CN115872959B - Light-emitting auxiliary material, preparation method and application thereof, and light-emitting device - Google Patents
Light-emitting auxiliary material, preparation method and application thereof, and light-emitting device Download PDFInfo
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Abstract
The invention discloses a luminescent auxiliary material, a preparation method and application thereof, and a luminescent device, which belong to the field of organic light electroluminescent materials, wherein the structural general formula of the luminescent auxiliary material is as shown in a chemical formula I:
the method comprises the steps of carrying out a first treatment on the surface of the Wherein n is selected from 1 or 2; m is selected from 0, 1 or 2; ar is condensed with an adjacent benzene ring; ar is selected from substituted or unsubstituted C6-C30 aryl. The luminescent auxiliary material provided by the invention is based on aromatic ring benzofurans, substituent groups exist on the aromatic ring, the aromatic ring benzofurans are directly connected with aromatic amine, one of the substituent groups on the aromatic amine is dibenzofuran, and the substituent groups exist on the benzene ring where the dibenzofuran is connected with the aromatic amine. The luminescent auxiliary material provided by the invention has the characteristics of reducing the driving voltage of the organic electroluminescent device, effectively improving the luminous efficiency and prolonging the service life of the device, and the like.
Description
Technical Field
The invention relates to the field of organic light electroluminescent materials, in particular to a luminescent auxiliary material, a preparation method and application thereof, and a luminescent device.
Background
Organic electroluminescence (OLED) is a type of self-luminous display element, and 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 using an organic light emitting phenomenon generally has a structure including an anode and a cathode with 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-layered 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.
However, 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.
Disclosure of Invention
The invention provides a luminescent auxiliary material, which is based on aromatic ring benzofurans, wherein substituent groups exist on the aromatic ring, benzene rings of the aromatic ring benzofurans are directly connected with aromatic amines, one of the substituent groups on the aromatic amines is dibenzofuran, and substituent groups exist on the benzene rings where the dibenzofuran is connected with the aromatic amines. The organic electroluminescent device prepared by the luminescent auxiliary material provided by the embodiment of the invention has the technical effects of high luminous efficiency, long service life and improvement of driving voltage.
Among them, triarylamines have excellent hole transport properties, and in general, a hole transport layer, a light-emitting auxiliary layer, and an electron blocking layer have triarylamine groups.
Taking triarylamine materials as an example of a light-emitting auxiliary layer, the energy level of the light-emitting auxiliary layer is matched with that of the light-emitting layer and the hole-transporting layer, so that three substituents in triarylamine groups need to be regulated. Obviously, the target values that need to be adjusted are different for different light emitting layers. The difference is large for the three light emitting layers of RGB. Even with the same blue light, there is a significant difference for different host, dopant materials.
The dibenzofuranyl is favorable for improving the triplet state energy level, and the dibenzofuranyl is introduced into the aryl of the triarylamine, so that the material can be matched with the requirement of a blue light luminescent auxiliary layer. The substituent on dibenzofuran can further distort the structure of the compound, and is not easy to crystallize in the evaporation process.
The conjugated area is enlarged, the conjugated system is prolonged, the mobility is improved, namely dibenzofuran is regulated to naphthobenzofuran and the like, and the luminescent efficiency, the driving voltage and the service life of the compound are all affected differently.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a blue light luminescent auxiliary material has a structural general formula as shown in a chemical formula I:
wherein n is selected from 1 or 2; m is selected from 0, 1 or 2;
Ar 1 、Ar 2 、Ar 3 r is independently selected from at least one of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl;
ar is condensed with an adjacent benzene ring; ar is selected from substituted or unsubstituted C6-C30 aryl.
Preferably, ar is selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and substituted or unsubstituted phenanthryl.
Preferably, the structural general formula of the light-emitting auxiliary material is any one of chemical formulas I-a, I-b and I-c:
preferably, R is selected from any one of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, methylphenyl, cyanophenyl;
Ar 1 、Ar 2 each independently selected from at least one of phenyl, naphthyl, methylphenyl, ethylphenyl, cyanophenyl, methoxyphenyl, phenylpyridyl, phenylpyrimidinyl, biphenyl, terphenyl, phenylnaphthyl, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, cyclopentyl, cyclohexyl;
Ar 3 any one selected from phenyl, naphthyl, phenanthryl, methylphenyl, ethylphenyl, cyanophenyl, methoxyphenyl, phenylpyridyl, phenylpyrimidinyl, biphenyl, terphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-phenyl-9H-carbazolyl, diphenylfluorenyl, dimethylfluorenyl, cyclopentyl and cyclohexyl.
