CN117003729B - 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 PDF

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CN117003729B
CN117003729B CN202311278750.0A CN202311278750A CN117003729B CN 117003729 B CN117003729 B CN 117003729B CN 202311278750 A CN202311278750 A CN 202311278750A CN 117003729 B CN117003729 B CN 117003729B
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light
auxiliary material
organic electroluminescent
emitting auxiliary
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CN117003729A (en
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汪康
李贺
王春梅
任卫华
张雪
李金磊
华伟东
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention belongs to the technical field of organic electroluminescent materials, and provides a luminescent auxiliary material, a preparation method thereof and an organic electroluminescent device, wherein the structural general formula of the luminescent auxiliary material is shown in the specification. The compound of the invention is that the 3-position of phenyl substituted dibenzothiophene and the 2-position of phenyl substituted dimethylfluorene are simultaneously connected with triarylamine, and the other group of the triarylamine is Ar with specific substituent group 1 Has higher capacitance than the prior art. As an auxiliary light-emitting material, the compound not only can reduce the driving voltage of the organic electroluminescent device, but also can greatly prolong the service life.

Description

Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device
Technical Field
The invention belongs to the field of organic electroluminescent materials, and particularly relates to a luminescent auxiliary material, a preparation method thereof and an organic electroluminescent 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 electric energy is converted into light energy by using an organic substance. 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. Particularly, the service life and the driving voltage of the OLED are not obviously improved, the performance of the material often needs to be greatly debugged and improved in structure to enable the performance of the device to reach an ideal state, and the material manufacturer can improve partial performance indexes such as capacitance, evaporation form, color cast and the like to achieve the purpose of improving the performance of the organic electroluminescent device.
Therefore, how to develop a light-emitting auxiliary material with long service life and low driving voltage, a preparation method thereof and an organic electroluminescent device 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 and a preparation method thereof, and the light-emitting auxiliary material is applied to a specific light-emitting device, and has low driving voltage, high light-emitting efficiency and long service life.
It should be noted that, for organic electroluminescent devices with different colors, the device has different requirements on the size of the capacitor, wherein the red organic electroluminescent device needs a larger capacitor. The compound of the invention is that the 3-position of phenyl substituted dibenzothiophene and the 2-position of phenyl substituted dimethylfluorene are simultaneously connected with triarylamine, and the other triarylamineAr with a radical of a specific substituent 1 The resulting compounds have a higher capacitance than the prior art. As an auxiliary light-emitting material, the compound not only can reduce the driving voltage of the organic electroluminescent device, but also can greatly prolong the service life.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the first technical purpose of the invention is to provide a luminescent auxiliary material, wherein the structural general formula of the luminescent auxiliary material is shown as formula I:
；
in formula I:
Ar 1 independently selected from one of the following structures:
。
* Representing the position of the radical attachment.
The substitution positions are defined as follows:
。
further, the light-emitting auxiliary material specifically has the following structure, but is not limited thereto:
/>
。
a second technical object of the present invention is to provide a method for preparing the above-mentioned light-emitting auxiliary material, which can be prepared by synthetic methods known to those skilled in the art. Alternatively, the following reaction scheme is preferred for preparation, the specific synthetic route being as follows:
；
the specific preparation method comprises the following steps:
step 1) after reactant a (1.0 eq) and reactant b (1.1-1.5 eq) were completely dissolved in xylene in a round bottom flask under nitrogen protection, base (2.0-2.5 eq), palladium catalyst (0.01-0.05 eq), phosphine ligand (0.02-0.15 eq) were added thereto, and then the resultant was heated to 130-140 ℃ and stirred for 8-12 hours. Filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were dried over magnesium sulfate and the remaining material was purified by column chromatography to afford intermediate c.
Step 2) after intermediate c (1.0 eq) and reactant d (1.1-1.5 eq) were completely dissolved in xylene in a round bottom flask under nitrogen protection, base (2.0-2.5 eq), palladium catalyst (0.01-0.05 eq), phosphine ligand (0.02-0.15 eq) were added thereto, and then the resultant was heated to 130-140 ℃ and stirred for 8-12 hours. Filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were dried over magnesium sulfate and the remaining material was purified by column chromatography to give formula i.
