CN116063293B - Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device - Google Patents
Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device Download PDFInfo
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Abstract
The invention discloses a luminescent auxiliary material, a preparation method thereof and an organic electroluminescent device, which belong to the technical field of organic light electroluminescent materials, and the structural general formula of the luminescent auxiliary material is shown in the specification: wherein Ar is 1 ，Ar 2 Each independently selected from the groups shown in the specification. The compound obtained by the invention is used as a material of the light-emitting auxiliary layer, so that the service life of the organic electroluminescent device is greatly prolonged under the condition that the efficiency is kept and the driving voltage is not affected. Dibenzofuran has a high triplet energy level, and is more suitable as a HOMO/LUMO energy level between the blue light emitting auxiliary layer material and the blue light emitting layer. The triarylamine material is used as a light-emitting auxiliary layer, so that the effect of improving mobility is achieved. The ortho-folding of benzene ring and dibenzofuran on 9-phenyl-9H-carbazole makes the space structure more distorted, and greatly prolongs the service life of the device.
Description
Technical Field
The invention belongs to the technical field of organic light-emitting materials, and particularly relates to a light-emitting auxiliary material, a preparation method thereof and an organic light-emitting device.
Background
Organic electroluminescence (OLED) is a type of self-luminous display element, and a display has advantages of high brightness, high resolution, wide viewing angle, low power consumption, and high response speed. In general, organic electroluminescence refers to a phenomenon in which an organic substance converts electric energy into light energy. An organic light emitting element utilizing an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic layer therebetween. Such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL).
In order to solve the lifetime and efficiency problems, a light-emitting auxiliary layer (multi-layer hole transport layer) is generally added between the hole transport layer and the light-emitting layer. The light-emitting auxiliary layer mainly functions as an auxiliary hole transport layer, and is therefore sometimes also referred to as a second hole transport layer. The light-emitting auxiliary layer can enable holes transferred from the anode to smoothly move to the light-emitting layer, and can block electrons transferred from the cathode so as to limit the electrons in the light-emitting layer, reduce potential barriers between the hole-transporting layer and the light-emitting layer, reduce driving voltage of the organic electroluminescent device, further increase utilization rate of the holes, and improve luminous efficiency and service life of the device.
But there are few materials that can form a light emitting auxiliary layer and have excellent device performance. In particular, the service life and luminous efficiency of the OLED are not obviously improved, so it is important to develop higher-performance organic functional materials to meet the requirements of panel manufacturing enterprises.
Therefore, how to develop a light-emitting auxiliary material with high light-emitting efficiency and long service life, a preparation method thereof and an organic electroluminescent device for improving driving voltage are technical problems to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a light-emitting auxiliary material, a method for preparing the same, and an organic electroluminescent device.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the 1,4 positions of the dibenzofuran are respectively connected with triarylamine and 9-phenyl-9H-carbazole, wherein the benzene ring on the 9-phenyl-9H-carbazole is connected with the dibenzofuran in an ortho-position substitution mode. The obtained compound is used as a material of the light-emitting auxiliary layer, so that the service life of the organic electroluminescent device is greatly prolonged under the condition that the efficiency is kept and the driving voltage is not influenced.
The structural general formula of the light-emitting auxiliary material is shown as formula I or formula II:
wherein, the liquid crystal display device comprises a liquid crystal display device,
Ar 1 ，Ar 2 each independently selected from the group shown below:
* Representing the position of the radical attachment.
