ₁₈ N ₂ O ₄ ) Theoretical value: c,48.52; h,1.40; n,3.23; test value: c,48.48; h,1.44, N,3.21.LC-MS: theoretical value: 866.05; measurement value ([ M+H)] ⁺ )：867.27。

Reference is made to: boknam Chae, sang Hyun Lee, seung Bin Kim, et al, two-dimensional correlation analysis study of the curing process of phenylethynyl end-capped imide model compounds, vibrational Spectroscopy,2012,60,137-141.

Preparation example 2, synthesis of compound 34:

1) Adding 0.01mol of C3 and 0.012mol of D3 into 150mL of DMF (N, N-dimethylformamide), adding 0.02mol of potassium carbonate under nitrogen protection, and adding 5×10 ^-5 mol Pd(PPh ₃ ) ₄ Stirring and mixing, heating to 90 ℃ for reaction for 16 hours, sampling a point plate, naturally cooling and filtering after the raw material C3 is completely reacted, carrying out reduced pressure distillation on filtrate to remove solvent, and passing the crude product through a silica gel column to obtain an intermediate B3; LC-MS: theoretical value: 373.05; measurement value: 374.18 ([ M+H)] ⁺ )。

2) 0.01mol of raw material A1, 0.024mol of intermediate B3, 0.024mol of isoquinoline and 2X 10 ^-5 mol of 4- (dimethylamino) pyridine is added into 150mL of N-methyl-2-pyrrolidone solvent, and the mixture is heated to 70 ℃ to react for 2 hours under the protection of nitrogen, and then heated to 205 ℃ to reflux and react for 15 hours. Sampling The method comprises the steps of (1) spotting a plate, naturally cooling to room temperature after the raw material A1 is completely reacted, adding 200mL of pure water into the mixed solution, precipitating solids, filtering the mixed solution, taking a filter cake, putting the filter cake into a vacuum drying oven, and drying to obtain a crude product, and passing through a silica gel column to obtain a compound 34; elemental analysis formula (C) ₄₉ H ₁₈ F ₂₄ N ₂ O ₄ ) Theoretical value: c,50.97; h,1.57; n,2.43; test value: c,50.93; h,1.61; n,2.40.LC-MS: theoretical value: 1154.09; measurement value ([ M+H)] ⁺ )：1155.21。

Reference is made to: mohamed M.Farah, philip C.Bulman Page, benjamin R.Buckey, et al, novel biphenyl organocatalysts for iminium ion-catalyzed asymmetric epoxidation, tetrahedron,2013,69 758-769.

https://doi.org/10.1016/j.tet.2012.10.076.

Preparation example 3 synthesis of compound 150:

1) Adding 0.01mol of C15, 0.012mol of D15 and 100mL of o-xylene, stirring and mixing, adding 0.02mol of sodium tert-butoxide and 1X 10 ^-5 mol PdCl ₂ (Ph ₃ P) ₂ ，1×10 ^-5 mol Ph ₃ P, stirring and heating to 145 ℃, carrying out reflux reaction for 10 hours, sampling a spot plate, and displaying that no raw material C15 remains and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate until no fraction exists, and passing through a neutral silica gel column to obtain a target intermediate S15; LC-MS: theoretical value: 630.04; measurement value: 631.13 ([ M+H) ] ⁺ )。

2) 0.01mol of intermediate S15, 0.015mol of hydrazine hydrate (0.73 mL), 30mL of Tetrahydrofuran (THF) and 30mL of ethanol are added and mixed with stirring, and the Raney nickel catalyst 1X 10 is prepared ^-5 mol is added into the mixture, the temperature is raised to 80 ℃ by stirring, the reflux reaction is carried out for 12 hours, a spot plate is sampled, no intermediate S15 remains, and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate until no fraction exists, and passing through a neutral silica gel column to obtain a target intermediate B15; LC-MS: theoretical value: 600.07; measurement value: 601.27 ([ M+H)] ⁺ )。

3) 0.01mol of raw material A1, 0.024mol of intermediate B15, 0.024mol of isoquinoline and 2X 10 ^-5 mol of 4- (dimethylamino) pyridine is added into 150mL of N-methyl-2-pyrrolidone solvent, and the mixture is heated to 70 ℃ to react for 2 hours under the protection of nitrogen, and then heated to 205 ℃ to reflux and react for 15 hours. Sampling point plate, after the reaction of raw material A1 is completed, naturally cooling to room temperature, adding 200mL of pure water into the mixed solution, precipitating solids, filtering the mixed solution, taking filter cake, placing the filter cake into a vacuum drying oven, drying to obtain crude product, and passing through a silica gel column to obtain compound 150; elemental analysis formula (C) ₆₅ H ₂₄ F ₃₆ N ₄ O ₄ ) Theoretical value: c,48.53; h,1.50; n,3.48; test value: c,48.58; h,1.53; n,3.44.LC-MS: theoretical value: 1608.12; measurement value ([ M+H) ] ⁺ )：1609.25。

