阅读说明：本技术 光敏型化合物、由其制备的抗溶剂型空穴传输层材料及其应用 (Photosensitive compound, anti-solvent type hole transport layer material prepared from photosensitive compound and application of anti-solvent type hole transport layer material ) 是由 易袁秋强 苏文明 刘扬 于 2021-09-23 设计创作，主要内容包括：本发明公开了一类含有二苯甲酮基与三芳基胺基组合的光敏型小分子空穴传输材料,该类材料具有与量子点发光材料匹配的合适能级与迁移率,其自身就可以作为QLED的空穴传输层材料,器件性能与基于TFB的器件接近。本发明还提供了所述光敏型小分子空穴传输材料的制备方法,以及由其制备的抗溶剂型空穴传输层材料及其应用。本发明的光敏型空穴传输材料与TFB制备的交联型空穴传输层,有效地克服了聚合物空穴传输材料TFB的不抗溶剂性,实现了空穴传输层100％的抗溶剂性,可以有效避免层间侵蚀问题。(The invention discloses a photosensitive micromolecule hole transport material containing a benzophenone group and triarylamine group combination, which has proper energy level and mobility matched with a quantum dot luminescent material, can be used as a hole transport layer material of a QLED, and has device performance close to that of a device based on TFB. The invention also provides a preparation method of the photosensitive micromolecule hole transport material, an anti-solvent type hole transport layer material prepared from the photosensitive micromolecule hole transport material and application of the anti-solvent type hole transport layer material. The crosslinking hole transport layer prepared from the photosensitive hole transport material and the TFB effectively overcomes the non-solvent resistance of the polymer hole transport material TFB, realizes 100% solvent resistance of the hole transport layer, and can effectively avoid the problem of interlayer erosion.)

1. A photosensitive compound having a structural formula as shown below:

wherein Ar is₁One selected from the following structures:

Ar₂one selected from the following structures:

R₁、R₂、R₃、L₁、L₂、L₃independently selected from C₁-C₆₀Alkyl of (C)₁-C₆₀Saturated alkyl containing hetero atoms, C₁-C₆₀Aryl and C₁-C₆₀One of the heteroaryl groups.

2. The photosensitive compound of claim 1, wherein R is₁、R₂、R₃、L₁、L₂、L₃Independently selected from one of methyl, tertiary butyl and phenyl.

3. The photosensitive compound of claim 1, wherein the photosensitive compound is one of the following compounds:

4. the process for preparing a photosensitive compound according to claim 1, comprising the steps of:

s1, under a protective atmosphere, enabling a first compound and a second compound to react in tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine tetrafluoroborate and NaO^tBu is catalyzed to react in a solvent; after the reaction is finished, collecting and purifying a product to obtain a first intermediate;

s2, under the protective atmosphere, enabling the first intermediate to react with BBr₃Reacting in a solvent; after the reaction is finished, collecting and purifying a product to obtain a second intermediate;

s3, reacting the second intermediate and the third compound under the action of inorganic base in a protective atmosphere; after the reaction is finished, collecting and purifying a product to obtain the photosensitive compound;

wherein the structural formulas of the first compound, the second compound, the third compound, the first intermediate and the second intermediate are respectively shown in formulas (I) to (V):

in step S1, the first compound, the second compound, tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine tetrafluoroborate and NaO^tThe equivalent ratio of Bu is 1: (2.2-3.0): 0.02: 0.04: (2.5-3.0); the reaction temperature is 60-130 ℃, and the reaction time is 12-36 hours;

in step S2, the first intermediate reacts with BBr₃The equivalent ratio of (A) to (B) is 1: 2.2-3.0;

in step S3, the equivalent ratio of the second intermediate, the third compound and the inorganic base is 1 (2.2-3.2) to (2.5-4.0); the reaction temperature is 50-100 ℃, and the reaction time is 2-24 hours.

