CN111995733A - Diphenyl ketone group-containing photocrosslinkable hole transport material and preparation method and application thereof - Google Patents

Diphenyl ketone group-containing photocrosslinkable hole transport material and preparation method and application thereof Download PDF

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CN111995733A
CN111995733A CN202010767667.XA CN202010767667A CN111995733A CN 111995733 A CN111995733 A CN 111995733A CN 202010767667 A CN202010767667 A CN 202010767667A CN 111995733 A CN111995733 A CN 111995733A
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crosslinking
benzophenone
hole
monomer
hole transport
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CN111995733B (en
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孙文建
尹晓宽
张清
郭小军
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Shanghai Jiaotong University
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Abstract

The invention discloses a benzophenone-group-containing photocrosslinkable hole-transport material and a preparation method and application thereof; the hole transport material is a polymer hole transport material which takes TFB as a parent nucleus and benzophenone as a crosslinking group, and has the following chemical structural formula:
Figure DDA0002615285360000011
wherein x and y are mole fractions of 0<x＜1，0＜y<1. The material film forms a three-dimensional network structure under ultraviolet radiation to realize the cross-linking of the material, and the cross-linked material with solvent resistance is obtained, so that the preparation of the luminescent device by a full-solution method is realized. Crosslinked materialThe material has high hole injection and transmission capability, the performance is obviously superior to that of a commercial TFB hole transmission material, an initiator or a catalyst is not required to be added in the photo-crosslinking method, the crosslinking time is short, no by-product is generated in the reaction process, the required ultraviolet excitation wavelength is long (365nm), the damage degree to the material is small, and the influence on the electrical and optical properties of the hole transmission material before and after crosslinking is small.

Description

Diphenyl ketone group-containing photocrosslinkable hole transport material and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic photoelectricity, in particular to a crosslinkable hole transport material, a preparation method and application thereof, and especially relates to a benzophenone-group-containing photocrosslinkable hole transport material, and a preparation method and application thereof.
Background
A quantum-dot light-emitting diode (QLED) is an electroluminescent device in which quantum dots are used as a light-emitting layer. The organic quantum dot light-emitting diode prepared based on the solution method has the advantages of high external quantum dot conversion efficiency, high brightness and color purity, wider color gamut and the like, and is more and more widely applied in the fields of flexible display, printing display and semiconductor illumination. QLED luminescence relies on electroluminescence, with holes injected from the anode and electrons injected from the cathode being transported under the influence of an electric field through a hole transport layer and an electron transport layer to the valence and conduction bands of the light emitting layer quantum dots, respectively. After relaxation, the electrons return to the LOMO energy level, and the holes return to the HOMO energy level to form excitons which radiate and emit light. The effective recombination of electrons and holes in the luminescent layer is the key for improving the luminous efficiency of the device, and the hole transport layer as an important component of the QLED can reduce the hole injection barrier, so that the holes are injected and transported to the luminescent layer from the anode in a stepped manner. Organic hole transport layers are receiving more and more attention from scientists due to their advantages such as molecular structure adjustability, flexibility and solution-processable methods.
The QLED is mainly prepared by vacuum evaporation and solution process at present. Compared with a vacuum evaporation process, the solution method preparation process, especially the ink-jet printing process, has the advantages of simple operation, high material utilization and relatively low cost, can realize the preparation of large-area devices and flexible panels, and is widely applied to the preparation of quantum dot light-emitting diodes. When the organic QLED is prepared by adopting a solution method, the problem of mixing and dissolving of the interface of the hole transport layer and the quantum dot light-emitting layer exists due to the solvent effect, and the overall performance of the device is further influenced. The orthogonal solvent and the crosslinking are two methods for solving interlayer cross-linking, organic materials generally have good solubility in common solvents, and a proper orthogonal solvent is difficult to find; and a crosslinking group is introduced to the hole transport material to realize crosslinking of the material, so that the material forms a three-dimensional network structure and can effectively resist the corrosion of an upper layer solvent. Thereby laying a foundation for preparing a high-efficiency quantum dot light-emitting device by a full-solution method.
