CN114835695A - Capping layer material, application thereof, light-emitting device and light-emitting device - Google Patents

Capping layer material, application thereof, light-emitting device and light-emitting device Download PDF

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CN114835695A
CN114835695A CN202210612128.8A CN202210612128A CN114835695A CN 114835695 A CN114835695 A CN 114835695A CN 202210612128 A CN202210612128 A CN 202210612128A CN 114835695 A CN114835695 A CN 114835695A
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capping layer
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金成寿
汪康
马晓宇
徐佳楠
韩瑞峰
张鹤
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Jilin Optical and Electronic Materials Co Ltd
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    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
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    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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Abstract

The invention is suitable for the technical field of materials, and provides a capping layer material and application thereof, a light-emitting device and a light-emitting device, wherein when the capping layer material is applied to a CPL layer in an OLED device, the electronic cloud height overlapping of HOMO (high energy density) orbitals and LUMO (low energy density) orbitals is ensured due to strong electron-withdrawing capability and more regular symmetry, so that the polarizability and the refractive index are very high, and the difference of the refractive indexes is small and about 0.1 in three wavelength ranges of red, green and blue; and the efficiency of the red, green and blue light device is uniformly improved, and the service life of the device is greatly prolonged.

Description

Capping layer material, application thereof, light-emitting device and light-emitting device
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a capping layer material, application thereof, a light-emitting device and a light-emitting device.
Background
Organic Light Emission Diodes (OLED) devices may be used in place of liquid crystal displays and fluorescent lighting to manufacture display devices and lighting products. Specifically, the OLED device can be widely applied to the fields of smart phones, tablet computers, televisions and the like.
Although the internal quantum efficiency is close to 100%, the external quantum efficiency is only about 20%. Most of the light is confined inside the light emitting device due to factors such as substrate mode loss, surface plasmon loss, and waveguide effect, resulting in a large amount of energy loss.
Until now, many improvements have been made for practical use of organic EL (electroluminescence) elements, and various functions have been subdivided, and an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided in this order according to their functions on a substrate. In organic electroluminescent devices, high efficiency and durability have been achieved by a light emitting element of a bottom emission structure that emits light from the bottom.
In recent years, a light emitting element of a top emission structure which emits light from above using a metal having a high work function as an anode has been started. In the light emitting element having the top emission structure, a translucent electrode such as LiF/Al/Ag, Ca/Mg, LiF/MgAg, or the like is used as a cathode.
In such a light-emitting element, when light emitted from the light-emitting layer enters another film, the light is totally reflected at the interface between the light-emitting layer and the other film when the light enters at a certain angle or more. Therefore, only a part of the emitted light can be utilized. In recent years, in order to improve light extraction efficiency, it has been proposed to provide a cap layer (CPL, also referred to as a cathode coating layer, a capping layer, or a light extraction layer) having a high refractive index outside a translucent electrode having a low refractive index, to adjust an optical interference distance, suppress external light reflection, and suppress extinction due to movement of surface plasmon energy, thereby improving light extraction efficiency and light emission efficiency.
As a coating layer for adjusting the refractive index, it is known to use aluminum tris (8-hydroxyquinoline) (hereinafter abbreviated as Alq 3). Alq3 is often used as a green light-emitting material or an electron-transporting material, but has weak absorption near 450nm used for a blue light-emitting element. Therefore, in the case of the blue light emitting element, there is a problem that the color purity is lowered and the light extraction efficiency is lowered together.
The existing CPL material improves the light extraction efficiency to a certain extent. However, the refractive index of the conventional CPL material is generally below 1.9, which cannot meet the requirement of high refractive index, and the light-emitting efficiency is low. In order to improve the characteristics of organic EL elements, particularly to greatly improve the light extraction efficiency, it is necessary to develop a material having a high refractive index to improve the light extraction efficiency and solve the problem of light emission efficiency. As a material for the cap layer, a material having a high refractive index and excellent thin film stability and durability is required.
Disclosure of Invention
The invention provides a capping layer material, aiming at solving the problems that the prior CPL material can not meet the requirement of high refractive index and has lower luminous efficiency.
