WO2024078314A1 - Anthryl-compound-containing composition and organic electroluminescent device comprising same - Google Patents

Abstract

Provided in the present application are an anthryl-compound-containing composition and an organic electroluminescent device comprising same. The composition comprises at least two compounds each having a structure represented by formula I. The composition is used as a material of a light-emitting layer of an organic electroluminescent device (OLED). In the present application, by means of designing the compound structures and using the composition having a specific composition as the material of the light-emitting layer of the OLED, the OLED has a low driving voltage, a relatively high current efficiency and a relatively long service life.

Description

Composition containing anthracene-based compound and organic electroluminescent device containing the same

This application claims the priority of the Chinese patent application number 202211260977.8 filed with the Chinese Patent Office on October 14, 2022. The entire contents of the above application are incorporated by reference into this application.

Technical Field

The present application belongs to the technical field of organic electroluminescent materials, and specifically relates to a composition containing an anthracene-based compound and an organic electroluminescent device containing the same.

Background technique

Compared with other flat panel displays (for example, liquid crystal displays (LCDs), plasma display panels (PDPs), field emission displays (FEDs), etc.), organic electroluminescent devices (OLEDs) have a simpler structure, various processing advantages, higher brightness, excellent viewing angle characteristics, faster response speeds, and lower driving voltages. Therefore, they are also fully developed to be used as light sources for flat panel displays (for example, wall-mounted TVs, etc.), or as backlight units for displays, illuminators, billboards, etc.

The structure of an organic electroluminescent device is specifically: an anode, a cathode, and an organic layer between the two. In order to improve the efficiency and stability of an organic electroluminescent element, the organic material layer includes multiple layers with different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer, a light-emitting layer, an electron transport layer (ETL), and an electron injection layer (EIL). Currently, organic electroluminescence has become a mainstream display technology, and accordingly, various new OLED materials have also been developed.

In order to meet people's higher requirements for OLED devices, the field is in urgent need of developing more types of materials to improve the performance of OLED devices in terms of current efficiency, life span, etc.

Summary of the invention

The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

In view of the shortcomings of the prior art, the purpose of the present application is to provide a composition containing an anthracene-based compound and an organic electroluminescent device containing the same. In the present application, by designing the compound structure and using a composition of a specific composition as a light-emitting layer material of an OLED light-emitting device, the OLED light-emitting device has a lower driving voltage, a higher current efficiency and a longer life.

To achieve this goal, this application adopts the following technical solutions:

In a first aspect, the present application provides a composition, comprising at least two compounds both having a structure as shown in Formula I;

wherein Ar ₁₁ and Ar ₁₂ are each independently selected from any one of substituted or unsubstituted phenyl, naphthyl or biphenyl;

X is selected from O or S;

The substituents in Ar ₁₁ and Ar ₁₂ are each independently selected from at least one of -F, -CN, C1-C12 alkyl, C1-C12 alkoxy, C6-C20 aryl, and C6-C20 heteroaryl;

The compound of formula I meets at least one of the following conditions:

(1) The compound represented by formula I does not contain a deuterium atom;

(2) All hydrogen atoms of at least one of the substituted substituents in Ar ₁₁ are replaced by deuterium atoms;

(3) All hydrogen atoms of at least one of the substituted substituents in Ar ₁₂ are replaced by deuterium atoms;

(4) at least one hydrogen atom in Ar ₁₁ is completely replaced by deuterium atoms;

(5) at least one hydrogen atom in Ar ₁₂ is completely replaced by deuterium atoms;

(6) All hydrogen atoms in ring A are replaced by deuterium atoms;

(7) All hydrogen atoms in ring B are replaced by deuterium atoms;

(8) All hydrogen atoms of ring C are replaced by deuterium atoms;

(9) All hydrogen atoms in ring E are replaced by deuterium atoms.

In the present application, by designing the compound structure and further selecting compounds with specific structural formulas for joint use, and using the composition as the material for the light-emitting layer of the OLED light-emitting device, the OLED light-emitting device has a lower driving voltage, higher current efficiency and longer life.

In the present application, the substituents substituted in Ar ₁₁ and Ar ₁₂ are each independently selected from at least one of -F, -CN, C1-C12 (for example, C1, C2, C5, C6, C8, C10 or C12, etc.) alkyl, C1-C12 (for example, C1, C2, C5, C6, C8, C10 or C12, etc.) alkoxy, C6-C20 (for example, C6, C7, C10, C12, C18 or C20) aryl, and C6-C20 (for example, C6, C7, C10, C12, C18 or C20) heteroaryl.