The substitution positions are defined as follows:
further, the above-mentioned light-emitting auxiliary material is selected from any one of the compounds represented by the following structural formulas:
the invention also provides a preparation method of the luminescent auxiliary material, which comprises the following steps:
(1)N 2 under the protection, adding the reactants A-I, the reactants B-I, a palladium catalyst and alkali into a mixed solvent of toluene, ethanol and water, heating for reaction, cooling to room temperature, and adding H 2 Filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-I;
(2)N 2 under the protection, adding an intermediate C-I and a reactant D-I into a reaction vessel, dissolving in dimethylbenzene, and adding a palladium catalyst, a phosphine ligand and alkali; after the addition, the reaction temperature is slowly raised, and the mixture is stirred; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; drying the combined organic layers with magnesium sulfate, and purifying the remaining materials by column chromatography to obtain a compound shown in formula I;
the synthetic route of formula I:
r' isOr->
Or, the method comprises the following steps:
①N 2 under protection, adding the reactant A-II, the reactant B-II, the palladium catalyst and the alkali toIn a mixed solvent of toluene, ethanol and water, heating for reaction, cooling to room temperature, adding H 2 Filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-II;
②N 2 under the protection, adding an intermediate C-II and a reactant D-II into a reaction vessel, dissolving in dimethylbenzene, and adding a palladium catalyst, a phosphine ligand and alkali; after the addition, the reaction temperature is slowly raised, and the mixture is stirred; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; drying the combined organic layers with magnesium sulfate, and purifying the remaining material by column chromatography to obtain a compound represented by formula II;
a synthetic route of formula II:
/>
r' isOr->
Further, in the step (1), the molar ratio of the reactants A-I, the reactants B-I, the palladium catalyst and the alkali is 1.0 (1-1.2): 0.01-0.02): 2.0-2.3;
in the step (2), the molar ratio of the intermediate C-I, the reactant D-I, the palladium catalyst, the phosphine ligand and the alkali is 1.0 (1.1-1.3): 0.01-0.05): 0.02-0.15): 2.0-2.4;
in the step (1), the mol ratio of the reactant A-II, the reactant B-II, the palladium catalyst and the alkali is 1.0 (1-1.2): 0.01-0.02): 2.0-2.3;
in the step (2), the molar ratio of the intermediate C-II, the reactant D-II, the palladium catalyst, the phosphine ligand and the alkali is 1.0 (1.1-1.3), 0.01-0.05, 0.02-0.15 and 2.0-2.4.
Further, in the mixed solvent of toluene, ethanol and water, the volume ratio of toluene, ethanol and water is (2-4): 1:1.
Further, in the step (1), the temperature is raised to 80-100 ℃ and the reaction is carried out for 8-12 hours; in the step (2), after the addition, the reaction temperature is slowly increased to 130-140 ℃, and the mixture is stirred for 8-12 hours; in the step (1), the temperature is raised to 80-100 ℃ and the reaction is carried out for 8-12 hours; in the step (2), the reaction temperature is slowly raised to 130-140 ℃ after the addition, and the mixture is stirred for 8-12h.
Further, the palladium catalyst is Pd 2 (dba) 3 、Pd(PPh 3 ) 4 、PdCl 2 、PdCl 2 (dppf)、Pd(OAc) 2 、Pd(PPh 3 ) 2 Cl 2 Or NiCl 2 One or more of (dppf);
the phosphine ligand is P (t-Bu) 3 、X-phos、PET 3 、PMe 3 、PPh 3 、KPPh 2 Or P (t-Bu) 2 One or more of Cl;
the above base is K 2 CO 3 、K 3 PO 4 、Na 2 CO 3 、CsF、Cs 2 CO 3 Or one or more of t-Buona.
The invention also provides an organic electroluminescent device, which comprises the luminescent auxiliary material or the luminescent auxiliary material prepared by the method.
Further, the organic electroluminescent device comprises one or a combination of several layers of a hole injection layer, a hole transport layer, an electron blocking layer, a luminescent auxiliary layer, a luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer or a capping layer, wherein the luminescent auxiliary layer comprises the luminescent auxiliary material or the luminescent auxiliary material prepared by the method.
Further, the organic electroluminescent device is formed with an organic layer by a vacuum evaporation method or by a solution coating method, which is a spin coating method, a dip coating method, a blade coating method, an inkjet printing method, a screen printing method, a spray method, or a roll coating method.
Further, the above-described organic electroluminescent device includes a top emission type, a bottom emission type, or a bi-directional emission type.
The invention has the beneficial effects that: the invention respectively connects triarylamine and 9-phenyl-9H-carbazole at 1,4 positions of dibenzofuran, wherein a benzene ring on the 9-phenyl-9H-carbazole is connected with the dibenzofuran in an ortho-position substitution mode. The obtained compound is used as a material of the light-emitting auxiliary layer, so that the service life of the organic electroluminescent device is greatly prolonged under the condition that the efficiency is kept and the driving voltage is not influenced.