The invention is realized by the following steps that a capping layer material is shown in a general formula 1:
Figure BDA0003670834440000031
wherein X represents an oxygen or sulfur atom;
L 1 、L 2 、L 3 are the same or different from each other and independently represent a bond, substituted or unsubstituted C 3 ～C 60 Cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C 6 ～C 60 Any one of an aryl group, a substituted or unsubstituted 3-to 30-membered heteroaryl group;
r independently represents hydrogen, hydrogen isotope, cyano, substituted or unsubstituted C1-C60 alkyl, C3-C60 cycloalkyl, substituted or unsubstituted C2-C60 alkenyl, C3-C60 cycloalkenyl, substituted or unsubstituted C3-C60 alkynyl, C3-C60 cycloalkynyl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C1878-C20 alkoxy, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted 3-10-membered heterocyclic group.
The invention also provides application of the capping layer material in the photoelectric field.
The invention also provides a light-emitting device which comprises the capping layer material.
The invention also provides a light-emitting device which comprises the capping layer material or the light-emitting device.
When the capping layer material provided by the invention is applied to a CPL layer in an OLED device, due to strong electron-withdrawing capability and regular symmetry, the electron cloud height overlapping of HOMO (highest energy occupied molecular orbital) and LUMO (Low energy occupied molecular orbital) is ensured, so that the polarizability and the refractive index are very high, and the difference of the refractive indexes is small and about 0.1 in three wavelength ranges of red, green and blue; and the efficiency of the red, green and blue light device is uniformly improved, and the service life of the device is greatly prolonged.
Drawings
FIG. 1 is a graph comparing the refractive index n of capping layer materials provided in examples of the present invention and comparative examples;
FIG. 2 is a graph comparing the extinction coefficient k values of capping layer materials provided in examples of the present invention and comparative examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a capping layer material, which has a structural general formula of formula 1:
Figure BDA0003670834440000041
wherein X represents an oxygen or sulfur atom;
in the formula L 1 、L 2 、L 3 Are the same or different from each other and independently represent a bond, substituted or unsubstituted C 3 ～C 60 Cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C 6 ～C 60 Any one of an aryl group, a substituted or unsubstituted 3-to 30-membered heteroaryl group;
further preferably, L 1 、L 2 、L 3 Identical to or different from each other and independently represent a connecting bond, a substituted or unsubstituted C 6 ～C 30 Any one of an aryl group, a substituted or unsubstituted 3-to 15-membered heteroaryl group;
r independently represents: hydrogen, isotopes of hydrogen, cyano, substituted or unsubstituted C1-C60 alkyl, C3-C60 cycloalkyl, substituted or unsubstituted C2-C60 alkenyl, C3-C60 cycloalkenyl, substituted or unsubstituted C3-C60 alkynyl, C3-C60 cycloalkynyl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C1878-C20 alkoxy, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted 3-10 membered heterocyclic group.
Or, each is linked to an adjacent substituent to form a substituted or unsubstituted monocyclic or polycyclic ring.
Preferably, the chemical structural formula of the material of the cover sealing layer is any one of the following:
Figure BDA0003670834440000051
Figure BDA0003670834440000061
Figure BDA0003670834440000071
the capping layer materials of the present invention can be prepared by synthetic methods known to those skilled in the art. Alternatively, the following reaction scheme is preferred.
The synthetic route is as follows:
Figure BDA0003670834440000081
step 1, preparation of intermediate 1
Under the protection of nitrogen, dissolving the raw material A (1eq) and the raw material B (1eq) in 280.00ml of a mixed solution of toluene, ethanol and water, adding potassium carbonate (2eq) and tetratriphenylphosphine palladium (0.01eq), uniformly stirring, heating and carrying out reflux reaction to prepare an intermediate 1.
Step 2, preparation of intermediate 2
Stirring the intermediate 1(2eq) and the raw material C (1eq) to DMF (3eq) for 5 minutes under the protection of nitrogen, adding Cs2CO3 to the reaction system, cooling to room temperature after the reaction is finished, slowly adding the reaction liquid to an ice water mixture, performing suction filtration after the product is separated out, washing a filter cake by using EtOH/PE in sequence, and performing vacuum drying to obtain an intermediate 2.