Preferably, R is selected from any one of phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, methylphenyl;
Ar 1 、Ar 2 each independently selected from at least one of phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, cyclopentyl and cyclohexyl;
Ar 3 each independently selected from any one of phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-phenyl-9H-carbazolyl, dimethylfluorenyl and diphenylfluorenyl.
In the above technical scheme, the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron base; C1-C30 alkyl; cycloalkyl of C3-C30; an alkoxy group; aryl of C6-C30; heteroaryl groups of 3-to 30-membered, or substituted with a substituent to which two or more of the substituents shown above are attached, or not having a substituent.
The term "C1-C30 alkyl" means a straight or branched alkyl group having 1 to 30 carbon atoms constituting a chain, wherein the number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10.
Specifically, the above alkyl group includes methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl and the like.
The term "cycloalkyl of C3-C30" means a mono-or polycyclic hydrocarbon having 3 to 30 ring backbone carbon atoms, wherein the number of carbon atoms is preferably 3 to 20, and more preferably 3 to 7.
Specifically, the cycloalkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and the like.
The term "aryl of C6-C30" means a monocyclic or fused ring group derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, wherein the number of ring backbone carbon atoms is preferably 6 to 25, more preferably 6 to 18. The aryl groups described above may be partially saturated and may contain spiro structures.
Specifically, the above aryl group includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, phenylterphenyl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, perylenyl, droyl, naphthacene, fluoranthryl, spirobifluorenyl, azulenyl, methylphenyl, ethylphenyl, methoxyphenyl, cyanophenyl and the like.
The term "3-to 30-membered heteroaryl" means an aryl group having 3 to 30 ring backbone atoms and including at least one heteroatom. The number of heteroatoms is preferably 1 to 4; the heteroatom is selected from at least one of B, N, O, S, si and P. The heteroaryl group may be a single ring or a condensed ring condensed with at least one benzene ring; may be partially saturated; may be heteroaryl formed by linking at least one heteroaryl or aryl group to a heteroaryl group via one or more single bonds; and may comprise a helical structure.
Wherein the number of ring backbone carbon atoms is preferably 3 to 24, more preferably 3 to 18.
Specifically, the above heteroaryl group may include monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl; and condensed ring type heteroaryl groups such as benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, benzoquinazolinyl, quinoxalinyl, benzoquinoxalinyl, naphthyridinyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, and dihydroacridinyl.
Preferably, the structural formula of the light-emitting auxiliary material is any one of the following structural formulas:
another object of the embodiments of the present invention is to provide a method for preparing the above luminescent auxiliary material, wherein a synthetic route of the luminescent auxiliary material is as follows:
wherein Hal is selected from Cl, br or I; r' is
Or->
；Ar 1 、Ar 2 、Ar 3 Ar and R are the same as the ranges; the preparation method of the luminescent auxiliary material comprises the following steps:
when R' is
When it is desired to add reactants A-I, reactant B-I, cu (OAc) 2 Reacting Myristic acid (Myristic acid) with 2,6-lutidine (2, 6-lutidine) to obtain an intermediate C-I; alternatively, when R' is +.>
When it is desired to add reactants A-I, reactant B-I, cu (OAc) 2 Triethylamine (Et) 3 N) dissolving in a mixed solvent of dried acetonitrile (MeCN) and EtOH, and heating to react to obtain an intermediate C-I;
and (3) dissolving the intermediate C-I and the reactant D-I (1.0-1.3 eq) in a solvent, then placing in a protective atmosphere, adding a palladium catalyst, a phosphine ligand and alkali, and heating to react to obtain the luminescent auxiliary material shown in the formula I.
Specifically, in practical application, the preparation method of the light-emitting auxiliary material may include the following steps:
s1, when R' is
When the reaction vessel was charged with reactants A-I (1.0 eq) and B-I (1.0-1.5 eq) at room temperatureAdding Cu (OAc) 2 (0.05-0.15 eq), myristic acid (0.05-0.4 eq), 2,6-lutidine (1.0-1.2 eq), stirring for 18-24h, purifying the remaining material by column chromatography to obtain intermediate C-I; alternatively, when R' is +.>
When the reaction vessel was charged with reactants A-I (1.0 eq) and B-I (1.0-1.5 eq), cu (OAc) was added 2 （1.0-2.0eq）、Et 3 N (2.0-3.0 eq) was dissolved in a dry mixed solvent of MeCN and EtOH, warmed to 75-95℃and stirred for 18-24h, and the remaining material was purified by column chromatography to give intermediate C-I.