5. Use of a photosensitive compound according to any one of claims 1 to 3 as a hole transport layer material.

6. An anti-solvent type hole transport layer material, wherein the anti-solvent type hole transport layer material is obtained by the crosslinking reaction of the photosensitive compound according to any one of claims 1 to 3 and polymer TFB.

7. The solvent-resistant hole transport layer material according to claim 6, wherein the mass ratio of the photosensitive compound to the polymer TFB is 1: 0.1-40.

8. Use of the solvent-resistant hole transport layer material of claim 6 in the preparation of quantum dot electroluminescent devices.

9. The application of claim 8, wherein the photosensitive compound and polymer TFB are dissolved in an organic solvent, and the film is formed by spin coating or ink-jet printing, and then the hole transport layer of the quantum dot electroluminescent device is obtained by photo-crosslinking.

10. The use according to claim 9, wherein the organic solvent is at least one of toluene, m-xylene, methyl benzoate, chlorobenzene, o-dichlorobenzene, cyclohexylbenzene, indene and anisole; the photo-crosslinking conditions are as follows: the wavelength is 254nm or 365nm, the power is 100-K and 1000 mW-cm^-2The ultraviolet lamp is used for illumination, and the crosslinking time is 5-240 minutes.

Technical Field

The invention relates to the technical field of display, in particular to a photosensitive compound, an anti-solvent type hole transport layer material prepared from the photosensitive compound and application of the anti-solvent type hole transport layer material.

Background

Quantum-dot Light Emitting diodes (QLEDs) are widely regarded as the main research direction in the future of the printing display technology due to their advantages of narrow electroluminescence spectrum, high color purity and wide color gamut, and capability of printing and preparing Light, thin and flexible display devices by a full solution method, and are therefore also receiving attention from manufacturers of various large display panels.

At present, the QLED adopts a classic sandwich device structure mainly composed of a carrier transport layer and a quantum dot light emitting layer. Therefore, the carrier transport layer, especially the hole transport layer, has a crucial influence on the luminous efficiency and lifetime of the device. For the QLED device prepared by the solution method, the preparation of the large-size QLED by large-area inkjet printing is a development trend of the industry in the future. Ink jet printing for the fabrication of QLED devices requires that the upper solution does not attack or damage the lower film, which requires good solvent resistance or orthogonal solvent resistance of the underlying functional layer. The traditional polymer or triarylamine small-molecule hole transport material has no universal solvent resistance. Therefore, the development of a hole transport layer material with a high solvent resistance is particularly critical for preparing a high-performance QLED device by ink-jet printing.

Disclosure of Invention

The invention aims to provide a small-molecule photosensitive compound, which is blended with a traditional polymer hole transport material TFB, can prepare a solvent-resistant hole transport layer under the synergistic action of ultraviolet light or ultraviolet light and heating, can effectively avoid the problem of interlayer corrosion of a QLED device, and forms a more stable device interface.

In order to solve the technical problems, the invention provides the following technical scheme:

the invention provides a photosensitive compound, which has a structural formula as shown in the following:

wherein Ar is₁One selected from the following structures:

Ar₂one selected from the following structures:

R₁、R₂、R₃、L₁、L₂、L₃independently selected from C₁-C₆₀Alkyl of (C)₁-C₆₀Saturated alkyl containing hetero atoms, C₁-C₆₀Aryl and C₁-C₆₀One of the heteroaryl groups.

Further, R₁、R₂、R₃、L₁、L₂、L₃Independently selected from one of methyl, tertiary butyl and phenyl.