Step 3, preparation of formula 1
Under the protection of nitrogen, dissolving the intermediate 2(1eq) and the raw material D in 280.00ml of mixed solution of toluene, ethanol and water, adding cesium carbonate (4eq), a palladium catalyst (0.1eq) and a phosphine ligand (0.1eq), uniformly stirring, heating and carrying out reflux reaction to prepare the compound shown in the general formula 1.
The invention also provides an application of the capping layer material in the photoelectric field.
The invention also provides a light-emitting device which comprises the capping layer material.
Specifically optionally, the light-emitting device comprises a light-emitting layer and a cathode covering layer; the light-emitting layer and/or the cathode cover layer comprise the capping layer material. That is, the light emitting layer and/or the cathode covering layer may be formed of one single compound or a mixture of two or more compounds represented by the above formula 1.
The present invention is not limited to the method for manufacturing the light emitting device, and any conventional method in the art may be used, and the present invention preferably forms an anode by depositing metal, conductive oxide, or an alloy thereof on a substrate by using a method such as thin film evaporation, electron beam evaporation, or physical vapor deposition, and then forms an organic layer and a cathode thereon to obtain the light emitting device.
The invention also provides a light-emitting device which comprises the capping layer material or the light-emitting device.
Specifically, the above light emitting device may be applied to an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), an electronic paper (e-paper), an Organic Photoreceptor (OPC), an Organic Thin Film Transistor (OTFT), or the like.
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, it should be noted that the numerical values given in the following examples are as precise as possible, but those skilled in the art will understand that each numerical value should be understood as a divisor rather than an absolutely exact numerical value due to measurement errors and experimental operational problems that cannot be avoided.
Example 1:
Figure BDA0003670834440000101
under the protection of nitrogen, dissolving a raw material A (40mmol) and a raw material B (40mmol) in a mixed solution of 300mL of toluene, ethanol and water (V: V: V ═ 4:1:1), adding potassium carbonate (80mmol) and palladium tetratriphenylphosphine (4mmol), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 6 h; after the reaction is finished, slightly cooling to separate liquid, filtering an organic phase by using diatomite to remove salt and a catalyst, cooling a filtrate to room temperature, washing the filtrate for three times by using water to retain the organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching with 300.00mL of absolute ethyl alcohol and 200.00mL of petroleum ether, and drying to obtain an intermediate 1(7.3g, yield: 86%, MW: 212.22);
under the protection of nitrogen, dissolving the intermediate 1(30mmol) and the raw material C (30mmol) in a mixed solution of 300.00mL of toluene, ethanol and water (V: V: V ═ 4:1:1), adding potassium carbonate (60mmol) and tetratriphenylphosphine palladium (0.6mmol), uniformly stirring, heating to 80 ℃, and carrying out reflux reaction for 6 h; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 2(10.5g, yield: 82%, MW: 428.35);
under the protection of nitrogen, dissolving the intermediate 2(18mmol) and the raw material D (36mmol) in a mixed solution of 300.00mL of toluene, ethanol and water (V: V: V ═ 4:1:1), adding cesium carbonate (72mmol), palladium acetate 1.8mmol) and X-Phos (1.8mmol), uniformly stirring, heating to 100 ℃, and carrying out reflux reaction for 10 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: V ═ 1:12) to obtain compound C01(7.69g, yield: 69%, MW: 611.71).
HPLC purity: is greater than 99.51%.
Elemental analysis:
the calculated values are: c, 90.32; h, 4.78; n, 2.29; o, 2.62.
The test values are: c, 90.18; h, 4.82; n, 2.33; o, 2.51.