Thermal crosslinking and photo crosslinking are two common crosslinking modes, the high crosslinking temperature in thermal crosslinking sometimes reduces the performance of the device, the crosslinking time is relatively long, most of the crosslinking temperature is higher than the glass transition temperature of a common flexible substrate, and the preparation of the flexible device cannot be carried out. Photo-crosslinking has the advantages of short crosslinking time, convenience for flexible device preparation, photoetching patterning and the like, and is used for crosslinking hole transport materials in recent years. Triarylamine hole transport materials are widely used as hole transport materials for organic electrons due to their high hole transport ability, good chemical properties, light and heat stability, good solubility and film forming ability, etc. The commercial polymer hole transport material TFB has high hole mobility (1 × 10)-3cm2V.s)), a suitable molecular orbital level (HOMO ═ 5.4eV) is a hole transport material commonly used in electroluminescent devices. However, when the QLED device is manufactured by the solution method, particularly by the inkjet printing process, TFB is dissolved by the benzene-based solvent of the quantum dot, and a high-performance stacked device cannot be obtained.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a benzophenone-group-containing photocrosslinkable hole transport material, and a preparation method and application thereof. The cross-linkable hole transport material prepared by the invention has higher hole transport capability and proper energy level, can effectively balance the injection and transport of electrons and holes, and improves the radiation recombination probability of the electrons and the holes, thereby improving the luminous efficiency. And the hole transport material with good solvent resistance can be obtained by crosslinking only by introducing less crosslinking groups into the side chain. The crosslinking process does not need a catalyst, does not generate byproducts, and has short crosslinking time.
The purpose of the invention is realized by the following technical scheme:
the first technical scheme of the invention is as follows: the invention provides a benzophenone-group-containing photo-crosslinking hole transport material TFB-BP, which has the following chemical structural formula:
Figure BDA0002615285340000021
in the formula, x and y are mole fractions, x is more than 0 and less than 1, and y is more than 0 and less than 1.
The hole transport material is a polymer hole transport material which takes TFB as a parent nucleus and benzophenone as a crosslinking group. Under ultraviolet radiation, photosensitive benzophenone generates free radicals, the free radicals extract hydrogen atoms in active C-H to form stable free radicals, a three-dimensional network structure is formed through coupling reaction among the free radicals to realize cross-linking of the material, and the cross-linking material with solvent resistance is obtained, so that the preparation of the light-emitting device by a full-solution method is realized. The cross-linked material has high hole injection and transmission capability, the performance is obviously superior to that of a commercial TFB hole transmission material, the carrier transmission balance of the luminescent material is realized, more excitons are effectively compounded, and the luminescent efficiency of the device is improved.
The second technical scheme of the invention is as follows: the invention provides a preparation method of a benzophenone-group-containing photo-crosslinking hole transport material, which comprises the following steps:
s1, reacting tri (4-bromophenyl) amine with n-butyllithium to obtain a mono-formylated bis-bromotriphenylamine monomer 1;
reducing aldehyde groups of the monomer 1 by sodium borohydride to obtain benzyl alcohol groups so as to obtain a monomer 2;
carrying out esterification reaction on the obtained monomer 2 and 3-benzoylbenzoic acid to obtain a bis-bromotriphenylamine monomer 3 containing a benzophenone group;
s2, carrying out Buchwald-Hartwig reaction on 4-n-butylaniline and p-bromoiodobenzene to obtain a double-bromo triphenylamine monomer 4 containing n-butyl;
s3, under the protection of inert gas, dissolving the dibenzoyl-containing bis-bromotriphenylamine monomer 3, the n-butyl-containing bis- bromotriphenylamine monomer 4 and 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-di-n-octylfluorene in a solvent, adding tetraethylammonium hydroxide and tetrakis (triphenylphosphine) palladium, and carrying out Suzuki coupling reaction to obtain the dibenzoyl-containing photo-crosslinking hole transport material.
Preferably, in step S3, the molar ratio of the dibenzoyl group-containing bis-bromotriphenylamine monomer 3, the n-butyl group-containing bis-bromotriphenylamine monomer 4, and the 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-di-n-octylfluorene is 0.1-1: 0.9-0: 1.
Preferably, in step S3, the tetrakis (triphenylphosphine) palladium is added in an amount of 5 wt% based on the weight of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-di-n-octylfluorene.
Preferably, in step S3, the tetraethylammonium hydroxide is 20% tetraethylammonium hydroxide aqueous solution by mass, and the volume ratio of the addition amount of the tetraethylammonium hydroxide to the addition amount of the solvent is 1: 3.6.
Preferably, in step S3, the solvent is toluene; the inert gas is nitrogen.
Preferably, in step S3, the temperature of the Suzuki coupling reaction is 85-95 ℃, and the reaction time is 72 h.
The cross-linked hole transport material prepared by the invention is suitable for preparing various organic electroluminescent display devices by a solution method, and is a cross-linked polymer hole transport material with excellent performance.
The third technical scheme of the invention is as follows: the invention provides an application of a benzophenone-group-containing photo-crosslinking hole transport material in preparing a hole transport layer of a quantum dot light-emitting diode, which comprises the steps of dissolving the benzophenone-group-containing photo-crosslinking hole transport material in an organic solvent, forming a film in a spin coating or ink-jet printing mode, and then carrying out photo-crosslinking to obtain the hole transport layer of the quantum dot light-emitting diode.
Preferably, the organic solvent is at least one of toluene, chlorobenzene, cyclohexylbenzene, indene and 3, 5-dimethyl anisole.