Further, the photosensitive compound is one of the following compounds:

the invention also provides a preparation method of the photosensitive compound, which comprises the following steps:

s1, under a protective atmosphere, enabling a first compound and a second compound to react in tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine tetrafluoroborate and NaO^tBu is catalyzed to react in a solvent; after the reaction is finished, collecting andpurifying the product to obtain a first intermediate;

s2, under the protective atmosphere, enabling the first intermediate to react with BBr₃Reacting in a solvent; after the reaction is finished, collecting and purifying a product to obtain a second intermediate;

s3, reacting the second intermediate and the third compound under the action of inorganic base in a protective atmosphere; after the reaction is finished, collecting and purifying a product to obtain the photosensitive compound;

wherein the structural formulas of the first compound, the second compound, the third compound, the first intermediate and the second intermediate are respectively shown in formulas (I) to (V):

further, in step S1, the first compound, the second compound, tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine tetrafluoroborate and NaO^tThe equivalent ratio of Bu is 1: (2.2-3.0): 0.02: 0.04: (2.5-3.0); the reaction temperature is 60-130 ℃, and the reaction time is 12-36 hours.

Further, in step S1, the solvent is toluene with water and oxygen removed.

Further, in step S2, the first intermediate reacts with BBr₃The equivalent ratio of (A) to (B) is 1: 2.2-3.0.

Further, in step S3, the equivalent ratio of the second intermediate, the third compound and the inorganic base is 1: (2.2-3.2): (2.5-4.0); the reaction temperature is 50-100 ℃, and the reaction time is 2-24 hours. Further, the inorganic base is potassium carbonate.

Further, in steps S1-S3, the steps of collecting and purifying the product are: cooling the reaction solution to room temperature, pouring the reaction solution into ice water, separating an organic phase, extracting a water phase by using dichloromethane, combining the organic phase, drying the organic phase by using anhydrous sodium sulfate, filtering, spin-drying the solvent, adding silica gel for preparing a sample, and separating and purifying by column chromatography.

The invention also provides application of the photosensitive compound as a hole transport layer material.

The invention also provides an anti-solvent type hole transport layer material which is obtained by the crosslinking reaction of the photosensitive compound and the polymer TFB.

Further, the mass ratio of the photosensitive compound to the polymer TFB is 1: 0.1-40, and more preferably 1: 1-20.

Further, the conditions for crosslinking are: the wavelength is 254nm or 365nm, the power is 100-1000 mW-cm^-2The ultraviolet lamp is used for illumination, and the crosslinking time is 5-240 minutes.

In the invention, a hole transport material TFB and the photosensitive compound are blended, so that the TFB with excellent solubility and the hole transport material are crosslinked to generate universal solvent resistance, thereby obtaining the high-efficiency hole transport layer of the high-performance QLED prepared by the all-solution method. The photosensitive compound seizes hydrogen atoms in active C-H in amine-containing groups under the irradiation of ultraviolet light, and forms a three-dimensional network structure through free radical coupling reaction, so that the cross-linking bonding of the material is realized, and the material can inherit or even surpass the electrical and optical properties of the original polymer hole transport material TFB or the hole transport material of the invention.

Furthermore, the invention also provides application of the anti-solvent type hole transport layer material in preparation of quantum dot electroluminescent devices.

Further, the application specifically comprises: dissolving a photosensitive compound and polymer TFB in an organic solvent, forming a film by spin coating or ink-jet printing, and then obtaining a hole transport layer of the quantum dot electroluminescent device by photo-crosslinking; the organic solvent can be at least one of toluene, m-xylene, methyl benzoate, chlorobenzene, o-dichlorobenzene, cyclohexylbenzene, indene and anisole.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention provides a photosensitive micromolecule hole transport material containing a benzophenone group and triarylamine group combination, which has proper energy level and mobility matched with a quantum dot luminescent material, can be used as a hole transport layer material of a QLED, and has device performance close to that of a device based on TFB.

2. The crosslinking type hole transport layer prepared based on the photosensitive type hole transport material and the TFB effectively overcomes the non-solvent resistance of the polymer hole transport material TFB, realizes 100 percent solvent resistance of the hole transport layer, and can effectively avoid the problem of interlayer erosion.

3. The cross-linking type hole transport layer material prepared by the invention is suitable for preparing a QLED device, is a solvent-resistant hole transport material with excellent performance, improves the compactness and high stability of a hole transport interface, can effectively improve the efficiency of the QLED device, and realizes high-quality ink-jet printing of the QLED device.