Example 2:
Figure BDA0003670834440000121
under the protection of nitrogen, dissolving a raw material A (40mmol) and a raw material B (40mmol) in a mixed solution of 300.00mL of toluene, ethanol and water (V: V: V ═ 4:1:1), adding potassium carbonate (80mmol) and tetratriphenylphosphine palladium (4mmol), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 6 h; after the reaction is finished, slightly cooling to separate liquid, filtering an organic phase by using diatomite to remove salt and a catalyst, cooling a filtrate to room temperature, washing the filtrate for three times by using water to retain the organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching with 300.00mL of absolute ethyl alcohol and 200.00mL of petroleum ether, and drying to obtain an intermediate 1(9.4g, yield: 84%, MW: 278.31);
under the protection of nitrogen, dissolving the intermediate 1(30mmol) and the raw material C (30mmol) in a mixed solution of 300.00mL of toluene, ethanol and water (V: V: V ═ 4:1:1), adding potassium carbonate (60mmol) and tetratriphenylphosphine palladium (0.6mmol), uniformly stirring, heating to 80 ℃, and carrying out reflux reaction for 6 h; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 2(11.9g, yield: 80%, MW: 494.33);
under the protection of nitrogen, dissolving the intermediate 2(18mmol) and the raw material D (36mmol) in a mixed solution of 300.00mL of toluene, ethanol and water (V: V: V ═ 4:1:1), adding cesium carbonate (72mmol), palladium acetate 1.8mmol) and X-Phos (1.8mmol), uniformly stirring, heating to 100 ℃, and carrying out reflux reaction for 10 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: V ═ 1:12) to obtain compound C23(8.1g, yield: 66%, MW: 677.80).
HPLC purity: is more than 99.52 percent.
Elemental analysis:
the calculated values are: c, 88.59; h, 4.61; n, 2.07; s, 4.73.
The test values are: c, 88.47; h, 4.81; n, 2.30; and S, 4.66.
Example 3:
Figure BDA0003670834440000141
under the protection of nitrogen, dissolving a raw material A (40mmol) and a raw material B (40mmol) in a mixed solution of 300.00mL of toluene, ethanol and water (V: V: V ═ 4:1:1), adding potassium carbonate (80mmol) and tetratriphenylphosphine palladium (4mmol), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 6 h; after the reaction is finished, slightly cooling to separate liquid, filtering an organic phase by using diatomite to remove salt and a catalyst, cooling a filtrate to room temperature, washing the filtrate for three times by using water to retain the organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching with 300.00mL of absolute ethyl alcohol and 200.00mL of petroleum ether, and drying to obtain an intermediate 1(7.4g, yield: 81%, MW: 229.20);
under the protection of nitrogen, dissolving the intermediate 1(30mmol) and the raw material C (30mmol) in a mixed solution of 300.00mL of toluene, ethanol and water (V: V: V ═ 4:1:1), adding potassium carbonate (60mmol) and tetratriphenylphosphine palladium (0.6mmol), uniformly stirring, heating to 80 ℃, and carrying out reflux reaction for 6 h; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salts and a catalyst, cooling the filtrate to room temperature, washing for three times by using water, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 2(10.5g, yield: 78%, MW: 445.21);
under the protection of nitrogen, dissolving the intermediate 2(18mmol) and the raw material D (36mmol) in a mixed solution of 300.00mL of toluene, ethanol and water (V: V: V ═ 4:1:1), adding cesium carbonate (72mmol), palladium acetate 1.8mmol) and X-Phos (1.8mmol), uniformly stirring, heating to 100 ℃, and carrying out reflux reaction for 10 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: V ═ 1:12) to obtain compound C40(9.2g, yield: 66%, MW: 780.88);
HPLC purity: is more than 99.53 percent.
Elemental analysis:
the calculated values are: c, 88.66; h, 4.65; n, 3.59; and S, 4.11.
The test values are: c, 88.55; h, 4.72; n, 3.63; and S, 4.22.
The synthesis of the other compounds is the same as the above-listed examples, and therefore, they are not illustrated here, and some of the mass spectra and molecular formulae are shown in table 1 below:
TABLE 1
Figure BDA0003670834440000151
Figure BDA0003670834440000161
Figure BDA0003670834440000171
Further, a deposited film having a thickness of 50nm was formed on a substrate using the compound provided in the example of the present invention, and refractive indices n and extinction coefficients k were measured at 460nm, 530nm and 620nm using a spectrometer, and for comparison, comparative compound 1 and comparative compound 2 in the following formula were also measured, and the test results are shown in table 2 and fig. 1-2.