The following are optional technical solutions for this application, but are not intended to limit the technical solutions provided in this application. Through the following optional technical solutions, the objectives and beneficial effects of this application can be better achieved and realized.

As an optional technical solution of the present application, the composition includes at least one compound of formula I that meets any one of conditions (2) to (9).

In one embodiment, the compound of formula I is selected from the compound of formula I-1 or the compound of formula I-2:

Wherein, Ar ₁₁ and Ar ₁₂ have the same protection scope as above;

In one embodiment, the compound of formula I is selected from the compound of formula I-3 or the compound of formula I-4:

Wherein, Ar ₁₁ and Ar ₁₂ have the same protection scope as above.

As an optional technical solution of the present application, one of Ar ₁₁ and Ar ₁₂ is selected from phenyl.

In one embodiment, one of Ar ₁₁ and Ar ₁₂ is a biphenyl group.

Preferably, Ar ₁₁ and Ar ₁₂ are both selected from phenyl.

Preferably, Ar ₁₁ and Ar ₁₂ are both selected from biphenyl groups.

In one embodiment, the substituents substituted in Ar ₁₁ and Ar ₁₂ are each independently selected from at least one of -F, -CN, methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl or naphthyl.

As an optional technical solution of the present application, the compound of formula I is selected from any one of the following substituted or unsubstituted compounds:

The substitution means that the hydrogen atoms in the above compound can be independently replaced by deuterium atoms.

It should be noted that D in the above compounds is a deuterium atom (the same below).

As an optional technical solution of the present application, the composition further comprises a compound having a structure as shown in Formula II:

wherein R ₂₁ , R ₂₂ and R ₂₃ are each independently selected from any one of hydrogen, C1-C12 (e.g., C1, C2, C4, C6, C8, C10 or C12) linear or branched alkyl, C6-C12 (e.g., C6, C7, C8, C9, C10, C11 or C12) cycloalkyl, and -NAr ₂₃ Ar ₂₄ ;

Ar ₂₁ , Ar ₂₂ , Ar ₂₃ , and Ar ₂₄ are each independently selected from substituted or unsubstituted C6-C20 (e.g., C6, C8, C10, C12, C14, C16, C18, or C20) aryl groups, substituted or unsubstituted C3-C20 (For example, it can be C3, C6, C8, C10, C12, C14, C16, C18 or C20, etc.) any one of heteroaryl;

The substituents in Ar ₂₁ , Ar ₂₂ , Ar ₂₃ and Ar ₂₄ are each independently selected from C1-C5 straight or branched alkyl (eg, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, etc.) or C6-C12 aryl (eg, phenyl, toluene, naphthyl, etc.).

As an optional technical solution of the present application, Ar ₂₁ , Ar ₂₂ , Ar ₂₃ , and Ar ₂₄ are each independently selected from The dotted line indicates the connection site.

In one embodiment, R ₂₁ , R ₂₂ and R ₂₃ are each independently selected from any one of hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl or adamantyl.

In one embodiment, the compound of formula II is selected from any one of the following compounds:

As an optional technical solution of the present application, the composition also includes a compound having formula III:

wherein Ar ₃₁ , Ar ₃₂ , Ar ₃₃ and Ar ₃₄ are each independently selected from any one of substituted or unsubstituted C6-C22 aryl (for example, C6, C8, C10, C12, C14, C16, C18 or C20, etc.), substituted or unsubstituted C12-C40 heteroaryl (for example, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.);

R ₃₁ is selected from any one of phenyl, naphthyl or biphenyl;

a is selected from 0 or 1;

The substituents in Ar ₃₁ , Ar ₃₂ , Ar ₃₃ and Ar ₃₄ are each independently selected from C1-C5 straight or branched alkyl groups (eg, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, etc.) or C6-C12 aryl groups (eg, phenyl, etc.).

In one embodiment, Ar ₃₁ , Ar ₃₂ , Ar ₃₃ and Ar ₃₄ are each independently selected from Any one or a combination of at least two of the above, and the dotted line indicates the connection site.

In one embodiment, the compound of formula III is selected from any one of the following compounds:

In a second aspect, the present application provides a compound, which includes any one of the following compounds:

The compound is used to prepare the composition as described in the first aspect.

It should be noted that D in the above compounds is a deuterium atom.

In a third aspect, the present application provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;

The material of the organic thin film layer includes the composition described in the first aspect.

In one embodiment, the organic thin film layer includes a light emitting layer;

The material of the light-emitting layer includes the composition described in the first aspect.

In a fourth aspect, the present application provides a display device, comprising the organic electroluminescent device as described in the third aspect.