Reference is made to: 1) Liangzhen Cai, xuanying Qian, wenjing Song, et al effects of solvent and base on the palladium-catalyzed amination:PdCl ₂ (Ph ₃ P) ₂ /Ph ₃ P-catalyzed selective arylation of primary anilines with aryl bromides.Tetrahedron,2014,70(32),4754–4759.doi:10.1016/j.tet.2014.05.048

2)Shunqi Yan,Todd Appleby,Esmir Gunic,et al.Isothiazoles as active-site inhibitors of HCV NS5B polymerase,Bioorganic&Medicinal Chemistry Letters,2007,17,28–33.https://doi.org/10.1016/j.bmcl.2006.10.002

The following objective compounds were synthesized by repeating the preparation procedures in preparation examples 1 to 3; the reaction conditions were the same except that raw material a and intermediate B listed in table 1 below were used; the detailed characterization data are shown in table 1.

TABLE 1

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Repeating the synthesis method of the intermediate B3 to synthesize the following intermediate target compound; the reaction conditions were the same except that raw material C and raw material D listed in table 2 below were used; the detailed characterization data are shown in table 2.

TABLE 2

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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 3 below.

TABLE 3 Table 3

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As can be seen from the data in table 3 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:

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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. At @10mA/cm ² The data under the conditions are based (i.e. the test current density reaches 10mA/cm ² Corresponding performance values).

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 1, 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 to 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 (2) 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: an Ag electrode layer, mg and Ag in a mass ratio of 1:9, is a second electrode (cathode) layer 400. Vacuum evaporating the compound 1 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 22

The device structure and fabrication method are similar to device embodiment 1, except that the first and second cap layer material types are changed; the specific coating materials and film thicknesses are described in Table 4 below.

Blue light device comparative example 1

The blue device comparative example 1 device structure and fabrication method is similar to device example 1 except that a double layer cap layer is not used and only a single layer cap layer is used; using a comparative compound CP-H1 as a second capping layer material without evaporating the first capping layer; the specific coating materials and film thicknesses are described in Table 4 below.

Blue light device comparative examples 2, 3, 5, 7

The blue device comparative examples 2, 3, 5 and 7 were similar in structure and fabrication to device example 1 except that no dual layer cap layer was used and only a single layer cap layer was used; using the inventive compound 1, the comparative compounds CP-R1, CP-R2 and CP-R3 as the first capping layer material, the second capping layer was not evaporated; the specific coating materials and film thicknesses are described in Table 4 below.

Blue device comparative examples 4, 6 and 8

The blue device comparative examples 4, 6 and 8 were similar in structure and fabrication to device example 1 except that the comparative compounds were used as the first capping layer material, respectively, and then vacuum evaporation of CP-H1 or CP-H12 was continued on the first capping layer as the second capping layer; the specific coating materials and film thicknesses are described in Table 4 below.

Blue light device comparative example 9

The blue device comparative example 9 device structure and fabrication method is similar to device example 1, except that no bilayer cap layer is used, but only a single layer cap layer is used; using a comparative compound CP-H12 as a second capping layer material without evaporating the first capping layer; the specific coating materials and film thicknesses are described in Table 4 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 4.

TABLE 4 Table 4

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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;1 jncd=0.004.

From the data in table 4, 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 13% 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 48 percent@30 degrees (device example 17) are reduced, 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 using the compound of the present invention as the double-layer coating of the low refractive Index first coating and the high refractive Index second coating is improved by 47% to 55%; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 34 percent@30 degrees are reduced (device example 17), so that the angle variation is smaller, and the color cast effect is obviously improved.

Blue OLED device Index using the inventive compounds as a bilayer cap for a low Index first cap in combination with a high Index second cap increased by 70% to 79% compared to comparative example 3 for a blue device having only a comparative compound CP-R1 cap; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 30 percent@30 degrees are reduced (device example 17), 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 6 to 11 percent; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 22.8 percent is reduced at 30 degrees (device example 17), so that the angle change amount is smaller, and the color cast effect is obviously improved.

Compared with the blue light device comparative example 5 with the comparative compound CP-R2 coating only, the blue light OLED device Index applied with the dual-layer coating of the present invention as the low refractive Index first coating and the high refractive Index second coating, respectively, was increased by 74% to 83%; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 28 percent@30 degrees are reduced (device example 17), 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-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 23 percent@30 degrees (device example 17) are reduced, so that the angle variation is smaller, and the color cast effect is obviously improved.