Figure BDA0003670834440000172
Table 2: results of thermal Property and refractive index measurements
Figure BDA0003670834440000173
As can be seen from Table 2 and FIGS. 1 and 2, the refractive indexes of the compounds provided by the embodiment of the present invention are greater than 2.0 and higher than those of the comparative compounds 1 and 2 for the visible light with the wavelength of 460-620 nm. The requirement of the light-emitting device on the refractive index of the cap layer is met, the extinction coefficient k value is almost 0 after the blue light wavelength is 430nm, and the light-emitting of the light-emitting layer material in a blue light region cannot be influenced. Therefore, the compound provided by the embodiment of the invention can bring higher luminous efficiency. In addition, it can be found in Table 2 that the glass transition temperatures of the compounds are all higher than 130 ℃, which indicates that the thin film state is stable in the compound of the present invention.
Red light device example 1
The following examples provide applications of the compounds of the present invention in organic light emitting devices, and illustrate the technical effects achieved by the compounds of the present invention in practical applications.
The structure of the prepared OLED device is as follows: ITO anode/HIL/HTL/EML/ETL/EIL/cathode/light extraction layer.
a. An ITO anode: cleaning an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, ultrasonically cleaning for 30min, repeatedly cleaning for 2 times by using distilled water, ultrasonically cleaning for 10min, transferring to a spin dryer for spin-drying after the cleaning is finished, finally baking for 2 hours at 220 ℃ by using a vacuum oven, and cooling after the baking is finished. And (3) taking the substrate as an anode, performing a device evaporation process by using an evaporation machine, and sequentially evaporating other functional layers on the substrate.
b. HIL (hole injection layer): to be provided with
Figure BDA0003670834440000181
The hole injection layer materials HT-1 and P-dopant were vacuum evaporated, and the chemical formulas are shown below. The evaporation rate ratio of HT-1 to P-dock is 97: 3, the thickness is 10 nm;
c. HTL (hole transport layer): to be provided with
Figure BDA0003670834440000182
The evaporation rate of (2), and evaporating 130nm HT-1 on the hole injection layer in vacuum to form a hole transport layer;
d. a light-emitting auxiliary layer: to be provided with
Figure BDA0003670834440000183
The evaporation rate of (2), and evaporating EB-1 with the thickness of 95nm as a luminous auxiliary layer on the hole injection layer in vacuum;
e. EML (light-emitting layer): then on the above-mentioned luminescence auxiliary layer so as to
Figure BDA0003670834440000191
The chemical formulae of Host and Dopant (span) are shown below, where Host and Dopant (span) are deposited as light-emitting layers in vacuum at a thickness of 40 nm. Wherein the evaporation rate ratio of Host to Dopantt is 97: 3.
f. HBL (hole blocking layer): to be provided with
Figure BDA0003670834440000192
The deposition rate of (3) was determined by vacuum deposition of HB-1 having a thickness of 5.0nm as a hole-blocking layer.
g. ETL (electron transport layer): to be provided with
Figure BDA0003670834440000193
The chemical formula of ET-1 is shown below, and ET-1 and Liq with the thickness of 35nm are vacuum evaporated to be used as electron transport layers. Wherein the evaporation rate ratio of ET-1 to Liq is 50: 50.
h. EIL (electron injection layer): to be provided with
Figure BDA0003670834440000194
The evaporation rate of (2) and the evaporation of the Yb film layer is 1.0nm to form the electron injection layer.
i. Cathode: to be provided with
Figure BDA0003670834440000195
The evaporation rate ratio of the (1) to the (9) is 1:9, and the OLED device is obtained.
j. Light extractionLayer (b): to be provided with
Figure BDA0003670834440000196
The compound C01 provided in the above example was vacuum-deposited on the cathode at a thickness of 70nm as a light extraction layer.
k. And then packaging the evaporated substrate. Firstly, coating the cleaned cover plate by using UV glue through gluing equipment, then moving the coated cover plate to a pressing working section, placing the evaporated substrate on the upper end of the cover plate, finally, attaching the substrate and the cover plate under the action of attaching equipment, and simultaneously, finishing the illumination and solidification of the UV glue.
The chemical structure of the corresponding compound used in the above device is shown below:
Figure BDA0003670834440000201
red light device embodiments 2 to 10
Organic electroluminescent devices, identified as device examples 2-10, were fabricated as device examples 1 by replacing the cathode cap material with compounds C05, C09, C16, C18, C23, C26, C32, C35, and C40, respectively.