Dibenzofuran has a high triplet energy level, and is more suitable as a HOMO/LUMO energy level between the blue light emitting auxiliary layer material and the blue light emitting layer. The triarylamine material is used as a light-emitting auxiliary layer, so that the effect of improving mobility is achieved. The ortho-folding of the benzene ring on 9-phenyl-9H-carbazole with dibenzofuran makes the spatial structure more distorted, and according to the two planes of distortion, the crystallinity may be reduced due to the reduction of intermolecular interactions. Thus, the melting point of the compound is lowered, thereby enabling to reduce clogging in deposition, on the one hand lowering the deposition temperature of the compound and, on the other hand, reducing the decomposition of the compound at too high a deposition temperature. Namely, in the preparation process of the organic electroluminescent device, the thermal stability is increased, and the service life of the device is greatly prolonged.
Drawings
FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of intermediate C-22.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 22.
FIG. 3 is a three-dimensional structure of compound 67 and comparative compounds 1-3.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention carries out a series of palladium catalytic coupling reactions, on one hand, utilizes the difference that the activity of Br is larger than that of Cl, on the other hand, controls the reaction sites by controlling the reaction conditions, and uses column chromatography or silica gel funnel purification reaction to remove byproducts, thus obtaining the target compound. The following are referred to in the common general knowledge:
transition metal organic chemistry (original sixth edition), robert H-crabtree (RobertH. Crabtree), press: publication time of Shanghai Shandong university Press: 2017-09-00, ISBN:978-7-5628-5111-0, page 388.
Organic chemistry and photoelectric Material Experimental Instructions, chen Runfeng, press: university of east south Press, publication time: 2019-11-00, ISBN:9787564184230, page 174.
Example 1: synthesis of Compound 22
CAS: reactant B-22:2183475-72-9
N 2 Under the protection, the reactant A-22 (50 mmol), the reactant B-22 (60 mmol), the tetrakis (triphenylphosphine) palladium (0.5 mmol) and the potassium carbonate (110 mmol) are respectively added into a mixed solvent of toluene, ethanol and water (150 mL:50 mL), the temperature is raised to 90 ℃, the reaction is carried out for 10 hours, the temperature is cooled to room temperature, and H is added 2 And O, filtering after the solid is precipitated, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-22. (17.54 g, yield: 76%, theory: 443.93, test MS (ESI, M/Z): [ M+H ]] + ＝444.14)。
The nuclear magnetic resonance hydrogen spectrum of the intermediate C-22 is shown in figure 1:
N 2 after the addition of intermediate C-22 (35 mmol) and reactant D-22 (38.5 mmol) in xylene (200 mL) to the reaction vessel under protection, pd (OAc) was added 2 (0.7 mmol), X-Phos (1.4 mmol), t-BuONa (77 mmol); after the addition, the reaction temperature was slowly raised to 135 ℃ and the mixture was stirred for 10h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature,adding distilled water into the filtrate for washing, separating the liquid, retaining an organic phase, and extracting the water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the remaining material was purified by column chromatography to give compound 22. (20.92 g, yield: 82%, theory: 728.90, test MS (ESI, M/Z): [ M+H ]] + ＝729.16)。
The nuclear magnetic resonance hydrogen spectrum of compound 22 is shown in fig. 2:
characterization:
HPLC purity: > 99.7%.