Drawings

FIG. 1 is a graph showing UV-VIS absorption spectra of films before and after crosslinking and after chlorobenzene cleaning in example 1;

FIG. 2 is a graph showing UV-VIS absorption spectra of films before and after crosslinking and after chlorobenzene cleaning in example 2;

FIG. 3 is a graph showing UV-VIS absorption spectra of films before and after crosslinking and after chlorobenzene cleaning in example 3;

FIG. 4 is the UV-VIS absorption spectra of the film of example 4 after cross-linking and before cross-linking and after chlorobenzene cleaning;

fig. 5 is a device structure view of the QLED.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.

Example 1

1. Synthesis of intermediate 1

A250 mL two-necked flask was charged with the first compound (3.12g, 10mmol), the second compound (4.38g, 22mmol), tris (dibenzylideneacetone) dipalladium (180mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (116mg, 0.4mmol), and then NaO was added to the glove box^tBu (2.40g, 25mmol), toluene (100mL) which is dehydrated and deoxidized in advance is added under the nitrogen atmosphere, the mixture reacts for 24 hours at the temperature of 100 ℃, the reaction solution is poured into ice water (200mL) after being cooled to the room temperature, dichloromethane is extracted for three times, organic phases are combined, anhydrous sodium sulfate is dried, the mixture is filtered, a solvent is dried in a spinning mode, silica gel is added for sample preparation, and column chromatography separation and purification are carried out, so that the mass of the intermediate 1 is 4.72g, light yellow powdery solid is obtained, the yield is 86%, and the theoretical relative molecular mass is as follows: 548.25 MS (EI) M/z [ M]+：548.67。

2. Synthesis of intermediate 2

Intermediate 1(4.40g,10mmol) was added to a 100mL three-necked flask under nitrogen, ultra-dry THF (100mL) was added and the reaction mixture was cooled to-20 ℃ and stirred. After 10 minutes, BBr was slowly added dropwise₃(1.0M methylene chloride solution, 22mL), after the addition, the temperature was slowly raised to room temperature and the reaction was allowed to proceed overnight. Pouring the reaction solution into ice water (200mL), extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, spin-drying a solvent, adding silica gel for sample preparation, and performing column chromatography separation and purification to obtain a fourth compound with the mass of 3.87g and a light yellow powdery solid with the yield of 74 percent, and the theoretical relative molecular mass: 520.22 MS (EI) M/z [ M]+：521.28。

3. Synthesis of target Compound 1

Intermediate 2(2.60g,5mmol) and the third compound (3.30g,12mmol) were added to a 100mL two-necked flask followed by the addition of potassium carbonate (2.07g, 15mmol) and dry DMF (50mL) and reacted under an argon atmosphere at 60 ℃ for 8 hours. Then, cooling to room temperature, pouring into 200mL of deionized water, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, spin-drying a solvent, adding silica gel for sample preparation, and performing column chromatography separation and purification to obtain the target compound 1 with the mass of 3.82g, a light yellow powdery solid with the yield of 84%, and theoretical relative molecular mass: 908.36, MS (EI) M/z [ M ] +: 909.81.

example 2

1. Synthesis of intermediate 1

A250 mL two-necked flask was charged with the first compound (6.24g, 20mmol), the second compound (10.90g, 44mmol), tris (dibenzylideneacetone) dipalladium (0.36g, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.23g, 0.8mmol), and then NaO was added to the glove box^tBu (4.80g, 50mmol), toluene (150mL) which is dehydrated and deoxidized in advance is added under the nitrogen atmosphere, the mixture reacts for 24 hours at the temperature of 100 ℃, the reaction solution is poured into ice water (300mL) after being cooled to the room temperature, dichloromethane is extracted for three times, organic phases are combined, anhydrous sodium sulfate is dried, the mixture is filtered, a solvent is dried in a spinning mode, silica gel is added for sample preparation, and column chromatography separation and purification are carried out to obtain an intermediate 1 with the mass of 9.48g and light yellow powdery solid with the yield of 73 percent, the theoretical relative molecular mass: 648.28 MS (EI) M/z [ M]+：648.77。