Blue OLED device Index using the inventive compounds as a bilayer cap for a low Index first cap in combination with a high Index second cap increased by 79% to 89% compared to device comparative example 7 which only has a comparative compound CP-R3 cap; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 34 percent@30 degrees are reduced (device example 17), so that the angle variation is smaller, and the color cast effect is obviously improved.

Compared with comparative example 8 of a blue light device with a double-layer coating matched with a comparative compound CP-R3, 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 11 percent; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even about 28 percent is reduced at 30 degrees (the second covering layer is CP-H12 in the device embodiment 12), so that the angle change is smaller, and the color cast effect is obviously improved.

Compared with the blue light device comparative example 9 with only the high refractive Index coating, the blue light OLED device Index using the compound of the present invention as the double-layer coating of the low refractive Index first coating and the high refractive Index second coating is improved by 6% to 12%; and the perceived color difference is obviously reduced at angles of 30 degrees, 45 degrees and 60 degrees, and even 49 percent@30 degrees are reduced (the second cover layer is CP-H12 in device example 12), 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 summary, the compound of the present invention is applied to an OLED device as a double-layered cap layer prepared by a first cap layer material in combination with a high refractive index second cap layer, so that the light extraction efficiency is greatly improved, the current efficiency is remarkably improved, and the angle dependence is improved.

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 of the diphthalimide type containing trifluoromethyl or perfluoroisopropyl, characterized in that the organic compound has a structure represented by the general formula (1):

in the general formula (7), X represents O or S;

z represents, independently of one another, identical or different, C-R or N;

the Ar is as follows ₂ Represented by formula a:

p=0, 1, 2, 3, 4 or 5;

m=1, 2, 3, 4 or 5; n=0, 1, 2, 3, 4 or 5; and m+n is more than or equal to 2;

k=1, 2, 3, 4 or 5; j=0 or 1;

2. The organic compound according to claim 1, wherein the organic compound has a structure represented by general formula (1-1) or general formula (1-2):

in the general formula (7), X represents O or S;

In the general formula (1-1), p=0, 1, 2, 3, 4 or 5;

3. The organic compound according to claim 1 or 2, wherein R ₁ And R is ₂ Each independently represents the following group substituted or unsubstituted with 1 or more fluorine atoms: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl;

the L is ₁ Represented by a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted benzophenanthrylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolylene group, a substituted or unsubstituted furanylene group, a substituted or unsubstituted naphthylene benzofuranyl group, a substituted or unsubstituted thienylene group, a substituted or unsubstituted pyrimidinylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted pyridazinylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted N-phenylcarbazolyl group, a substituted or unsubstituted N-bisbenzofuranyl carbazolyl group, a substituted or unsubstituted quinolinylene group, a substituted or unsubstituted isoquinolene group, a substituted or unsubstituted benzofuranyl group; l (L) ₁ Can be represented as a single bond;

the Ar is as follows ₁ Represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, a difluoromethyl group, a difluoromethoxy group, a fluoromethyl group, a fluoromethoxy group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl groupA group, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted pyridylene, substituted or unsubstituted carbazolyl, substituted or unsubstituted furyl, substituted or unsubstituted naphthofuranphenyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted N-diphenylcarbazolyl, substituted or unsubstituted N-naphthyridocarbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted naphthyridine;

The substituent of the "substituted or unsubstituted" is optionally selected from one or more of 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, naphthyl group, biphenyl group, pyridyl group, naphthyridinyl group;

the formula a is represented by the following structure:

4. the organic compound according to claim 2, wherein the structure of the organic compound is represented by the general formulae (3-1) to (3-3):

z, R, L, m, n, p, k, j has the same meaning as in claim 2.

5. The organic compound according to claim 2, wherein the structure of the organic compound is represented by the general formulae (4-1) to (4-7):

z, R, L, m, n, p, k, j has the same meaning as in claim 2.

6. The organic compound according to claim 1, wherein the specific structural formula of the organic compound is any one of the following structures:

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7. an organic electroluminescent device, the 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 capping layer over the second electrode;

the cover layer is characterized in that the cover layer comprises one or more of the organic compounds of the diphthalimides containing trifluoromethyl or perfluoroisopropyl groups 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 above the first cover layer;

the first cover layer is characterized in that the first cover layer contains one or more of the organic compounds of the diphthalimides containing trifluoromethyl or perfluoroisopropyl groups as defined in any one of claims 1 to 6.

9. The organic electroluminescent device of claim 8, wherein the refractive index of the first cover layer material is less than the refractive index of the second cover layer material;

10. The organic electroluminescent device according to any of claims 7-9, wherein the total film thickness of the cover layer is 15-300nm, more preferably 30-200nm, more preferably 40-100 nm, most preferably 50-80nm; 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.