In the above, ar 1 Hal as defined in formula I above 1 、Hal 2 Each independently selected from chlorine, bromine or iodine.
In particular, those skilled in the art can employ classical Suzuki coupling reactions and/or Buchwald-Hartwig coupling reactions to synthesize and apply to the present invention, as opposed to starting materials not disclosed.
Alternatively, the palladium catalyst is at least selected from Pd 2 (dba) 3 Tris (dibenzylideneacetone) dipalladium, pd (PPh) 3 ) 4 Tetrakis (triphenylphosphine) palladium, pdCl 2 Palladium dichloride, pdCl 2 (dppf) 1,1' -bis (diphenylphosphino) ferrocene Palladium dichloride, pd (OAc) 2 Palladium acetate, pd (PPh) 3 ) 2 Cl 2 One of bis (triphenylphosphine) palladium dichloride;
the phosphine ligand comprises PPh 3 Triphenylphosphine, P (t-Bu) 3 Tri-tert-butylphosphine, X-phos 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropylbiphenyl, PET 3 Triethylphosphine, PMe 3 Trimethylphosphine, PPh 3 Triphenylphosphine, KPPh 2 Potassium diphenyl phosphate;
the alkali at least comprises AcOK potassium acetate, K 2 CO 3 、K 3 PO 4 、Na 2 CO 3 、CsF、Cs 2 CO 3 One of t-Buona tert-butoxide sodium.
The invention also discloses application of the luminescent auxiliary material in preparation of an organic electroluminescent device.
Specifically, the organic electroluminescent device includes a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode; and, in addition, the method comprises the steps of,
the organic layer at least comprises one of 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 and a cap layer; and, in addition, the method comprises the steps of,
the light-emitting auxiliary layer contains the light-emitting auxiliary material.
And, the organic electroluminescent device of the invention can be used in an organic electroluminescent device.
Such organic electroluminescent devices include, but are not limited to, flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signals, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, photo books, personal Digital Assistants (PDAs), wearable devices, notebook computers, digital cameras, video cameras, viewfinders, micro-displays, three-dimensional displays, virtual or augmented reality displays, video walls including a plurality of displays tiled together, theatre or venue screens, phototherapy devices, and signs.
Compared with the prior art, the invention has the following beneficial effects:
the compound of the invention is that the 3-position of phenyl substituted dibenzothiophene and the 2-position of phenyl substituted dimethylfluorene are simultaneously connected with triarylamine, and the other group of the triarylamine is Ar with specific substituent group 1 The resulting compounds have a higher capacitance than the prior art. As an auxiliary light-emitting material, the compound not only can reduce the driving voltage of the organic electroluminescent device, but also can greatly prolong the service life.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a compound 30 prepared in example 1 of the present invention.
Fig. 2 is a capacitance test chart of comparative example 12 and application example 15.
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 embodiment of the invention discloses a preparation method of a luminescent auxiliary material.
In addition, it should be noted that the numerical values set forth in the following examples are as precise as possible, but those skilled in the art will understand that each numerical value should be construed as a divisor rather than an absolute precise numerical value due to measurement errors and experimental operation problems that cannot be avoided.