Preferably, the photocrosslinking condition is an ultraviolet lamp with the wavelength of 365nm, and the crosslinking time is 5-15 min.
The invention provides a crosslinkable hole transport material which is obtained by introducing crosslinkable groups into a hole transport material TFB to endow the material with crosslinking capability, and is an effective method for preparing a high-performance QLED by an all-solution method. The benzophenone-based polymer extracts hydrogen atoms in active C-H under the irradiation of ultraviolet light to form stable free radicals, and a three-dimensional network structure is formed through coupling reaction among the free radicals to realize the crosslinking of the material. The photo-crosslinking method does not need to add an initiator or a catalyst, has short crosslinking time, no by-product in the reaction process, and small damage degree to the material due to the long required ultraviolet excitation wavelength (365nm) and has small influence on the electrical and optical properties of the hole transport material before and after crosslinking.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a novel photo-crosslinking method, can realize complete crosslinking only by introducing a very small amount of crosslinking groups, and the introduction of the crosslinking groups into side chains has little influence on the photo-physical and electrochemical properties of the material.
(2) The invention adopts photosensitive cross-linking group benzophenone, no catalyst is needed in the cross-linking process, no by-product is generated, the needed ultraviolet lamp has longer cross-linking wavelength, short cross-linking time and small damage degree to materials;
(3) the crosslinked hole transport layer obtained by the invention has smooth surface and excellent thermal stability and solvent resistance.
(4) The hole transport performance of the cross-linked hole transport material obtained by the invention is superior to that of a commercial TFB material, and the good solvent resistance is beneficial to spin coating or ink-jet printing preparation of a high-performance organic electroluminescent display device, and the cross-linked hole transport material is a cross-linked polymer hole transport material with excellent performance.
(5) If the number of the crosslinking groups is increased in proportion, the organic silicon-based organic.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of the non-limiting embodiments with reference to the following drawings:
FIG. 1 shows NMR spectra of monomer 3: (1H NMR)；
FIG. 2 shows NMR spectrum of monomer 3: (13C NMR)；
FIG. 3 shows the NMR spectrum of a photo-crosslinked hole transporting material TFB-BP (1H NMR)；
FIG. 4 is a Thermogravimetric (TGA) and Differential Scanning Calorimetry (DSC) plot of a photocrosslinked hole transport material TFB-BP; wherein, figure 4a is a TGA curve; FIG. 4b is a DSC curve;
FIG. 5 is the UV-VIS absorption spectra before and after TFB-BP crosslinking;
FIG. 6 is a cyclic voltammogram before and after TFB-BP crosslinking;
FIG. 7 is the UV absorption spectra before and after immersion in chlorobenzene and toluene after TFB-BP crosslinking; wherein, FIG. 7a is an ultraviolet diagram of polymer 1 being crosslinked for 15min, FIG. 7b is an ultraviolet diagram of polymer 2 being crosslinked for 10min, and FIG. 7c is an ultraviolet diagram of polymer 3 being crosslinked for 5 min;
FIG. 8 shows device performance of red QLEDs with TFB and cross-linked TFB-BP as hole transport layers;
FIG. 9 is an ink jet printing device performance of red QLEDs with crosslinked TFB-BP hole transport layers; wherein, fig. 9a is a current density-voltage-luminance curve; FIG. 9b is a graph of luminous efficiency versus luminance versus power efficiency; FIG. 9c is an external quantum dot efficiency-luminance curve; FIG. 9d is an electroluminescence spectrum;
FIG. 10 is a current density-voltage curve for a single hole device (HOD) based on different hole materials;
FIG. 11 is a schematic view of the principle of crosslinking of a hole transport material.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1 preparation of TFB-BP
1) Preparation of monomer 1
Tris (4-bromophenyl) amine (16.00g,33.2mmol) was dissolved in anhydrous THF (88.0mL) under nitrogen, the reaction was placed in an ethanol bath at-78 ℃ with stirring, n-butyllithium (17.26mL,2.5M in hexane,43.15 mmol) was added dropwise to the reaction, and after 1h of reaction at-78 ℃, anhydrous DMF (16mL) was added to the reaction flask. After the dropwise addition, the reaction is continued for 1h at-78 ℃, the temperature of the system is restored to room temperature, the reaction is continued for 1h, and deionized water is added to quench the reaction. The mixture was extracted three times with ether, the organic phases were combined, the organic layer was washed three times with saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and the solvent was evaporated off by a rotary evaporator. The crude product was purified by silica gel column chromatography using petroleum ether/ethyl acetate (V/V, 15:1) as eluent and dried under vacuum to give a pale yellow solid (monomer 1) 5.0g, with a yield of 37%.1H NMR(500MHz,CDCl3) 9.86(s,1H),7.74(d, J ═ 9.0Hz,2H), 7.46(d, J ═ 9.0Hz,4H), 7.07-7.02 (m,6H).