Comparative examples 1 to 2 of Red light device
Comparative examples 1-2 of organic electroluminescent red devices were prepared according to the method of red device example 1. Except that the CPL layer material compound was replaced with comparative compound 1 and comparative compound 2, and the materials of the other materials such as the light-emitting layer were the same and were respectively referred to as device comparative examples 1-2.
The organic electroluminescent devices obtained in the above device examples 1 to 10 and device comparative examples 1 to 2 were characterized for driving voltage, luminous efficiency and lifetime at 6000(nits) luminance, and the test results are as follows in table 3:
TABLE 3
Figure BDA0003670834440000202
Figure BDA0003670834440000211
Green device example 1
The following examples provide applications of the compounds of the present invention in organic light emitting devices, and illustrate the technical effects achieved by the compounds of the present invention in practical applications.
The structure of the prepared OLED device is as follows: ITO anode/HIL/HTL/EML/ETL/EIL/cathode/light extraction layer
a. An ITO anode: cleaning an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, ultrasonically cleaning for 30min, repeatedly cleaning for 2 times by using distilled water, ultrasonically cleaning for 10min, transferring to a spin dryer for spin-drying after the cleaning is finished, finally baking for 2 hours at 220 ℃ by using a vacuum oven, and cooling after the baking is finished. And (3) taking the substrate as an anode, performing a device evaporation process by using an evaporation machine, and sequentially evaporating other functional layers on the substrate.
b. HIL (hole injection layer): to be provided with
Figure BDA0003670834440000212
The hole injection layer materials HT-1 and P-dopant were vacuum evaporated, and the chemical formulas are shown below. The evaporation rate ratio of HT-1 to P-dock is 97: 3, the thickness is 10 nm;
c. HTL (hole transport layer): to be provided with
Figure BDA0003670834440000213
The evaporation rate of (2), and evaporating 130nm HT-1 on the hole injection layer in vacuum to form a hole transport layer;
d. a light-emitting auxiliary layer: to be provided with
Figure BDA0003670834440000214
The evaporation rate of (2), evaporating EB-2 with the thickness of 45nm as a luminous auxiliary layer on the hole transmission layer in vacuum;
e. EML (light-emitting layer): then on the above-mentioned luminescence auxiliary layer so as to
Figure BDA0003670834440000215
The Host material (Host1 and Host2) and the Dopant material (Dopant) were vacuum-deposited to a thickness of 40nm as the light-emitting layer, and the chemical formulae of Host and Dopant are shown below. Wherein the evaporation rate ratio of Host1 to Host2 to Dopantt is 47: 47: 6.
f. HBL (hole blocking layer): to be provided with
Figure BDA0003670834440000221
The deposition rate of (3) was determined by vacuum deposition of HB-2 having a thickness of 5.0nm as a hole-blocking layer.
g. ETL (electron transport layer): to be provided with
Figure BDA0003670834440000222
The chemical formula of ET-2 is shown below, and ET-2 and Liq with the thickness of 35nm are vacuum evaporated to be used as electron transport layers. Wherein the evaporation rate ratio of ET-2 to Liq is 50: 50.
h. EIL (electron injection layer): to be provided with
Figure BDA0003670834440000223
The evaporation rate of (2) and the evaporation of the Yb film layer is 1.0nm to form the electron injection layer.
i. Cathode: to be provided with
Figure BDA0003670834440000224
The evaporation rate ratio of the (1) to the (9) is 1:9, and the OLED device is obtained.
j. Light extraction layer: to be provided with
Figure BDA0003670834440000225
The compound 2 provided in the above example was vacuum-deposited on the cathode at a thickness of 70nm as a light extraction layer.
k. And then packaging the evaporated substrate. Firstly, coating the cleaned cover plate by using UV glue through gluing equipment, then moving the coated cover plate to a pressing working section, placing the evaporated substrate on the upper end of the cover plate, finally, attaching the substrate and the cover plate under the action of attaching equipment, and simultaneously, finishing the illumination and solidification of the UV glue.
The chemical structure of the corresponding compound used in the above device is shown below:
Figure BDA0003670834440000231
green device examples 2-10
Organic electroluminescent devices, designated as green device examples 2-10, were fabricated as green device examples 1 by replacing the cathode cap material with compounds C05, C09, C16, C18, C23, C26, C32, C35, and C40, respectively.