EXAMPLE 1 Synthesis of Compound 30
；
CAS: reactants a-30:2770667-11-1
CAS reactants b-30:2758134-82-4
N 2 Pd (OAc) after the reaction vessel was charged with reactants a-30 (1.0 eq) and b-30 (1.3 eq) dissolved in xylene under protection 2 (0.02 eq), X-Phos (0.05 eq), t-Buona (2.2 eq); after the addition, the reaction temperature is raised to 130 ℃, and the mixture is stirred for 12 hours; filtering with diatomaceous earth, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and filtering with ethyl acetateEster extraction of the aqueous phase; the combined organic layers were dried over magnesium sulfate and purified by column chromatography to give intermediate c-30 (yield: 82.6%, test value MS (ESI, M/Z): [ M+H ]]+= 543.48）。
N 2 Under protection, after adding intermediate c-30 (1.0 eq) and reactant d-30 (1.2 eq) to the reaction vessel and dissolving in xylene, pd was added 2 (dba) 3 （0.02eq）、P(t-Bu) 3 (0.04 eq), t-Buona (2.4 eq); after the addition, the reaction temperature is raised to 130 ℃, and the mixture is stirred for 10 hours; 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 dried over magnesium sulfate and purified by column chromatography to give compound 30 (yield: 86.1%, test value MS (ESI, M/Z): [ M+H ]]+= 695.52）。
The nuclear magnetic resonance hydrogen spectrum of compound 30 is shown in fig. 1.
Characterization:
HPLC purity: > 99.7%.
Elemental analysis:
theoretical value: c, 88.02; h, 5.36; n, 2.01; s, 4.61
Test value: c, 87.87; h, 5.48; n, 2.07; s, 4.65
EXAMPLE 2 Synthesis of Compound 168
；
CAS reactants a-168:2554964-52-0
CAS reactants b-168:2033140-75-7
N 2 Pd (OAc) after the reaction vessel was charged with reactants a-168 (1.0 eq) and b-168 (1.2 eq) dissolved in xylene under protection 2 (0.02 eq), X-Phos (0.04 eq), t-Buona (2.3 eq); after the addition, the reaction temperature is raised to 130 ℃, and the mixture is stirred for 12 hours; filtering with diatomaceous earth, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting with ethyl acetateTaking a water phase; the combined organic layers were dried over magnesium sulfate and purified by column chromatography to give intermediate c-168 (yield: 78.6%, test value MS (ESI, M/Z): [ M+H ]]+= 543.37）。
N 2 Under protection, after adding intermediate c-168 (1.0 eq) and reactant d-168 (1.3 eq) to the reaction vessel and dissolving in xylene, pd was added 2 (dba) 3 （0.02eq）、P(t-Bu) 3 (0.05 eq), t-Buona (2.2 eq); after the addition, the reaction temperature is raised to 130 ℃, and the mixture is stirred for 10 hours; 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 dried over magnesium sulfate and purified by column chromatography to give compound 168 (yield: 81.9%, test value MS (ESI, M/Z): [ M+H ]]+= 709.41）。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 86.29; h, 4.97; n, 1.97; o, 2.25; s, 4.52
Test value: c, 86.08; h, 5.14; n, 2.01; o, 2.30; s, 4.57
Examples 3 to 35
The compounds of formula I were prepared by the synthetic methods of examples 1-2 and their molecular formulas and mass spectra are shown in table 1 below.
Table 1 molecular formula and mass spectrum
Further, since other compounds of the present application can be obtained by referring to the synthetic methods of the examples listed above, they are not exemplified herein. The mass spectrometer model adopted in the mass spectrum test is Waters XEVO TQD, and the ESI source test is low-precision.
An organic electroluminescent device has a structure including one or more of 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, and a capping layer as an organic layer. The structure of the organic light emitting element is not limited thereto, and includes a smaller or larger number of organic layers.
The compound shown in the formula I prepared by the invention is used as a light-emitting auxiliary material.
In the case of manufacturing an organic light-emitting device, the compound represented by formula I is used to form an organic layer by vacuum vapor deposition or solution coating. Among them, the solution coating method includes spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, but is not limited thereto.
The organic light emitting element of the present invention is classified into a top emission type, a bottom emission type, or a bi-directional emission type according to the materials used.