Elemental analysis:
theoretical value: c,88.98; h,4.98; n,3.84; o,2.19
Test value: c,88.83; h,5.12; n,3.92; o,2.23
Example 2: synthesis of Compound 59
Intermediate C-22 and intermediate C-59 have the same reaction route;
N 2 after the intermediate C-59 (35 mmol) and the reactant D-59 (38.5 mmol) were added to the reaction vessel and dissolved in xylene (200 mL) under protection, pd (OAc) was added 2 (0.7 mmol), X-Phos (1.4 mmol), t-BuONa (77 mmol); after the addition, the reaction temperature was slowly raised to 130 ℃, and the mixture was stirred for 10h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the remaining material was purified by column chromatography to give compound 59. (20.82 g, yield: 75%, theory: 792.94, test MS (ESI, M/Z): [ M+H)] + ＝793.12)。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c,87.86; h,4.58; n,3.53; o,4.04
Test value: c,87.55; h,4.77; n,3.65; o,4.11
Example 3: synthesis of Compound 95
CAS: reactant B-95:2252237-87-7
N 2 Under the protection, the reactant A-95 (50 mmol), the reactant B-95 (60 mmol), the tetrakis (triphenylphosphine) palladium (0.5 mmol) and the potassium carbonate (110 mmol) are respectively added into a mixed solvent of toluene, ethanol and water (150 mL:50 mL), the temperature is raised to 95 ℃, the reaction is carried out for 10 hours, the temperature is cooled to room temperature, and H is added 2 And O, filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-95. (17.32 g, yield: 78%, theory: 443.93, test MS (ESI, M/Z): [ M+H ]] + ＝444.23)。
N 2 After the intermediate C-95 (35 mmol) and the reactant D-95 (38.5 mmol) were dissolved in xylene (200 mL) and Pd (OAc) was added to the reaction vessel under protection 2 (0.7 mmol), X-Phos (1.4 mmol), t-BuONa (77 mmol); after the addition, the reaction temperature was slowly raised to 135 ℃ and the mixture was stirred for 10h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the remaining material was purified by column chromatography to give compound 95. (23.45 g, yield: 86%, theory: 778.96, test MS (ESI, M/Z): [ M+H ]] + ＝779.21)。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c,89.43; h,4.92; n,3.60; o,2.05
Test value: c,89.21; h,5.09; n,3.64; o,2.13
Example 4: synthesis of Compound 97
The reaction route of the intermediate C-97 is consistent with that of the intermediate C-95;
N 2 after the intermediate C-97 (35 mmol) and the reactant D-97 (38.5 mmol) were added to the reaction vessel and dissolved in xylene (200 mL) under protection, pd (OAc) was added 2 (0.7 mmol), X-Phos (1.4 mmol), t-BuONa (77 mmol); after the addition, the reaction temperature was slowly raised to 135 ℃ and the mixture was stirred for 10h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the remaining material was purified by column chromatography to give compound 97. (22.55 g, yield: 80%, theory: 804.99, test MS (ESI, M/Z): [ M+H)] + ＝805.32)。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c,89.52; h,5.01; n,3.48; o,1.99
Test value: c,89.37; h,5.13; n,3.52; o,2.04
Examples 5 to 53
The synthesis of the following compounds, whose molecular formulas and mass spectra are shown in table 1 below, was accomplished with reference to the synthesis methods of examples 1 to 4.
Table 1 molecular formula and mass spectrum
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Further, since other compounds of the present invention can be obtained by referring to the synthetic methods of the above-described examples, they are not exemplified herein.
The present invention provides an organic electroluminescent device having a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, etc. as an organic layer. However, the structure of the organic light emitting element is not limited thereto, and may include a smaller or larger number of organic layers.
According to one embodiment of the present specification, the compound of formula I prepared according to the present invention is used as a light-emitting auxiliary layer material.
In the case of manufacturing an organic light-emitting device, the compound represented by the formula I is formed into an organic layer by vacuum vapor deposition or by +solution coating. The solution coating method is, but not limited to, spin coating, dip coating, blade coating, ink jet printing, screen printing, spray coating, roll coating, and the like.
The organic light emitting element of the present invention is of a top emission type, a bottom emission type or a bi-directional emission type depending on the materials used.
The device of the present invention may be used in organic light emitting devices including, but not limited to, flat panel displays, computer monitors, a medical monitor, a television, billboards, a light for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, a laser printer, a telephone, a cell phone, a tablet, a photo album, a Personal Digital Assistant (PDA), a wearable device, a notebook, a digital camera, a video camera, a viewfinder, a micro-display, a three-dimensional display, a virtual reality or augmented reality display, a vehicle, a video wall comprising a plurality of displays tiled together, theatre or venue screens, phototherapy devices, and signs.