S2, adding an intermediate C-I (1.0 eq) and a reactant D-I (1.0-1.3 eq) into a reaction vessel, dissolving in toluene, adding a palladium catalyst (0.01-0.1 eq), a phosphine ligand (0.02-0.2 eq) and a base (2.0-4.0 eq) under the protection of nitrogen, heating to 75-95 ℃, and stirring for 6-12h; filtering with diatomaceous earth while hot, retaining organic phase, and purifying the rest material by column chromatography to obtain luminescent auxiliary material shown in formula I.
Wherein the palladium catalyst may be: pd (Pd) 2 (dba) 3 ，Pd(PPh 3 ) 4 ，PdCl 2 ，PdCl 2 (dppf)，Pd(OAc) 2 ，Pd(PPh 3 ) 2 Cl 2 ，NiCl 2 (dppf), etc.;
the phosphine ligand may be: p (t-Bu) 3 ，X-phos，PET 3 ，PMe 3 ，PPh 3 ，KPPh 2 ，P(t-Bu) 2 Cl, etc.;
the base may be: k (K) 2 CO 3 ，K 3 PO 4 ，Na 2 CO 3 ，CsF，Cs 2 CO 3 t-Buona, etc.
Another object of an embodiment of the present invention is to provide an application of the above light-emitting auxiliary material in preparing a light-emitting device and/or a display apparatus.
Another object of an embodiment of the present invention is to provide a light emitting device, namely an organic electroluminescent device, which includes an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer including the above-described light emitting auxiliary material.
Preferably, the organic layer includes at least a hole transport layer, a light emitting layer, and a light emitting auxiliary layer disposed between the hole transport layer and the light emitting layer; the light-emitting auxiliary layer contains the light-emitting auxiliary material partially or entirely.
The luminescent auxiliary material provided by the invention is based on aromatic ring benzofurans, substituent groups exist on the aromatic ring, the aromatic ring benzofurans are directly connected with aromatic amine, one of the substituent groups on the aromatic amine is dibenzofuran, and the substituent groups exist on the benzene ring where the dibenzofuran is connected with the aromatic amine. The luminescent auxiliary material provided by the invention has the characteristics of reducing the driving voltage of the organic electroluminescent device, effectively improving the luminous efficiency and prolonging the service life of the device, and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of intermediate C-5 prepared in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the compound 5 produced in example 1 of the present invention.
FIG. 3 is a fluorescence attenuation spectrum of application example 25 of the present invention.
FIG. 4 is an HPLC chromatogram of compound 112 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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.
Example 1
This example provides a method for preparing a luminescent auxiliary material (compound 5), which is synthesized by the following steps:
s1, adding reactant A-5 (100 mmol, CAS: 2305718-56-1), reactant B-5 (120 mmol) and 2,6-lutidine (100 mmol) to the reaction vessel, adding Cu (OAc) at room temperature 2 (5 mmol), myristic acid (10 mmol), stirring for 24H, purifying the remaining material by column chromatography to obtain intermediate C-5 (29.08 g, yield: 63%, mass Spectrometry theory: 461.56, test value MS (ESI, M/Z): [ M+H ]]+= 461.71). Wherein the nuclear magnetic resonance hydrogen spectrum of the intermediate C-5 is shown in figure 1.
S2, after adding intermediate C-5 (50 mmol) and reactant D-5 (55 mmol, CAS: 1821235-69-1) to the reaction vessel and dissolving in toluene, pd2 (dba) was added under nitrogen protection 3 （0.5mmol）、P(t-Bu) 3 (1 mmol), t-BuONa (110 mmol); heating to 80deg.C, stirring for 8 hr, filtering with diatomaceous earth while hot, retaining organic phase, and purifying the rest material by column chromatography to obtain compound 5 (30.28 g, yield: 86%, mass spectrum theoretical value: 703.84, test value MS (ESI, M/Z): [ M+H ]]+= 704.20）。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 88.74, H, 4.73, N, 1.99, O, 4.55
Test value: c, 88.56, H,4.85, N, 2.03, O, 4.61.
The nuclear magnetic resonance hydrogen spectrum of the above-mentioned compound 5 is shown in FIG. 2.