The device of the present invention is used in organic electroluminescent devices including, but not limited to, flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, photo books, personal Digital Assistants (PDAs), wearable devices, notebook computers, digital cameras, video cameras, viewfinders, micro-displays, three-dimensional displays, virtual reality or augmented reality displays, vehicles, video walls including 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 selected so that holes can be smoothly injected into the organic layer. Specific examples of the anode material which can be used in the present invention include vanadium, chromium, copper, zinc, gold, or an alloy thereof; metal oxides zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO); combination of metal and oxide ZnO A1 or SnO 2 Sb; polypyrrole, polyaniline and other conductive polymers.
The hole injection layer selects a p-doped hole injection layer, which means a hole injection layer doped with a p-dopant. A p-dopant is a material capable of imparting p-type semiconductor characteristics. The p-type semiconductor property means a property of injecting holes or transporting holes at the HOMO level, that is, a property of a material having high hole conductivity.
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 is a material having high hole mobility, and is selected from the group consisting of arylamine derivatives, conductive polymers, and block copolymers in which conjugated portions and non-conjugated portions are simultaneously present.
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 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 comprises a host material and a dopant material, and the mass ratio of the host material to the dopant material is 90-99.5:0.5-10.
The main body material is aromatic condensed ring derivative or heterocyclic compound. Specifically, the aromatic condensed ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, or a fluoranthene compound, and the heterocyclic compound includes a carbazole derivative, a dibenzofuran derivative, or a pyrimidine derivative.
The dopant material of the present invention includes fluorescent doping and phosphorescent doping, and is specifically selected from aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds or metal complexes.
The electron transport layer may function to promote electron transport, the electron transport material being a material that advantageously receives electrons from the cathode and transports the electrons to the light emitting layer, in particular selected from materials having high electron mobility; and 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 and have an ability to transport electrons to prevent 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, 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 alloys thereof, metal complexes, or nitrogen-containing 5-membered ring derivatives.
The cathode is made of a material having a small work function so that electrons are smoothly injected into the organic material layer, which has a thickness of between 0.5 and 5 nm. Specifically, the cathode material includes magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof: liF/A1 or LiO 2 And (3) A1, mg/Ag multilayer structure substance.
Other layer materials in the OLED device are not particularly limited except that the disclosed light-emitting auxiliary layer includes formula I. Existing hole injection materials, hole transport auxiliary materials, dopant materials, hole blocking layer materials, electron transport layer materials, and electron injection materials may be used.
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 red organic electroluminescent device preparation:
a. ITO anode: washing ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 14nm/150nm/14nm in distilled water for 2 times, washing with ultrasonic waves for 30min, washing with distilled water repeatedly for 2 times, washing with ultrasonic waves for 10min, transferring into a spin dryer for spin drying after washing, baking with a vacuum oven at 220 ℃ for 2 hours, and cooling after baking is finished to use; 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): vacuum evaporating the hole injection layer materials HT and P-dopant at an evaporation rate of 1 Å/s, wherein the chemical formulas are shown as follows; and the evaporation rate ratio of HT to P-dock is 95:5, the thickness is 10nm;
c. HTL (hole transport layer): vacuum evaporating 135nm HT as a hole transport layer on the hole injection layer at an evaporation rate of 1.5 Å/s;
d. prime (light-emitting auxiliary layer): vacuum evaporating the compound 3 of the present invention as a light-emitting auxiliary material at a deposition rate of 0.5 Å/s over the hole transport layer at 90 nm;
e. EML (light emitting layer): on the light-emitting auxiliary layer, a Host material (Host) and a doping material (dopent) with a thickness of 40nm were vacuum-evaporated as light-emitting layers at an evaporation rate of 1 Å/s, wherein the chemical formulas of Host and dopent are as follows, and the evaporation rate ratio of Host and dopent is 97:3.
f. HB (hole blocking layer): HB with a thickness of 5.0nm was vacuum deposited as a hole blocking layer on top of the light emitting layer at a deposition rate of 0.5. 0.5 Å/s.
g. ETL (electron transport layer): vacuum evaporating ET and Liq with thickness of 30nm on the hole blocking layer as electron transport layer at evaporation rate of 1 Å/s; wherein the chemical formulas of ET and Liq are shown as follows, and the evaporation rate ratio of ET and Liq is 50:50.