As the anode material, a material having a large work function is generally selected so that holes can be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO A1 or SnO 2 A combination of metals such as Sb and the like and oxides; and conductive polymers such as polypyrrole and polyaniline.
The hole injection layer employs a material that advantageously receives holes from the anode at low voltages, and the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, and polyaniline-based and polythiophene-based conductive polymer, etc., but are not limited thereto, and further include additional compounds capable of p-doping.
The hole transporting material is a material capable of receiving holes from the anode or the hole injecting layer and transporting the holes to the light emitting layer, and has high hole mobility. The hole transporting material is selected from arylamine derivatives, conductive polymers, block copolymers having conjugated portions and non-conjugated portions.
A light-emitting auxiliary layer (multilayer hole-transporting layer) is interposed between the hole-transporting layer and the light-emitting layer. The light-emitting auxiliary layer mainly functions as an auxiliary hole transport layer, and is therefore sometimes also referred to as a second hole transport layer. The light emitting auxiliary layer enables holes transferred from the anode to smoothly move to the light emitting layer, and can block electrons transferred from the cathode to confine electrons in the light emitting layer, reduce potential barrier between the hole transporting layer and the light emitting layer, reduce driving voltage of the organic electroluminescent device, further increase utilization ratio of holes, thereby improving luminous efficiency and lifetime of the device.
The electron blocking layer is disposed between the hole transport layer and the light emitting layer. As the electron blocking layer, materials known in the art, such as an arylamine-based organic material, may be used.
The light-emitting substance of the light-emitting layer is a substance capable of receiving holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combining them to emit light in the visible light region, and a substance having high quantum efficiency for fluorescence or phosphorescence is selected.
The light emitting layer includes a host material and a dopant material.
The mass ratio of the host material to the doping material is 90-99.5:0.5-10.
The host material includes aromatic condensed ring derivatives, heterocyclic compounds, and the like. Specifically, examples of the aromatic condensed ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocyclic compound include carbazole derivatives, dibenzofuran derivatives, and pyrimidine derivatives.
The dopant materials of the present invention include fluorescent doping and phosphorescent doping. Selected from aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes.
The hole blocking layer may be disposed between the electron transport layer and the light emitting layer, and materials known in the art, such as triazine-based compounds, may be used.
The electron transport layer may function to facilitate electron transport. The electron transporting material is a material that advantageously receives electrons from the cathode and transports the electrons to the light emitting layer, and a material having high electron mobility is selected. The electron transport layer comprises an electron buffer layer, a hole blocking layer and an electron transport layer.
The electron injection layer may function to promote electron injection. Has an ability to transport electrons, and prevents excitons generated in the light emitting layer from migrating to the hole injection layer. The material of the electron injection layer includes, but is not limited to, metal such as oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylmethane, anthrone, their derivatives, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, ytterbium, or their alloys, metal complexes, nitrogen-containing 5-membered ring derivatives, and the like.
The cathode is made of a material having a small work function so that electrons are smoothly injected into the organic material layer, and the layer thickness of the layer is 0.5-5nm. The cathode material is usually selected to have a small work function so that electrons can be easily injected into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof: liF/A1, liO2/A1, mg/Ag and other multilayer structural materials.
In addition to the inclusion of formula I in the light emitting auxiliary layers disclosed herein, existing hole injection materials, hole transport auxiliary materials, dopant materials, hole blocking layer materials, electron transport layer materials, and electron injection materials are used for other layer materials in OLED devices.
The organic electroluminescent composition and the organic electroluminescent device according to the present invention are described in detail below with reference to specific examples.