Figure BDA0002615285340000061
2) Preparation of monomer 2
Monomer 1(3.840g,8.9mmol) is added into a mixed solvent of anhydrous ether (30mL) and anhydrous ethanol (30mL) and stirred uniformly, NaOH (0.1M, 9mL) containing sodium borohydride (0.1700g,4.45mmol) is slowly added into the reaction system, the reaction system is stirred at room temperature for 4h, and deionized water is added into the system. The reaction mixture was extracted with dichloromethane, the organic extract was washed three times with deionized water, dried over anhydrous sodium sulfate, evaporated under reduced pressure to remove the organic solvent, and dried under vacuum to give 3.8g of a white solid (monomer 2), with a yield of 98.8%.1H NMR(500MHz,CDCl3) 7.35-7.28 (m,6H),7.08(d, J ═ 8.0Hz,2H),6.96(d, J ═ 9.0Hz,4H),4.67(s,2H).
Figure BDA0002615285340000062
3) Preparation of monomer 3
Under the protection of nitrogen, 3-benzoylbenzoic acid (0.5200g, 2.30mmol), 4-pyrrolidinylpyridine (0.0344 g, 0.232mmol) and N, N-dicycloethylcarbodiimide (0.4800g,2.32mmol) were added to a mixed solution of dichloromethane (20 mL) and diethyl ether (5mL), and the mixture was stirred for 15 minutes to form a reaction system. A dichloromethane solution (10mL) of monomer 2(1.000g, 2.32mmol) was added dropwise into the reaction system, and the reaction was stirred at room temperature for 12 h. And (3) washing the filtrate after suction filtration with deionized water and dilute acetic acid solution for 3 times respectively, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and mixing the crude product with ethyl acetate: petroleum ether (1:3 volume ratio) as eluent was separated and purified by silica gel column, and dried in vacuum to obtain yellow solid (monomer 3)0.597g, with a yield of 40.3%. The chemical reaction equation is as follows:
Figure BDA0002615285340000063
FIG. 1 shows the NMR spectra of benzophenone-containing bis-bromotriphenylamine monomer 3 prepared in this example ((R))1H-NMR)；
FIG. 2 shows the NMR spectrum of benzophenone-containing bis-bromotriphenylamine monomer 3 prepared in this example (C: (R))13H-NMR)。
Nuclear magnetic hydrogen spectrum:1H NMR(500MHz,CDCl3):8.52(s,1H),8.32(d,J＝7.8Hz,1H),8.0(t,J ＝8.0Hz,1H),7.83(d,J＝7.7Hz,2H),7.60-7.64(m,2H),7.52(dd,J＝8.5,8.5Hz 2H), 7.35-7.38(m,6H),7.08(m,2H),6.98(t,J＝7.0Hz,4H),5.35(s,2H).
nuclear magnetic carbon spectrum:1C NMR(100MHz,CDCl3):195.7,165.7,147.1,146.2,138.0,137.0,134.2, 133.3,132.9,132.4,131.0,130.5,130.1,129.9,128.6,125.7,124.0,115.9,66.7.
4) preparation of monomer 4
Under a nitrogen atmosphere, 4-n-butylaniline (4.00g,26.8mmol), 1-bromo-4-iodobenzene (16.7g,59.0mmol), potassium hydroxide (13.7g,243mmol), 1.10-phenanthroline (0)176g,0.970mmol) and cuprous chloride (0.100g, 0.950mmol) were added to toluene (50mL) and heated at reflux for 12 h. Cooling the reaction solution to room temperature, adding saturated salt solution into the filtrate after suction filtration, extracting with toluene, drying the organic phase with anhydrous sodium sulfate, evaporating to remove the solvent, and separating and purifying the crude product with silica gel chromatographic column, wherein the eluent is n-hexane. Drying in vacuo afforded a colourless wax (monomer 4, 7.9g, 64% yield).1H NMR(500MHz,CDCl3) 7.30(dd, J is 5.5Hz, 5.5Hz 4H),7.07(d, J is 8.4Hz,2H),6.96(d, J is 8.4Hz,2H),6.90(dd, J is 5.0,5.0Hz 4H),2.56(t, J is 15.5Hz,2H), 1.63-1.52 (m,2H), 1.41-1.29 (m,2H),0.93(t, J is 14.5Hz,3H), chemical reaction equations are as follows:
Figure BDA0002615285340000071
5) preparation of hole transport Material TFB-BP (Polymer 1)
Monomer 4(0.2000g,0.432mmol), monomer 3(0.0308g,0.048mmol) and 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-di-n-octylfluorene (0.3084g,0.480mmol) were added to a 50mL polymerization tube. Tetrakis (triphenylphosphine) palladium (0.015g,12.9mmol), tetraethylammonium hydroxide (20% aq,2.8mL), three drops of methyltrioctylammonium chloride, and toluene (10mL) were then added to the system in a glove box and the mixture reacted for 72h at 95 ℃ under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, it was poured into methanol (300 mL). Filtering the obtained precipitate, sequentially performing Soxhlet extraction with methanol, petroleum ether and acetone for 48h, extracting the target product with chloroform, precipitating the extract in methanol again, filtering and drying to obtain yellow solid (TFB-BP)0.292g with yield of 87%. The chemical reaction equation is as follows:
Figure BDA0002615285340000081
FIG. 3 shows the hydrogen nuclear magnetic resonance spectrum (polymer 1) of the hole transport material TFB-BP prepared in this example1H-NMR)；
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3):7.78-7.77(m,Ar-H),7.62-7.58(m,Ar-H), 7.17(m,Ar-H),5.39(s,-CH2-),2.64(t,-CH2-),2.05(t,-CH2-),1.67-1.61(m,-CH2-), 1.45-0.76(m,-CH2-and–CH3).