h. EIL (electron injection layer): an electron injection layer was formed by vacuum deposition of a Yb film layer of 1.0nm on the electron transport layer at a deposition rate of 0.5 Å/s.
i. And (3) cathode: and vacuum evaporating magnesium and silver on the electron injection layer at an evaporation rate ratio of 1 Å/s of 13nm, wherein the evaporation rate ratio is 1:9, so as to obtain the OLED device.
j. Light extraction layer: CPL having a thickness of 60nm was vacuum deposited on the cathode at a deposition rate of 1 Å/s as a light extraction layer, wherein the chemical formula of CPL is shown below.
k. 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 materials required for each layer are as follows:
。
device application examples 2 to 71
The organic electroluminescent devices of application examples 2 to 71 were prepared according to the above-described preparation method of the organic electroluminescent device, except that compound 3 of application example 1 was replaced with the corresponding compound (as shown in table 2), respectively, to form a light-emitting auxiliary layer.
Device comparative examples 1 to 17
The organic electroluminescent devices of comparative examples 1 to 17 were prepared according to the above-described preparation method of the organic electroluminescent device, except that compound 3 in application example 1 was replaced with comparative compound 1 to comparative compound 17, and the structural formula of comparative compound 1 to comparative compound 17 was as follows:
。
the organic electroluminescent devices obtained in the above device application examples 1 to 71 and device comparative examples 1 to 17 were characterized in terms of driving voltage, luminous efficiency, life span, and capacitance at 6000 (nits) luminance, and the test results are shown in table 2 below:
TABLE 2 luminescence property test results (brightness value 6000 nits)
/>
The capacitance requirements of the devices for the organic electroluminescent devices with different colors are different, the capacitance is required to be larger in the red organic electroluminescent device, the capacitance of the red organic electroluminescent devices obtained by application examples 1-71 and comparative compounds 1-17 is tested, an impedance analyzer is adopted, the bias voltage is started to be-2V and the end voltage is 4V under 1000Hz, and the capacitance test is carried out under the condition of scanning step length of 0.04V, and the test results are shown in Table 2. Wherein FIG. 2 is a capacitance test chart of comparative example 12, application example 15.
From the capacitance test results, the capacitance of the comparative compounds 1-7 is about 3.42-3.58nF, and the substitution positions on the aromatic amine-linked dimethylfluorene and dibenzothiophene are different compared with the compound of the present invention; comparative compounds 10-14, having a capacitance of about 3.15-3.30nF, do not all have substituted phenyl groups on dimethylfluorene and dibenzothiophene as compared to the compounds of the present invention; comparative compounds 8-9, comparative compounds 15-17 have a capacitance of about 2.65-2.80nF, and the substitution positions and substituted phenyl groups on dimethylfluorene and dibenzothiophene are different from the present invention; application example 1 to application example 60, application example 71, ar used for the compound of the present invention 1 Ar used in application examples 61 to 70 of the compound of the present invention was aryl, having a capacitance of about 4.30 to 4.55nF 1 Is heteroaryl and has a capacitance of about 4.00 nF to about 4.20nF.
Under the same device test condition, the capacitance of the compound affects the voltage and the service life, and in a red light device, the compound has large capacitance, and a large number of research tests show that the whole device has low driving voltage and the service life of the device is greatly prolonged. The driving voltage of comparative examples 1-7 was 3.50-3.53V, and the lifetime was 1467-1488h; the driving voltage of comparative examples 10-14 was 3.55-3.58V, and the life was 1444-1457h; comparative examples 8 to 9, comparative examples 15 to 17 had a driving voltage of 3.62 to 3.66V and a lifetime of 1405 to 1420h; the driving voltage of application examples 1-60 and 71 is 3.31-3.36V, and the service life is 1634-1677h; the driving voltage of application examples 61-70 is 3.40-3.46V, and the service life is 1548-1588h; the service life is improved by at least 60h, and is prolonged by 233h at most, so that the service life is obviously improved.