Compared with the prior art, this application has the following beneficial effects:

In the present application, the specific composition of the composition is designed, and further compounds with specific structural formulas are selected for joint use, and the composition is used as the main material of the light-emitting layer of the OLED light-emitting device, so that the OLED light-emitting device has a lower driving voltage, higher current efficiency and longer life.

Still other aspects will be apparent upon reading and understanding the detailed description.

Detailed ways

To facilitate understanding of the present application, the present application lists the following embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

Synthesis Example 1

This synthesis example provides compound BH3 and its synthesis method, the synthesis method is as follows:

Under nitrogen protection, 100 mL of toluene, 20 mL of ethanol and 10 mL of water were added in sequence to a 250 mL three-necked flask, and then BH3-1 (3.5 g), BH3-2 (3.0 g), sodium carbonate (2.1 g) and tetrakistriphenylphosphine palladium (0.15 g) were added, and the temperature was slowly raised to reflux for reaction for 8 h. The temperature was lowered to room temperature, and water was added to separate. The organic layer was washed with water and dried over magnesium sulfate. After the magnesium sulfate was removed by filtration, the solvent was removed under reduced pressure, and the mixture was separated by silica gel column chromatography and eluted with petroleum ether: ethyl acetate: dichloromethane = 10:1:0.2 (volume ratio) to obtain compound BH3 (3.9 g).

The mass spectrometry detection of compound BH3: the mass-to-charge ratio (m/z) was measured to be 514.17.

Synthesis Example 2-7

Synthesis Examples 2-7 respectively provide a compound and a synthesis method thereof. The synthesis method of the compound refers to the synthesis method of compound BH3 in Example 1, except that the corresponding bromide and boronic acid compounds are used to synthesize the corresponding compounds (see Table 1 for details); and the synthesized compounds are subjected to mass spectrometry detection, and the mass-to-charge ratio (m/z) of the compounds is measured and shown in Table 1 below.

Table 1

Other compounds for which the specific synthesis steps are not listed can be prepared by common knowledge in the art in combination with the above embodiments.

The specific structures of the compounds used in the following device examples and device comparative examples are as follows:

The specific structures of the compounds used in the following examples are shown below:

Device Example 1

The device embodiment provides an organic electroluminescent device, wherein the structure of the organic electroluminescent device is ITO/HT (40nm)/light-emitting layer (30nm): BD-1 (3%)/TPBI (30nm)/LiF (0.5nm)/Al (150nm);

The preparation method of the organic electroluminescent device is as follows:

(1) a glass substrate coated with an ITO transparent conductive layer (as an anode) is ultrasonically treated in a cleaning agent, then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, and then dried in a clean environment to completely remove water, then cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam to improve the properties of the ITO surface and enhance the binding ability with the hole injection layer;

(2) placing the glass substrate in a vacuum chamber, evacuating the chamber to 1×10 ^-5 to 1×10 ^-4 Pa, and vacuum evaporating HT on the anode as a hole transport layer at a rate of 0.01 nm/s and a thickness of 40 nm;

(3) vacuum evaporating a light-emitting layer on the hole transport layer, with an evaporation rate of 0.01 nm/s and a total film thickness of 30 nm. The composition of the main material of the light-emitting layer is BH5 and BH5-D (the volume ratio of the two is 1:1), the doping material is BD-1, and the volume ratio of the main material of the light-emitting layer to the doping material is 100:3; when the main material of the light-emitting layer is more than two substances, different main materials are placed in different evaporation sources respectively, and the evaporation speed of different main materials is controlled so that mixtures with different volume ratios are used as the main material of the light-emitting layer in the organic electroluminescent device;

(4) Vacuum evaporation of TPBI on the organic light-emitting layer as an electron transport agent for organic electroluminescent devices layer; the evaporation rate is 0.01nm/s, and the total evaporation film thickness is 30nm;

(5) Vacuum evaporation was performed on the electron transport layer to form an electron injection layer and a cathode to obtain the organic electroluminescent device.

Device Examples 2-11

Device Examples 2-11 respectively provide an organic electroluminescent device, which differs from Device Example 1 only in that the main material of the light-emitting layer is different. The specific composition of the main material of the light-emitting layer is shown in Table 2 below. The volume ratio of each compound in the main material of the light-emitting layer is the same (if the main material of the light-emitting layer is two compounds, the volume ratio of the two compounds is 1:1; if the main material of the light-emitting layer is three compounds, the volume ratio of the three compounds is 1:1:1), and other structures, materials and preparation methods are the same as those in Device Example 1.