Application example 1 preparation of organic electroluminescent device:
a. ITO anode: washing ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing with ultrasonic waves for 30min, washing with distilled water for 2 times repeatedly, washing with ultrasonic waves for 10min, baking with a vacuum oven at 220 ℃ for 2 hours after washing, and cooling after baking is finished, so that the glass substrate can be used. The substrate is used as an anode, a vapor deposition device process is performed by using a vapor deposition machine, and other functional layers are sequentially vapor deposited on the substrate.
b. HIL (hole injection layer): to be used forThe vacuum evaporation of the hole injection layer materials HT and P-dopant is performed, and the chemical formulas are shown below. The evaporation rate ratio of HT to P-dock is 97:3, the thickness is 10nm;
c. HTL (hole transport layer): to be used forVacuum evaporating 120nm HT as a hole transport layer on the hole injection layer;
d. prime (light-emitting auxiliary layer): to be used forVacuum evaporating 10nm of the compound 1 of the present invention as a light-emitting auxiliary layer on top of the hole transport layer;
e. EML (light emitting layer): then put onOn the light-emitting auxiliary layer toThe Host material (Host) and the Dopant material (Dopant) having a thickness of 25nm were vacuum-deposited as light-emitting layers, and the chemical formulas of Host and Dopant are shown below. Wherein the evaporation rate ratio of Host to Dopant is 97:3.
f. HB (hole blocking layer): to be used forIs used for vacuum evaporation of a hole blocking layer with a thickness of 5.0 nm.
g. ETL (electron transport layer): to be used forET and Liq having a thickness of 35nm were vacuum-deposited as electron transport layers. Wherein the evaporation rate ratio of ET to Liq is 50:50.
h. EIL (electron injection layer): to be used forThe vapor deposition rate of Yb film layer was 1.0nm to form an electron injection layer.
i. And (3) cathode: to be used forThe vapor deposition rate ratio of magnesium and silver is 18nm, and the vapor deposition rate ratio is 1:9, so that the OLED device is obtained.
j. Light extraction layer: to be used forCPL with a thickness of 70nm was vacuum deposited on the cathode as a light extraction layer.
k. And packaging the substrate subjected to evaporation. Firstly, a gluing device is adopted to carry out a coating process on a cleaned cover plate by UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to vapor deposition is placed at the upper end of the cover plate, and finally the substrate and the cover plate are bonded under the action of a bonding device, and meanwhile, the UV glue is cured by illumination.
The device structure is as follows:
ITO/Ag/ITO/HT P-Dopant (10 nm, 3%)/HT (120 nm)/prime (formula I) (10 nm)/Host: dopant
(25nm,3％)/HB(5nm)/ET:Liq(35nm,50％)/Yb(1nm)/Mg:Ag(18nm,1:9)/CPL(70nm)。
Application examples 2 to 53
The organic electroluminescent devices of application examples 2 to 53 were prepared according to the above-described preparation method of the organic electroluminescent device, except that compound 1 of application example 1 was replaced with the corresponding compound, respectively, to form a light-emitting auxiliary layer.
Comparative example 1
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 in application example 1 was replaced with comparative compound 1, wherein the structural formula of comparative compound 1 is as follows:
comparative example 2
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 2, wherein the structural formula of comparative compound 2 is as follows:
comparative example 3
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 3, wherein the structural formula of comparative compound 3 is as follows:
comparative example 4
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 4, wherein the structural formula of comparative compound 4 is as follows:
comparative example 5
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 5, wherein the structural formula of comparative compound 5 is as follows:
comparative example 6
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 6, wherein the structural formula of comparative compound 6 is as follows:
comparative example 7
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 7, wherein the structural formula of comparative compound 7 is as follows:
comparative example 8
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 8, wherein the structural formula of comparative compound 8 is as follows:
comparative example 9
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 9, wherein the structural formula of comparative compound 9 is as follows:
the organic electroluminescent devices obtained in the above device examples 1 to 53 and device comparative examples 1 to 9 were characterized in terms of driving voltage, luminous efficiency, BI value and lifetime at a luminance of 1000 (nits), and the test results are shown in table 2 below:
TABLE 2 luminescence property test results (brightness value 1000 nits)
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It is known to those skilled in the art that the energy level of the light-emitting auxiliary layer is matched with the light-emitting layer and the hole-transporting layer, and the target value to be adjusted is different for different light-emitting layers. The difference is larger for the light emitting layers of different colors. Even with the same blue light, there is a significant difference for different host, dopant materials.