6) preparation of hole transport Material TFB-BP (Polymer 2)
Monomer 4(0.2000g,0.432mmol), monomer 3(0.0693g,0.108mmol) and 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-di-n-octylfluorene (0.3469g,0.540mmol) were added to a 50mL polymerization tube. Tetrakis (triphenylphosphine) palladium (0.017g,13.9mmol), tetraethylammonium hydroxide (20% aq,2.8mL), three drops of methyltrioctylammonium chloride, and toluene (10mL) were then added to the system in a glove box and the mixture reacted for 72h at 95 ℃ under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, it was poured into methanol (300 mL). Filtering the obtained precipitate, sequentially performing Soxhlet extraction with methanol, petroleum ether and acetone for 48h, extracting the target product with chloroform, precipitating the extract in methanol again, filtering and drying to obtain yellow solid (TFB-BP)0.348g with yield of 88.9%.1H NMR(400 MHz,CDCl3):7.78-7.76(m,Ar-H),7.62-7.56(m,Ar-H),7.17(m,Ar-H),5.39(s,-CH2-), 2.64(t,-CH2-),2.05(t,-CH2-),1.67-1.61(m,-CH2-),1.45-0.78(m,-CH2-and–CH3).
Figure BDA0002615285340000091
7) Preparation of hole transport Material TFB-BP (Polymer 3)
Monomer 4(0.2000g,0.432mmol), monomer 3(0.2772g,0.432mmol) and 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-di-n-octylfluorene (0.5550g,0.864mmol) were added to a 50mL polymerization tube. Tetrakis (triphenylphosphine) palladium (0.028g,23.9mmol), tetraethylammonium hydroxide (20% aq,2.8mL), three drops of methyltrioctylammonium chloride, and toluene (10mL) were then added to the system in a glove box and the mixture reacted for 72h at 95 ℃ under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, it was poured into methanol (300 mL). The obtained precipitateFiltering the precipitate, sequentially Soxhlet extracting with methanol, petroleum ether and acetone for 48h, extracting the target product with chloroform, precipitating the extract in methanol again, filtering and drying to obtain yellow solid (TFB-BP)0.568g with yield of 84.8%.1H NMR(400 MHz,CDCl3):7.78(m,Ar-H),7.62-7.57(m,Ar-H),7.16(m,Ar-H),5.39(s,-CH2-),2.64(t, -CH2-),2.05(t,-CH2-),1.67-1.61(m,-CH2-),1.46-0.77(m,-CH2-and–CH3).
Figure BDA0002615285340000092
Example 2 thermal stability, photophysical and electrochemical Properties, solvent resistance and tables of TFB-BP hole transport materials Characterization and analysis of surface morphology
FIG. 4 is a Thermogravimetry (TGA) and a Differential Scanning Calorimetry (DSC) chart of the photo-crosslinked hole transport material TFB-BP (polymer 1) prepared in example 1, and it can be seen from FIG. 4 that the decomposition temperature of the polymer TFB-BP with the thermogravimetry fraction of 5% is 326 ℃, the glass transition temperature is 123.8 ℃, and the polymer TFB-BP has good thermal stability.
FIG. 5 shows UV-visible absorption spectra before and after crosslinking of TFB-BP (Polymer 1), wherein the initial absorption wavelengths of the film before and after crosslinking of TFB-BP were 429nm and 432nm, respectively, and the initial absorption wavelengths and the maximum absorption peak positions of both before and after crosslinking were almost unchanged, indicating that the conjugation length of TFB-BP was not changed after crosslinking. The optical band gaps (Eg) of the two films were calculated from the initial absorption wavelengths in the ultraviolet absorption spectra of the two films, and were 2.89eV and 2.87eV, respectively.