Device Comparison Examples 1-5

Device comparison examples 1-5 respectively provide an organic electroluminescent device, which differs from device example 1 only in that the main material of the light-emitting layer is different. The specific composition of the main material of the light-emitting layer is shown in Table 2 below. The volume ratio of each compound in the main material of the light-emitting layer is 1:1, and the other structures, materials and preparation methods are the same as those of device example 1.

Performance Testing:

The OLED-1000 multi-channel accelerated aging life and light color performance analysis system produced by Hangzhou Yuanfang was used to test the driving voltage, current efficiency and life LT90 of the organic electroluminescent devices provided above; wherein LT90 refers to the time required for the brightness to drop to 90% of the original brightness while maintaining the current density unchanged when the initial brightness is 2000nit. The specific test results are shown in Table 2, wherein the driving voltage, current efficiency and LT90 are all relative values.

Table 2

Note: “/” in Table 2 means that the light-emitting layer host material of the device example or device comparison example does not contain the compound.

It can be seen from the contents of Table 2 that in the present application, by designing the specific composition of the composition, further by selecting compounds with specific structural formulas for joint use, and using the composition as the main material of the light-emitting layer of the OLED light-emitting device, the OLED light-emitting device has a lower driving voltage, a higher current efficiency and a longer life.

It can be seen from device examples 1, 4, 6-11 and device examples 2-3, 5 that in the present application, by controlling the composition to contain at least one compound containing a deuterium atom, the OLED device prepared has more excellent comprehensive performance.

It can be seen from device examples 1-9 and device examples 10-11 that the present application selects three compounds of formula I to form a composition, uses the three compounds in combination, and uses the composition as the main material of the light-emitting layer of the OLED device, which can further improve the life of the OLED.

It can be seen from device embodiments 1-11 and device comparison examples 1-2 and 5 that in the present application, by selecting compounds with a specific structure to form a composition, and using this composition as the main material of the light-emitting layer of the OLED light-emitting device, the OLED light-emitting device can have a lower driving voltage, a higher current efficiency and a longer life.

It can be seen from device examples 1-11 and device comparative examples 3-4 that in the present application, by selecting at least two compounds of formula I to form a composition, an OLED device with better comprehensive performance can be prepared.

Device Examples 12-13

Device Examples 12-13 respectively provide an organic electroluminescent device, which differs from Device Example 1 only in that BD-2 is used instead of BD-1. In addition, the main material of the light-emitting layer is different. The specific composition of the main material of the light-emitting layer is shown in Table 3 below. The volume ratio of each compound in the main material of the light-emitting layer is 1:1. The other structures, materials and preparation methods are the same as those of Device Example 1.

Device Comparison Examples 6-7

Device comparison examples 6-7 respectively provide an organic electroluminescent device, which differs from device example 12 only in that the main material of the light-emitting layer is different. The specific composition of the main material of the light-emitting layer is shown in Table 3 below. The volume ratio of each compound in the main material of the light-emitting layer is 1:1, and the other structures, materials and preparation methods are the same as those of device example 12.

Performance Testing:

The OLED-1000 multi-channel accelerated aging life and light color performance analysis system produced by Hangzhou Yuanfang was used to test the driving voltage, current efficiency and life LT90 of the organic electroluminescent devices provided above; LT90 refers to the current density when the initial brightness is kept at 2000nit and the brightness drops to 90% of the original brightness. The specific test results are shown in Table 2, where the driving voltage, current efficiency and LT90 are all relative values.

table 3

It can be seen from the contents of Table 3 that in the present application, a compound having a specific structure represented by formula I and a compound having a structure represented by formula III are used together to obtain a composition, and this is used as the main material of the light-emitting layer of an OLED light-emitting device, so that the OLED light-emitting device has a lower driving voltage, a higher current efficiency and a longer life.

The applicant declares that the present application uses the above-mentioned embodiments to illustrate the detailed process flow of the present application, but the present application is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present application must rely on the above-mentioned detailed process flow to be implemented. The technicians in the relevant technical field should understand that any improvement to the present application, the equivalent replacement of the raw materials of the product of the present application, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

Claims (10)

1. A composition containing anthracene-based compounds, the composition comprising at least two compounds both having a structure as shown in Formula I;
   

   wherein Ar ₁₁ and Ar ₁₂ are each independently selected from any one of substituted or unsubstituted phenyl, naphthyl or biphenyl;

   X is selected from O or S;

   The substituents in Ar ₁₁ and Ar ₁₂ are each independently selected from at least one of -F, -CN, C1-C12 alkyl, C1-C12 alkoxy, C6-C20 aryl, and C6-C20 heteroaryl;

   The compound of formula I meets at least one of the following conditions:

   (1) The compound represented by formula I does not contain a deuterium atom;