The blue light organic electroluminescent device is influenced by microcavity effect, and the luminous efficiency is greatly influenced by chromaticity, so that a BI value is introduced as the basis of the efficiency of the blue light luminescent material, and BI=luminous efficiency/CIEy. And the problem of short lifetime of blue devices has been one of the problems that those skilled in the art are urgent to solve in the art.
As can be seen from table 2, compared with the existing organic electroluminescent devices provided in comparative examples 1 to 9, the organic electroluminescent devices prepared using the blue light emitting auxiliary materials provided in the examples 1 to 53 have a lifetime of generally 200 to 250 hours, and the comparative compound has a technical effect of improving driving voltage and efficiency while exhibiting an ultra-long device lifetime at 150 hours.
Wherein, compared with the comparative compounds 1-3, the compound 67 provided by the embodiment of the invention adopts the substitution mode that phenyl on 9-phenyl-9H-carbazole is connected with dibenzofuran in ortho position. The spatial structure of the compound constituted by the ortho-fold is distorted, whereas the compound constituted by the comparative compound 1 (para position on the benzene ring) is distorted to a low degree in space, and the crystallinity may be lowered due to a decrease in intermolecular interaction depending on the two planes of the distortion. Thus, the melting point of the compound is lowered, thereby enabling to reduce clogging in deposition, on the one hand lowering the deposition temperature of the compound and, on the other hand, reducing the decomposition of the compound at too high a deposition temperature. That is, the thermal stability is increased during the manufacturing process of the organic electroluminescent device. Fig. 3 shows three-dimensional structures of the organic electroluminescent compound 67 of the present invention and the comparative compounds 1 to 3. The spatial structure of compound 67 exhibits a highly folded state with a large degree of distortion. The service life of the compound 67 device reaches 201h, the service life of the comparative compounds 1-3 is increased by 30% at about 150h, and meanwhile, the driving voltage is improved.
Between the compound 1 and the comparative compound 5 and the comparative compound 6, the space structure of the compound caused by ortho-folding is more distorted, and the service life of the device is greatly prolonged. Compound 1 had a lifetime of 247 hours, which was about 100 hours longer and about 68% longer than comparative compound 5, comparative compound 6.
According to the analysis of the result of the device data, in the compound disclosed by the invention, the 1-position of dibenzofuran is connected with the phenyl on 9-phenyl-9H-carbazole, so that the obtained service life effect is more remarkable and is generally 230-250 hours; the 4-position of dibenzofuran is connected with phenyl on 9-phenyl-9H-carbazole, the service life is prolonged to be about 200V, and the driving voltage is reduced by about 0.1V.
It can be seen that within the scope of the present invention, the position of the phenyl substitution on 9-phenyl-9H-carbazole, despite the presence of similar species, directly affects the degree of spatial distortion of the compound, affecting the device performance in its organic electroluminescence. The compound of the formula I is respectively connected with triarylamine and 9-phenyl-9H-carbazole at the 1,4 positions of dibenzofuran, wherein the benzene ring on the 9-phenyl-9H-carbazole is connected with the dibenzofuran in an ortho-position substitution mode. The obtained compound is used as a material of the light-emitting auxiliary layer, so that the service life of the organic electroluminescent device is greatly prolonged under the condition that the efficiency is kept and the driving voltage is not influenced.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The luminous auxiliary material is characterized by having a structural general formula shown in formula I or formula II:
wherein, the liquid crystal display device comprises a liquid crystal display device,
Ar 1 ，Ar 2 each independently selected from the group shown below:
* Representing the position of the radical attachment.