FIG. 6 is a cyclic voltammogram before and after TFB-BP (Polymer 1) crosslinking, from which it can be seen that the HOMO/LUMO values of the film before and after crosslinking are-5.38 eV/-2.49eV and-5.40 eV/-2.53eV, respectively. The hole transport material TFB-BP has similar HOMO/LOMO energy levels before and after crosslinking, which shows that the redox performance of the material is not influenced by crosslinking.
FIG. 7a is the UV absorption spectrum before and after soaking in chlorobenzene and toluene after TFB-BP (Polymer 1) crosslinking for 15min, and it can be seen from the figure that after the polymer film is crosslinked by UV irradiation under a 365nm UV lamp for 15min, the UV absorption intensity of the film before and after soaking in toluene and chlorobenzene is tested, and it can be seen that the UV absorption intensity is not significantly changed before and after soaking in a solvent, which indicates that the film with excellent solvent resistance can be obtained by complete crosslinking under the condition (the absorption intensity curve of the toluene washing is basically overlapped with the curves of the chlorobenzene washing and crosslinking TFB-BP). FIG. 7b is the UV absorption spectra before and after TFB-BP (Polymer 2) crosslinking for 10min and before and after soaking in chlorobenzene and toluene, and it can be seen that the UV absorption intensity before and after soaking in chlorobenzene is tested after the polymer film is crosslinked by UV irradiation under an ultraviolet lamp with a wavelength of 365nm for 10min, and it can be seen that the UV absorption intensity before and after soaking in solvent is not significantly changed, indicating that the film with excellent solvent resistance can be obtained by complete crosslinking under the conditions. FIG. 7c is the UV absorption spectra before and after TFB-BP (Polymer 3) crosslinking in chlorobenzene and toluene for 5min, it can be seen that when the polymer film is crosslinked by UV irradiation under 365nm UV for 5min, the UV absorption intensity of the film before and after chlorobenzene soaking is tested, and it can be seen that the UV absorption intensity before and after solvent soaking is not significantly changed, indicating that the film with excellent solvent resistance can be obtained by complete crosslinking under the condition.
FIG. 11 is a schematic diagram of the cross-linking principle of the TFB-BP hole transport material prepared by the present invention.
In conclusion, the photo-crosslinking TFB hole transport material provided by the invention only needs to introduce a few crosslinking groups into side chains, and the preparation of the crosslinked hole transport material under the conditions of normal temperature, no metal catalyst and no byproducts is realized on the premise of not influencing the intrinsic performance of the material, and the obtained material is used as a hole transport layer material and is suitable for QLEDs (quantum dots light emitting diodes) prepared by a solution method. The main contribution of the invention lies in that fewer photocrosslinking groups are introduced to realize the anti-solvent hole transport material with higher hole transport performance, and the problem that the prior TFB can not adopt non-orthogonal solvent to prepare the high-performance quantum dot light-emitting diode is solved. The preparation process is simple, the obtained material has excellent hole transport performance, is suitable for preparing high-performance QLEDs by a solution method, and has wide application prospect.
Example 3 preparation and characterization of Single hole devices (HODs) based on different hole transport materials
In order to verify that a cross-linked material TFB-BP has high hole transport performance, a single-hole device is prepared on the basis of TFB, uncrosslinked TFB-BP and cross-linked TFB-BP, and the structure of the device is as follows: ITO (160nm)/PEDOT PSS (32 nm)/HTL (25nm)/QDs (15nm)/MoO3(2nm)/Al(100nm)。
FIG. 8 is a current density-voltage curve of a single hole device (HOD) based on different hole transport materials, and it can be seen that the current densities before and after TFB-BP photo-crosslinking are lower than those of a reference TFB at low voltage, and low leakage current is shown; the crosslinked TFB-BP (polymer 1) has a lower leakage current than before crosslinking (TFB-BP in fig. 8), due to the fact that the crosslinked film is more dense and can effectively prevent leakage current; when the voltage is more than 2.1V, the current density of the cross-linked TFB-BP is higher than that of the reference TFB, which indicates that the cross-linked TFB-BP film has higher hole mobility; meanwhile, the hole-electron balance is more favorable.
EXAMPLE 4 preparation of Quantum dot light emitting diodes based on Cross-linkable hole transport materials containing benzophenone groups Prepare for
The control was poly [ (9, 9-di-N-octylfluorenyl-2.7-diyl) -alt- (4, 4' - (N- (4-N-butyl) phenyl) -diphenylamine (TFB) hole transport material.