Comparative examples 1-2 of Green devices
Comparative examples 1-2 of organic electroluminescent green devices were prepared according to the method of green device example 1. Except that the CPL layer material compound was replaced with comparative compound 1 and comparative compound 2, and the materials of the other materials, such as the light emitting layer, were the same and were respectively identified as comparative green device examples 1-2.
The organic electroluminescent devices obtained in the above green device examples 1 to 10 and green device comparative examples 1 to 2 were characterized at a luminance of 6000(nits) for driving voltage, luminous efficiency and lifetime, and the test results are as follows in table 4:
TABLE 4
Figure BDA0003670834440000232
Figure BDA0003670834440000241
Blue light device example 1
The following examples provide applications of the compounds of the present invention in organic light emitting devices, and illustrate the technical effects achieved by the compounds of the present invention in practical applications.
The structure of the prepared OLED device is as follows: ITO anode/HIL/HTL/EML/ETL/EIL/cathode/light extraction layer
a. An ITO anode: cleaning an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, ultrasonically cleaning for 30min, repeatedly cleaning for 2 times by using distilled water, ultrasonically cleaning for 10min, transferring to a spin dryer for spin-drying after the cleaning is finished, finally baking for 2 hours at 220 ℃ by using a vacuum oven, and cooling after the baking is finished. And (3) taking the substrate as an anode, performing a device evaporation process by using an evaporation machine, and sequentially evaporating other functional layers on the substrate.
b. HIL (hole injection layer): to be provided with
Figure BDA0003670834440000242
The hole injection layer materials HT-1 and P-dopant were vacuum evaporated, and the chemical formulas are shown below. The evaporation rate ratio of HT-1 to P-dock is 97: 3, the thickness is 10 nm;
c. HTL (hole transport layer): to be provided with
Figure BDA0003670834440000243
The evaporation rate of (2), and evaporating 130nm HT-1 on the hole injection layer in vacuum to form a hole transport layer;
d. a light-emitting auxiliary layer: to be provided with
Figure BDA0003670834440000244
The evaporation rate of (2) and evaporating EB-3 with the thickness of 5nm on the hole transport layer in vacuum to be used as a luminous auxiliary layer;
e. EML (light-emitting layer): then on the above-mentioned luminescence auxiliary layer so as to
Figure BDA0003670834440000251
The chemical formulae of Host and Dopant (span) are shown below, where Host and Dopant (span) materials with a thickness of 20nm are vacuum-deposited as the light-emitting layer. Wherein the evaporation rate ratio of Host to Dopantt is 98: 2.
f. ETL (electron transport layer): to be provided with
Figure BDA0003670834440000252
The chemical formula of ET-3 is shown below, and ET-3 and Liq with the thickness of 35nm are vacuum evaporated to be used as electron transport layers. Wherein the evaporation rate ratio of ET-3 to Liq is 50: 50.
g. EIL (electron injection layer): to be provided with
Figure BDA0003670834440000253
The evaporation rate of (2) and the evaporation of the Yb film layer is 1.0nm to form the electron injection layer.
h. Cathode: to be provided with
Figure BDA0003670834440000254
The evaporation rate ratio of the (1) to the (9) is 1:9, and the OLED device is obtained.
i. Light extraction layer: to be provided with
Figure BDA0003670834440000255
The compound 2 provided in the above example was vacuum-deposited on the cathode at a thickness of 70nm as a light extraction layer.
j. And then packaging the evaporated substrate. Firstly, coating the cleaned cover plate by using UV glue through gluing equipment, then moving the coated cover plate to a pressing working section, placing the evaporated substrate on the upper end of the cover plate, finally, attaching the substrate and the cover plate under the action of attaching equipment, and simultaneously, finishing the illumination and solidification of the UV glue.
The chemical structure of the corresponding compound used in the above device is shown below:
Figure BDA0003670834440000261
blue device examples 2-10
Organic electroluminescent devices, designated as blue device examples 2-10, were fabricated by substituting the cathode capping layer materials with C05, C09, C16, C18, C23, C26, C32, C35, and C40, respectively, in accordance with the method of blue device example 1.