2. A light-emitting auxiliary material according to claim 1, wherein the light-emitting auxiliary material is selected from any one of the compounds represented by the following structural formulae:
3. a method for preparing a luminescent auxiliary material as claimed in any one of claims 1-2, characterized by comprising the steps of:
(1)N 2 under the protection, adding the reactants A-I, the reactants B-I, a palladium catalyst and alkali into a mixed solvent of toluene, ethanol and water, heating for reaction, cooling to room temperature, and adding H 2 Filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-I;
(2)N 2 under the protection, adding an intermediate C-I and a reactant D-I into a reaction vessel, dissolving in dimethylbenzene, and adding a palladium catalyst, a phosphine ligand and alkali; after the addition, the reaction temperature is slowly raised, and the mixture is stirred; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; drying the combined organic layers with magnesium sulfate, and purifying the remaining materials by column chromatography to obtain a compound shown in formula I;
the synthetic route of formula I:
r' is
Or, the method comprises the following steps:
①N 2 under the protection, adding the reactant A-II, the reactant B-II, a palladium catalyst and alkali into a mixed solvent of toluene, ethanol and water, heating for reaction, cooling to room temperature, and adding H 2 Filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-II;
②N 2 under the protection, adding an intermediate C-II and a reactant D-II into a reaction vessel, dissolving in dimethylbenzene, and adding a palladium catalyst, a phosphine ligand and alkali; after the addition, the reaction temperature is slowly raised, and the mixture is stirred; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; drying the combined organic layers with magnesium sulfate, and purifying the remaining material by column chromatography to obtain a compound represented by formula II;
a synthetic route of formula II:
r' is
4. A method for producing a light-emitting auxiliary material according to claim 3, wherein in the step (1), the molar ratio of the reactants a to I, the reactants B to I, the palladium catalyst and the base is 1.0 (1 to 1.2): 0.01 to 0.02): 2.0 to 2.3;
in the step (2), the molar ratio of the intermediate C-I, the reactant D-I, the palladium catalyst, the phosphine ligand and the alkali is 1.0 (1.1-1.3): 0.01-0.05): 0.02-0.15): 2.0-2.4;
in the step (1), the mol ratio of the reactant A-II to the reactant B-II to the palladium catalyst to the alkali is 1.0 (1-1.2): 0.01-0.02): 2.0-2.3;
in the step (2), the mol ratio of the intermediate C-II, the reactant D-II, the palladium catalyst, the phosphine ligand and the alkali is 1.0 (1.1-1.3): 0.01-0.05): 0.02-0.15): 2.0-2.4.
5. A method of preparing a luminescent auxiliary material according to claim 3, wherein in step (1), the temperature is raised to 80-100 ℃ and the reaction is carried out for 8-12 hours; in the step (2), after the addition, the reaction temperature is slowly increased to 130-140 ℃, and the mixture is stirred for 8-12 hours; in the step (1), the temperature is raised to 80-100 ℃ and the reaction is carried out for 8-12h; in step (2), the reaction temperature is slowly raised to 130-140 ℃ after the addition, and the mixture is stirred for 8-12h.
6. A method for preparing a luminescent auxiliary material according to claim 3, wherein the palladium catalyst is Pd 2 (dba) 3 、Pd(PPh 3 ) 4 、PdCl 2 、PdCl 2 (dppf)、Pd(OAc) 2 Or Pd (PPh) 3 ) 2 Cl 2 One or more of the following;
the phosphine ligand is P (t-Bu) 3 、X-phos、PET 3 、PMe 3 、PPh 3 、KPPh 2 Or P (t-Bu) 2 One or more of Cl;
the alkali is K 2 CO 3 、K 3 PO 4 、Na 2 CO 3 、CsF、Cs 2 CO 3 Or one or more of t-Buona.
7. An organic electroluminescent device comprising a luminescent auxiliary material as claimed in any one of claims 1 to 2 or a luminescent auxiliary material prepared by a method as claimed in any one of claims 3 to 6.
8. An organic electroluminescent device as claimed in claim 7, comprising one or a combination of several layers of hole injection layer, hole transport layer, electron blocking layer, light emitting auxiliary layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer or capping layer, the light emitting auxiliary layer comprising the light emitting auxiliary material according to any one of claims 1 to 2 or the light emitting auxiliary material prepared by the method according to any one of claims 3 to 6.
9. The organic electroluminescent device according to claim 8, wherein the organic electroluminescent device is formed with a vacuum evaporation method or with a solution coating method, which is a spin coating method, a dip coating method, a doctor blading method, an inkjet printing method, a screen printing method, a spray method, or a roll coating method.
10. The organic electroluminescent device according to claim 8, wherein the organic electroluminescent device comprises a top emission type, a bottom emission type, or a bi-directional emission type.
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