And (3) carrying out ultrasonic cleaning on Indium Tin Oxide (ITO) glass sequentially by using deionized water, acetone and isopropanol, and then carrying out oxygen plasma treatment on the precleaned ITO glass for 3 min. PEDOT: the PSS (Baytron PVP Al 4083) solution is filtered through a 0.45 mu m nylon filter head and then is spin-coated on a precleaned ITO glass substrate, the rotating speed is 4000rpm, and the time is 45 s; annealing at 150 deg.C for 15min to remove residual water, transferring into glove box (O)2<1ppm,H2O<1ppm), then TFB-BP or TFB in chlorobenzene solution (10mg/mL) was spin coated at 3000rpm for 30s spin coating parameters on PEDOT: annealing the PSS surface and TFB-BP spin-coated device on a hot plate at 140 ℃ for 20min, and irradiating the device under an LED ultraviolet lamp with the wavelength of 365nm for 15minAnd min, performing crosslinking. The quantum dots were dispersed in n-octane to make a 15mg/mL solution, which was spin coated onto the crosslinked HTL at 3000rpm with spin coating parameters of 30 s. Zn0.95Mg0.05O nanocrystals (ethanol solution, 30mg/mL) were then spin coated onto the surface of the quantum dot layer at 3000rpm for 30s, followed by annealing at 80 ℃ for 15 min. And finally, depositing an Al electrode on the surface of the electron transport layer through vacuum evaporation to obtain the QLED prepared by the solution method. In the ink-jet printing device, the HTL is dissolved in a chlorobenzene solvent to form a film through spin coating, the quantum dots are dissolved in cyclohexylbenzene and n-tetradecane to prepare ink for ink-jet printing to form a film, and other parameters and other layers are prepared as described above.
Based on a crosslinked TFB-BP hole transport material (polymer 1), red, green and blue three-primary-color QLEDs are prepared, and the prepared quantum dot light-emitting device has the following structure: ITO/PEDOT PSS (30nm)/HTL (25nm)/QDs (15 nm)/Zn0.9Mg0.1O (50nm)/Al (100nm), since the red light device has significantly improved performance, the performance of the red light device is summarized below.
The optoelectronic properties of quantum dot light emitting devices based on TFB and TFB-BP hole transport layers are shown in table 1.
TABLE 1 optoelectronic Properties of Quantum dot light emitting devices based on TFB-BP hole transport layers of different thicknesses
Figure BDA0002615285340000121
As can be seen from Table 1, compared with the photoelectric performance of the quantum dot light-emitting device using the commercial TFB as the hole transport layer, the overall performance of the quantum dot device based on the TFB-BP is obviously improved, wherein the maximum current efficiency reaches 32.3cd A-1Maximum power efficiency up to 42.3lm W-1The maximum external quantum dot efficiency reaches 21.4 percent.
Device performance of red QLEDs based on TFB and TFB-BP as hole transport layers: the current density-voltage-luminance (J-V-L), external quantum dot efficiency-luminance (EQE-L), power efficiency-luminance-current efficiency (PE-L-CE) characteristic curves and electroluminescence spectra are shown in FIG. 9. As can be seen from the figure, based onThe turn-on voltage of the red devices of the cross-linked TFB-BP, respectively, was 1.8V, which was lower (1.9V) than the TFB-based devices. The maximum external quantum dot efficiency of the red light device based on the crosslinked TFB-BP is 21.4 percent respectively; the current efficiencies are respectively 32.3cd A-1(ii) a Power efficiency of 42.3lm W-1。
Device performance of red inkjet printed QLEDs based on crosslinked TFB-BP as hole transport layer: the current density-voltage-luminance (J-V-L), external quantum dot efficiency-luminance (EQE-L), power efficiency-luminance-current efficiency (PE-L-CE) characteristic curves and electroluminescence spectra are shown in FIG. 10. As can be seen from the figure, the maximum external quantum dot efficiency of the red-light printing devices based on crosslinked TFB-BP was 18.1%, respectively; the current efficiencies are respectively 26.5cd A-1(ii) a Power efficiency of 37.8lm W-1。
Compared with the performances of a red light device based on commercial TFB and a red light device based on cross-linked TFB-BP, the overall performance of the device based on the cross-linked material is obviously superior to the performance of the device based on the commercial TFB, and the result shows that the cross-linked TFB-BP film has higher hole injection and transmission capacity and electron blocking capacity, and can improve the efficiency of effective recombination of holes and electrons in a quantum dot layer, thereby improving the performance of the device. This result is consistent with the single hole device results of the characterization analysis of fig. 8.
Compared with the performances of the spin-coated red light QLED device (figure 9) and the ink-jet printed red light QLED device (figure 10), the external quantum dot efficiency of the ink-jet printed device is close to the efficiency of the spin-coated device, and the result shows that the cross-linked TFB-BP has excellent solvent resistance and hole transmission performance, so that the cross-linked TFB-BP can form a more compact film, the leakage current is effectively reduced, and the material mobility is improved.
The corresponding test performance of the single-hole device and the quantum dot light-emitting diode prepared by using the polymers 2 and 3 in the embodiment 1 is equal to or better than that of the device prepared by using the polymer 1.