2. Synthesis of intermediate 2

Intermediate 1(9.73g,15mmol) was added to a 500mL three-necked flask under nitrogen, ultra-dry THF (200mL) was added and the reaction mixture was cooled to-20 ℃ and stirred. After 10 minutes, BBr was slowly added dropwise₃(1.0M methylene chloride solution, 34mL) was added dropwise, and the mixture was slowly warmed to room temperature overnight. Pouring the reaction solution into ice water (200mL), extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, spin-drying solvent, adding silica gel for sample preparation, and separating and purifying by column chromatography to obtain intermediate 2The amount was 8.29g, pale yellow solid, yield 89%, theoretical relative molecular mass: 620.50 MS (EI) M/z [ M]+：621.01。

3. Synthesis of target Compound 2

The intermediate (6.20g,10mmol) and the third compound (3.30g,22mmol) were added to a 100mL two-necked flask followed by the addition of potassium carbonate (2.07g, 15mmol) and dry DMF (50mL) and reacted under an argon atmosphere at 60 ℃ for 8 hours. Then, cooling to room temperature, pouring into 200mL of deionized water, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, spin-drying a solvent, adding silica gel for sample preparation, and performing column chromatography separation and purification to obtain the target compound 1 with the mass of 3.82g, a light yellow powdery solid with the yield of 84%, and theoretical relative molecular mass: 1008.39, MS (EI) M/z [ M ] +: 1009.41.

example 3

1. Synthesis of intermediate 1

A250 mL two-necked flask was charged with the first compound (6.24g, 20mmol), the second compound (13.88g, 44mmol), tris (dibenzylideneacetone) dipalladium (0.36g, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.23g, 0.8mmol), and then NaO was added to the glove box^tBu (4.80g, 50mmol), toluene (200mL) which is dehydrated and deoxidized in advance is added under the nitrogen atmosphere, the mixture reacts for 24 hours at the temperature of 100 ℃, the reaction solution is poured into ice water (300mL) after being cooled to the room temperature, dichloromethane is extracted for three times, organic phases are combined, anhydrous sodium sulfate is dried, the mixture is filtered, a solvent is dried in a spinning mode, silica gel is added for sample preparation, and column chromatography separation and purification are carried out to obtain an intermediate 1, wherein the mass of the intermediate 1 is 12.34g, light yellow powdery solid is obtained, the yield is 79%, and the theoretical relative molecular mass is as follows: 780.37 MS (EI) M/z [ M]+：781.65。

2. Synthesis of intermediate 2

Intermediate 1(7.81g,10mmol) was added to a 250mL three-necked flask under nitrogen, ultra-dry THF (150mL) was added and the reaction mixture was cooled to-20 ℃ and stirred. After 10 minutes, BBr was slowly added dropwise₃(1.0MDichloromethane solution, 25mL), after the dropwise addition, slowly warming to room temperature, and reacting overnight. Pouring the reaction liquid into ice water (150mL), extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, spin-drying a solvent, adding silica gel for sample preparation, and performing column chromatography separation and purification to obtain an intermediate 2 with the mass of 7.03g and a light yellow solid, wherein the yield is 93 percent, and the theoretical relative molecular mass is as follows: 752.34 MS (EI) M/z [ M]+：753.41。

3. Synthesis of target Compound 3

The intermediate (11.30g,15mmol) and the third compound (9.90g,36mmol) were added to a 500mL two-necked flask followed by the addition of potassium carbonate (5.53g, 40mmol) and dry DMF (150mL) and reacted under an argon atmosphere at 60 ℃ for 8 hours. Then, cooling to room temperature, pouring into 200mL of deionized water, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, spin-drying a solvent, adding silica gel for sample preparation, and performing column chromatography separation and purification to obtain the target compound 1 with the mass of 8.56g, a light yellow solid, the yield of 75%, and the theoretical relative molecular mass: 1141.49, MS (EI) M/z [ M ] +: 1141.65.