   (2) All hydrogen atoms of at least one of the substituted substituents in Ar ₁₁ are replaced by deuterium atoms;

   (3) All hydrogen atoms of at least one of the substituted substituents in Ar ₁₂ are replaced by deuterium atoms;

   (4) at least one hydrogen atom in Ar ₁₁ is completely replaced by deuterium atoms;

   (5) at least one hydrogen atom in Ar ₁₂ is completely replaced by deuterium atoms;

   (6) All hydrogen atoms in ring A are replaced by deuterium atoms;

   (7) All hydrogen atoms in ring B are replaced by deuterium atoms;

   (8) All hydrogen atoms of ring C are replaced by deuterium atoms;

   (9) All hydrogen atoms in ring E are replaced by deuterium atoms.
2. The composition according to claim 1, wherein the composition comprises at least one A compound of formula I according to any one of conditions (2) to (9);

   Optionally, the compound of formula I is selected from the compound of formula I-1 or the compound of formula I-2:
   

   Wherein, Ar ₁₁ and Ar ₁₂ have the same protection scope as claim 1;

   Optionally, the compound of formula I is selected from the compound of formula I-3 or the compound of formula I-4:
   

   Wherein, Ar ₁₁ and Ar ₁₂ have the same protection scope as that of claim 1.
3. The composition according to claim 1 or 2, wherein one of Ar ₁₁ and Ar ₁₂ is selected from phenyl;

   Optionally, one of Ar ₁₁ and Ar ₁₂ is a biphenyl group;

   Optionally, Ar ₁₁ and Ar ₁₂ are both selected from phenyl;

   Optionally, Ar ₁₁ and Ar ₁₂ are both selected from biphenyl;

   Optionally, the substituents substituted in Ar ₁₁ and Ar ₁₂ are each independently selected from -F, -CN, methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl or naphthyl. At least one of .
4. The composition according to any one of claims 1 to 3, wherein the compound of formula I is selected from any one of the following substituted or unsubstituted compounds:
   
   
   
   

   The substitution means that the hydrogen atoms in the above compound can be independently replaced by deuterium atoms.
5. The composition according to any one of claims 1 to 4, wherein the composition further comprises a compound having a structure as shown in Formula II:
   

   wherein R ₂₁ , R ₂₂ and R ₂₃ are each independently selected from any one of hydrogen, C1-C12 straight or branched alkyl, C6-C12 cycloalkyl, and -NAr ₂₃ Ar ₂₄ ;

   Ar ₂₁ , Ar ₂₂ , Ar ₂₃ , and Ar ₂₄ are each independently selected from any one of a substituted or unsubstituted C6-C20 aryl group and a substituted or unsubstituted C3-C20 heteroaryl group;

   The substituents of Ar ₂₁ , Ar ₂₂ , Ar ₂₃ and Ar ₂₄ are each independently selected from C1-C5 straight-chain or branched alkyl groups or C6-C12 aryl groups.
6. The composition according to claim 5, wherein Ar ₂₁ , Ar ₂₂ , Ar ₂₃ , and Ar ₂₄ are each independently selected from Any of the above, the dotted line indicates the connection site;

   Optionally, R ₂₁ , R ₂₂ and R ₂₃ are each independently selected from any one of hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl or adamantyl.
7. The composition according to any one of claims 1 to 6, wherein the composition further comprises a compound having a structure as shown in Formula III:
   

   wherein Ar ₃₁ , Ar ₃₂ , Ar ₃₃ and Ar ₃₄ are each independently selected from any one of a substituted or unsubstituted C6-C22 aryl group and a substituted or unsubstituted C12-C40 heteroaryl group;

   R ₃₁ is selected from any one of phenyl, naphthyl or biphenyl;

   a is selected from 0 or 1;

   The substituents of Ar ₃₁ , Ar ₃₂ , Ar ₃₃ and Ar ₃₄ are each independently selected from C1-C5 straight or branched chain alkyl or C6-C12 aryl;

   Optionally, Ar ₃₁ , Ar ₃₂ , Ar ₃₃ and Ar ₃₄ are each independently selected from Any one or a combination of at least two of the above, and the dotted line indicates the connection site.
8. A compound, comprising any one of the following compounds:
   

   The compound is used to prepare the composition according to any one of claims 1 to 7.
9. An organic electroluminescent device, comprising an anode, a cathode and an organic thin film layer arranged between the anode and the cathode;

   The material of the organic thin film layer comprises the composition according to any one of claims 1 to 7;

   Optionally, the organic thin film layer includes a light-emitting layer;

   The material of the light-emitting layer includes the composition according to any one of claims 1 to 7.
10. A display device, comprising the organic electroluminescent device according to claim 9.