Blue device comparative examples 1-2
Comparative examples 1-2 of organic electroluminescent blue devices were prepared according to the method of blue device example 1. Except that the CPL layer material compound was replaced with comparative compound 1. comparative compound 2, and the materials of other materials such as the light emitting layer were the same and are respectively labeled as comparative examples 1-2 of the blue light device.
The organic electroluminescent devices obtained in examples 1 to 10 of the blue device and comparative examples 1 to 2 of the blue device were characterized at a luminance of 6000(nits) for driving voltage, luminous efficiency and lifetime, and the test results are shown in the following table 5:
TABLE 5
Figure BDA0003670834440000262
Figure BDA0003670834440000271
Note: in a blue top-emitting device, current efficiency is greatly affected by chromaticity, so that the influence factor of chromaticity on efficiency is taken into consideration, and the ratio of luminous efficiency to CIEy is defined as a BI value, i.e., (cd/a)/CIEy.
As can be seen from the tables 3-5, the red light device, the green light device and the blue light device are respectively prepared by using the compound, compared with a device comparative example, the luminous efficiency of the device adopting the compound as a CPL material is obviously improved. This means that: by containing a compound having a high refractive index in the cover layer, the light extraction efficiency can be greatly improved. The compound of the present invention has a high absorption coefficient and a high refractive index, can greatly improve the light extraction efficiency, and has a stable thin film state, and therefore, is a very excellent compound for an organic EL device. The organic EL element prepared by the compound can improve the luminous efficiency of the device, and is an ideal CPL material.
The present invention has been described above by way of example, and various modifications can be made by those skilled in the art to which the present invention pertains without departing from the essential characteristics of the invention. Therefore, the embodiments disclosed in the present specification are not intended to limit the present invention but to illustrate it, and the spirit and scope of the present invention should not be limited by such embodiments. The scope of the invention should be construed by the claims that follow, and all techniques that come within the range of equivalents thereof should be construed as being included in the scope of the claims.

Claims (7)

1. A capping layer material, wherein the structure of the capping layer material is shown in formula 1:
Figure FDA0003670834430000011
wherein X represents an oxygen or sulfur atom;
L 1 、L 2 、L 3 identical to or different from each other and independently represent a connecting bond, a substituted or unsubstituted C 3 ～C 60 Cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C 6 ～C 60 Any one of an aryl group, a substituted or unsubstituted 3-to 30-membered heteroaryl group;
r independently represents hydrogen, hydrogen isotope, cyano, substituted or unsubstituted C1-C60 alkyl, C3-C60 cycloalkyl, substituted or unsubstituted C2-C60 alkenyl, C3-C60 cycloalkenyl, substituted or unsubstituted C3-C60 alkynyl, C3-C60 cycloalkynyl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C1878-C20 alkoxy, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted 3-10-membered heterocyclic group.
2. The capping layer material of claim 1, wherein said L is 1 、L 2 、L 3 Are the same or different from each other and independently represent a bond, substituted or unsubstituted C 6 ～C 30 Any one of an aryl group and a substituted or unsubstituted 3-to 15-membered heteroaryl group.
3. The capping layer material of claim 1, wherein the capping layer material has a chemical formula of any one of:
Figure FDA0003670834430000021
Figure FDA0003670834430000031
Figure FDA0003670834430000041
4. use of a capping layer material according to any one of claims 1 to 3 in the field of optoelectronics.
5. A light emitting device comprising the capping layer material of any one of claims 1-3.
6. The light-emitting device according to claim 5, wherein the light-emitting device comprises a light-emitting layer and a cathode cover layer; the light-emitting layer and/or the cathode cladding layer comprises a capping layer material according to any one of claims 1 to 3.
7. A light-emitting device comprising the capping layer material according to any one of claims 1 to 3 or the light-emitting device according to claim 5 or 6.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115557921A (en) * 2022-12-02 2023-01-03 吉林奥来德光电材料股份有限公司 Cap layer material, preparation method, organic electroluminescent device and display device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115557921A (en) * 2022-12-02 2023-01-03 吉林奥来德光电材料股份有限公司 Cap layer material, preparation method, organic electroluminescent device and display device

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