example 4

1. Synthesis of intermediate 1

A250 mL two-necked flask was charged with the first compound (3.52g, 10mmol), the second compound (4.78g, 24mmol), tris (dibenzylideneacetone) dipalladium (0.18g, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.12g, 0.4mmol), and then NaO was added to the glove box^tBu (2.88g, 30mmol), toluene (100mL) which is dehydrated and deoxidized in advance is added under the nitrogen atmosphere, the mixture reacts for 24 hours under the condition of 100 ℃, the reaction solution is poured into ice water (200mL) after being cooled to room temperature, dichloromethane is extracted for three times, organic phases are combined, anhydrous sodium sulfate is dried, the mixture is filtered, a solvent is dried in a spinning mode, silica gel is added for sample preparation, and column chromatography separation and purification are carried out, so that the mass of the intermediate 1 is 5.07g, a light yellow solid is obtained, the yield is 86%, and the theoretical relative molecular mass: 588.28 MS (EI) M/z [ M]+：589.01。

2. Synthesis of intermediate 2

Intermediate 1(11.78g,20mmol) was added to a 250mL three-necked flask under nitrogen, ultra-dry THF (200mL) was added and the reaction mixture was cooled to-20 ℃ and stirred. After 10 minutes, BBr was slowly added dropwise₃(1.0M methylene chloride solution, 48mL), after the addition was complete, the temperature was slowly raised to room temperature and the reaction was allowed to proceed overnight. Pouring the reaction solution into ice water (300mL), extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, spin-drying a solvent, adding silica gel for sample preparation, and performing column chromatography separation and purification to obtain an intermediate 2 with the mass of 9.87g and light yellow solid, wherein the yield is 88%, and the theoretical relative molecular mass is as follows: 560.25 MS (EI) M/z [ M]+：560.77。

3. Synthesis of target Compound 4

The intermediate (5.60g,10mmol) and the third compound (6.60g,24mmol) were added to a 250mL two-necked flask followed by the addition of potassium carbonate (4.14g, 30mmol) and dry DMF (150mL) and reacted under an argon atmosphere at 50 ℃ for 6 hours. Then, cooling to room temperature, pouring into 200mL of deionized water, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, spin-drying a solvent, adding silica gel for sample preparation, and performing column chromatography separation and purification to obtain the target compound 1 with the mass of 6.36g, a pale yellow solid with the yield of 67 percent, and the theoretical relative molecular mass: 948.39, MS (EI) M/z [ M ] +: 948.61.

through the collocation of different functional groups, the target compound provided by the embodiment of the invention has appropriate electrochemical energy level and hole mobility matched with the quantum dot luminescent material. The electrochemical energy levels of the synthesized target compounds are shown in table 1 below through theoretical simulation calculation on the target molecules.

TABLE 1

Target compoundsArticle (A)	HOMO(eV)	LUMO(eV)	Hole mobility (cm)2 V-1s-1)
				Object Compound 1	-5.82	-2.45	2.27×10-4
Target Compound 2	-5.79	-2.50	5.75×10-4
				Target Compound 3	-5.76	-2.47	9.12×10-4
Target Compound 4	-5.80	-2.55	1.87×10-4

Example 5: preparation of crosslinked films

The target compounds prepared in examples 1 to 4 were mixed with TFB, respectively, in a mass ratio of 1:1 to prepare 8mg/mL chlorobenzene solutions, spin-coated on a substrate at a rotation speed of 1500 rpm for 45 seconds, annealed at 140 ℃ for 5 minutes, then crosslinked under ultraviolet light (365nm) for 10 minutes, and then left to stand for half an hour after crosslinking annealing for sufficient cooling, and the crosslinked films were washed with toluene and chlorobenzene in sequence.