The results of the examples of the invention show that the overall performance of the red devices based on the crosslinked TFB-BP hole transport material is significantly higher than that of the devices based on the commercial TFB. The reason for improving the performance of the crosslinked TFB-BP device is that the crosslinked TFB-BP has good hole injection and transmission capability, so that electrons and holes are injected into a light-emitting layer more in balance, and the electron hole radiation recombination efficiency is higher. The performance of the red light ink-jet printing device based on the crosslinked TFB-BP hole transport material is equivalent to that of a spin coating device, and the crosslinked TFB-BP has excellent solvent resistance and hole transport performance.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (10)

1. A benzophenone-group-containing photo-crosslinking hole transport material is characterized in that the chemical structural formula of the material is as follows:
Figure FDA0002615285330000011
in the formula, x and y are mole fractions, x is more than 0 and less than 1, and y is more than 0 and less than 1.
2. A method for producing the benzophenone-group-containing photocrosslinkable hole-transporting material of claim 1, comprising the steps of:
s1, reacting tri (4-bromophenyl) amine with n-butyllithium to obtain a mono-formylated bis-bromotriphenylamine monomer 1;
reducing aldehyde groups of the monomer 1 by sodium borohydride to obtain benzyl alcohol groups so as to obtain a monomer 2;
carrying out esterification reaction on the obtained monomer 2 and 3-benzoylbenzoic acid to obtain a bis-bromotriphenylamine monomer 3 containing a benzophenone group;
s2, carrying out Buchwald-Hartwig reaction on 4-n-butylaniline and p-bromoiodobenzene to obtain a double-bromo triphenylamine monomer 4 containing n-butyl;
s3, under the protection of inert gas, dissolving the dibenzoyl-containing bis-bromotriphenylamine monomer 3, the n-butyl-containing bis-bromotriphenylamine monomer 4 and 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-di-n-octylfluorene in a solvent, adding tetraethylammonium hydroxide and tetrakis (triphenylphosphine) palladium, and carrying out Suzuki coupling reaction to obtain the dibenzoyl-containing photo-crosslinking hole transport material.
3. The method for preparing the benzophenone-group-containing photo-crosslinking hole-transporting material according to claim 2, wherein in step S3, the molar ratio of the benzophenone-group-containing bis-bromotriphenylamine monomer 3, the n-butyl-containing bis-bromotriphenylamine monomer 4, and the 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-di-n-octylfluorene is 0.1-1: 0.9-0: 1.
4. The method for producing a benzophenone-based photo-crosslinkable hole transporting material of claim 2 wherein in step S3 the amount of tetrakis (triphenylphosphine) palladium added is 5 wt% based on the weight of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-di-n-octylfluorene.
5. The method according to claim 2, wherein the tetraethylammonium hydroxide in step S3 is 20% tetraethylammonium hydroxide aqueous solution, and the volume ratio of the amount of tetraethylammonium hydroxide added to the amount of solvent added is 1: 3.6.
6. The method for producing a benzophenone-group containing photo-crosslinking hole-transporting material according to claim 2 wherein in step S3 the solvent is toluene; the inert gas is nitrogen.
7. The method for preparing a benzophenone group containing photo-crosslinking hole transporting material of claim 2 wherein in step S3 the temperature of the Suzuki coupling reaction is 85 ℃ to 95 ℃ and the reaction time is 72 h.
8. The use of the benzophenone-group-containing photocrosslinkable hole-transporting material of claim 1 in the preparation of a hole-transporting layer of a quantum dot light-emitting diode, which comprises dissolving the benzophenone-group-containing photocrosslinkable hole-transporting material in an organic solvent, forming a film by spin coating or ink-jet printing, and then photocrosslinking to obtain the hole-transporting layer of the quantum dot light-emitting diode.
9. The use of the benzophenone-group containing photo-crosslinking hole transport material of claim 8, wherein the organic solvent is at least one of toluene, chlorobenzene, cyclohexylbenzene, indene, 3, 5-dimethylanisole.
10. The use of the benzophenone-group-containing photocrosslinkable hole transporting material of claim 8, wherein the photocrosslinking condition is an ultraviolet lamp with a wavelength of 365nm, and the crosslinking time is 5-15 min.
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CN112952014B (en) * 2021-04-14 2024-04-19 北京京东方技术开发有限公司 Light emitting diode and preparation method thereof, display panel and preparation method thereof
CN113861050A (en) * 2021-09-23 2021-12-31 材料科学姑苏实验室 Photosensitive compound, anti-solvent type hole transport layer material prepared from photosensitive compound and application of anti-solvent type hole transport layer material
CN113861050B (en) * 2021-09-23 2023-08-18 材料科学姑苏实验室 Photosensitive compound, anti-solvent type hole transport layer material prepared from photosensitive compound and application of photosensitive compound

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