In the production and research, material manufacturers can debug the structure of the compound through a large number of experimental screening to achieve the purpose of changing the performance of a certain aspect of the compound, so that the voltage, the service life and the efficiency of the organic electroluminescent device are beyond the expected effects,the compound of the invention is that the 3-position of phenyl substituted dibenzothiophene and the 2-position of phenyl substituted dimethylfluorene are simultaneously connected with triarylamine, and the other group of the triarylamine is Ar with specific substituent group 1 The resulting compounds have higher capacitance than the prior art. And has the effects of reducing the driving voltage and remarkably prolonging the service life of the device.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (6)

1. The luminous auxiliary material is characterized by having a structural general formula shown in formula I:
；
in the formula I, the compound (I),
Ar 1 independently selected from one of the following structures:
。
2. the light-emitting auxiliary material according to claim 1, wherein the light-emitting auxiliary material is selected from any one of compounds represented by the following structural formulae:
。
3. a method for preparing a luminescent auxiliary material as claimed in claim 1, characterized in that the method comprises in particular the following steps:
(1) After 1.0eq of reactant a and 1.1-1.5eq of reactant b are completely dissolved in xylene in a round bottom flask under the protection of nitrogen, 2.0-2.5eq of base, 0.01-0.05eq of palladium catalyst and 0.02-0.15eq of phosphine ligand are added, and then the obtained product is heated to 130-140 ℃ and stirred for 8-12 hours; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding 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 afford intermediate c;
(2) After 1.0eq of intermediate c and 1.1-1.5eq of reactant d were completely dissolved in xylene in a round bottom flask under nitrogen protection, 2.0-2.5eq of base, 0.01-0.05eq of palladium catalyst, 0.02-0.15eq of phosphine ligand were added, and the resultant was heated to 130-140 ℃ and stirred for 8-12 hours; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were dried over magnesium sulfate and the remaining material was purified by column chromatography to give formula i;
the specific synthetic route is as follows:
；
wherein,
Hal 1 、Hal 2 each independently selected from chlorine, bromine or iodine;
Ar 1 having the definition as defined in claim 1.
4. The method for preparing a light-emitting auxiliary material according to claim 3, wherein the palladium catalyst is at least one selected from the group consisting of tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, palladium dichloride, 1' -bis (diphenylphosphino) ferrocene palladium dichloride, palladium acetate, and bis (triphenylphosphine) palladium dichloride;
the phosphine ligand comprises triphenylphosphine, tri-tert-butylphosphine, 2-dicyclohexyl phosphorus-2, 4, 6-triisopropylbiphenyl, triethylphosphine, trimethylphosphine and potassium diphenylphosphate;
the alkali at least comprises AcOK, K 2 CO 3 、K 3 PO 4 、Na 2 CO 3 、CsF、Cs 2 CO 3 One of t-BuONa.
5. Use of a light-emitting auxiliary material according to claim 1 for the preparation of an organic electroluminescent device.
6. The use according to claim 5, wherein the organic electroluminescent device comprises a first electrode, a second electrode, one or more organic layers interposed between the first electrode and the second electrode; and, in addition, the method comprises the steps of,
the organic layer at least comprises one of 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 and a cap layer; and, in addition, the method comprises the steps of,
the light-emitting auxiliary layer contains the light-emitting auxiliary material.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109293516A (en) * 2018-11-03 2019-02-01 长春海谱润斯科技有限公司 A kind of tri-arylamine group compound and its organic luminescent device
CN113620818A (en) * 2021-08-12 2021-11-09 长春海谱润斯科技股份有限公司 Triarylamine compound containing condensed ring and organic light-emitting device thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109293516A (en) * 2018-11-03 2019-02-01 长春海谱润斯科技有限公司 A kind of tri-arylamine group compound and its organic luminescent device
CN113620818A (en) * 2021-08-12 2021-11-09 长春海谱润斯科技股份有限公司 Triarylamine compound containing condensed ring and organic light-emitting device thereof

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