The change of the ultraviolet absorption intensity of the film before and after crosslinking and chlorobenzene cleaning is researched by adopting an ultraviolet-visible absorption spectrum, and whether the film is corroded by a solvent or not can be clearly judged. The method specifically comprises the following steps: testing the ultraviolet absorption intensity of a film before crosslinking (namely the film formed after the chlorobenzene solution of the blending material is spin-coated on a substrate and is not irradiated by ultraviolet rays and heated); the crosslinked film (i.e., the film irradiated with ultraviolet rays and heated) was washed with toluene and chlorobenzene in this order, and the ultraviolet absorption intensity of the film was measured again after the solvent was dried, and the results are shown in fig. 1 to 4.

As can be seen from the figure, the film absorption strength before crosslinking and after chlorobenzene cleaning is basically unchanged, which shows that 100% crosslinking is realized, and the hole transport layer film has excellent solvent resistance.

Example 6: preparation of quantum light emitting device

A QLED device was prepared by a solution method on the basis of the anti-solvent type hole transport layer prepared in example 5, and the device structure of the QLED was as shown in fig. 5.

The device structure is as follows: ITO (160nm)/PEDOT PSS (30nm)/HTL (25nm)/QDs (15nm)/Zn_xMg_1-xO(5nm)/Al(100nm)。

The preparation method of the device comprises the following steps: and scrubbing the ITO glass by using a glass cleaning agent, sequentially ultrasonically cleaning the ITO glass by using water and ethanol, and treating the ITO glass for 5 minutes by using oxygen plasma. And statically spin-coating PEDOT (PSS) on the surface of the ITO at the speed of 4000 revolutions per minute for 30 seconds. After the spin coating is finished, transferring the ITO sheet into a glove box to anneal for 5 minutes at 120 ℃; subsequently, the hole transport layer was spin-coated, a mixed solution of the hole transport material and the photocrosslinker (TFB and chlorobenzene solution of the hole transport material in examples 1 to 4) was dynamically spin-coated at 1800 rpm for 30 seconds, annealed at 100 ℃ for 15 minutes after the spin-coating, then crosslinked for 30 minutes under conditions of ultraviolet light (365nm) and heating at 60 ℃ for 15 minutes, and left to stand for half an hour for sufficient cooling after the crosslinking annealing. Dynamically spin-coating the quantum dot luminescent material on the anti-solvent hole transport layer at the speed of 3000 r/min for 30 seconds; and annealing for 5 minutes at 100 ℃ after the spin coating is finished, standing for 2-3 minutes, and cooling. At a speed of 3000 rpmDynamic spin coating of Zn_0.9Mg_0.1O solution, annealing at 70 ℃ for 15 minutes. After all the solution treatment layers are prepared, the sheet is transferred to a high vacuum thermal evaporation device to evaporate the aluminum of the top electrode. The evaporation rate is 3-5 angstrom/s, and the electrode thickness is 100 nm. And packaging with ultraviolet curing adhesive after evaporation.

As a control, a QLED device was prepared in the same manner with TFB, the target compound prepared in examples 1 to 4, respectively, as a hole transport layer material.

Table 2 shows the performance parameters of the red QLED devices prepared above.

TABLE 2

From the results in table 2, it can be seen that the photosensitive hole transport material provided by the present invention can be used as a hole transport layer of a QLED, and the device performance of the photosensitive hole transport material is close to that of the commercial polymer TFB.

In addition, the overall performance of the QLED device prepared by the anti-solvent type hole transport layer based on the target compounds 1-4 and TFB is remarkably improved, wherein the maximum current efficiency reaches 32.0 cd.A^-1The maximum power efficiency reaches 33.1 lm.W^-1The maximum external quantum dot efficiency reaches 20.8%, and the half-peak width and the color coordinate of the external quantum dot are inherited by 100%.

The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.