Example 2
This example provides a method for preparing a luminescent auxiliary material (compound 55), which is synthesized by the following steps:
s1, adding reactant A-55 (100 mmol, CAS: 2324189-56-0) and reactant B-55 (110 mmol, CAS: 108714-73-4) to the reaction vessel, adding Cu (OAc) 2 （110mmol）、Et 3 N (250 mmol), dissolved in dried MeCNAnd EtOH, heating to 80deg.C, stirring for 24 hr, and purifying the remaining material by column chromatography to obtain intermediate C-55 (29.10 g, yield: 58%, mass spectrum theory: 501.63, test value MS (ESI, M/Z): [ M+H ]]+= 501.84）。
S2, after adding reactant C-55 (50 mmol) and reactant D-55 (55 mmol, CAS: 2641790-04-5) to the reaction vessel and dissolving in toluene, pd was added under nitrogen 2 (dba) 3 （0.5mmol）、P(t-Bu) 3 (1 mmol) and t-Buona (110 mmol), heating to 80deg.C, stirring for 8 hr, filtering with diatomaceous earth while hot, and purifying the remaining material by column chromatography to give compound 55 (29.76 g, yield: 80%, mass spectrum theory: 743.91, test value MS (ESI, M/Z): [ M+H ]]+= 744.15）。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 88.80, H, 5.01, N, 1.88, O, 4.30
Test value: c, 88.55, H, 5.15, N, 1.91, O, 4.42.
Example 3
This example provides a method for preparing a luminescent auxiliary material (compound 112), which is synthesized by the following steps:
s1, adding reactant A-112 (100 mmol, CAS: 2774588-09-7) and reactant B-112 (110 mmol, CAS: 3366-65-2) to the reaction vessel, adding Cu (OAc) 2 （110mmol）、Et 3 N (250 mmol) was dissolved in a dry mixture of MeCN and EtOH, warmed to 80℃and stirred for 24H, and the remaining material was purified by column chromatography to give intermediate C-112 (26.24 g, yield: 54%, mass Spectrometry theory: 485.59, test MS (ESI, M/Z): [ M+H ]]+= 485.96）。
S2, after adding reactant C-112 (50 mmol) and reactant D-112 (55 mmol, CAS: 2247893-30-5) to the reaction vessel and dissolving in toluene,pd is added under the protection of nitrogen 2 (dba) 3 （0.5mmol）、P(t-Bu) 3 (1 mmol) and t-Buona (110 mmol), heating to 80deg.C, stirring for 8 hr, filtering with diatomaceous earth while hot, and purifying the remaining material by column chromatography to give compound 112 (30.95 g, yield: 85%, mass Spectrometry theory: 727.86, test value MS (ESI, M/Z): [ M+H ]]+= 728.03）。
Characterization:
HPLC purity: > 99.8%.
The HPLC spectrum of the above-mentioned compound 112 is shown in FIG. 4, and the chromatographic peak analysis results are shown in Table 1.
Elemental analysis:
theoretical value: c, 89.11, H, 4.57, N, 1.92, O, 4.40
Test value: c, 88.96, H, 4.68, N, 1.97, O, 4.46.
Examples 4 to 41
Preparation of the following compounds, the molecular formulas and mass spectra of which are shown in table 2 below, was accomplished with reference to the preparation methods of examples 1 to 3 above.
The other compounds claimed in the present invention can be prepared by referring to the preparation methods of the above-listed examples, and thus are not exemplified herein.
In another embodiment of the present invention, there is also provided an organic electroluminescent device that may have 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, and the like as an organic layer. However, the structure of the organic electroluminescent device is not limited thereto, and may include a smaller or larger number of organic layers.
In the case of manufacturing an organic electroluminescent device, the compound represented by the formula I may be formed by vacuum vapor deposition or solution coating. Among them, the solution coating method is: spin coating, dip coating, knife coating, ink jet printing, screen printing, spray coating, roll coating, and the like, but are not limited thereto.
The organic electroluminescent device provided by the embodiment of the invention can be classified into a top-emission type, a bottom-emission type or a bi-directional emission type according to the materials used.
The organic electroluminescent device provided by the embodiments of the present invention may be used in applications 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 albums, personal digital assistants, 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, signs, and the like.
In addition, as the anode material, a material having a large work function is generally preferable in order to enable holes to be smoothly injected into the organic layer. Anode materials that may be used in embodiments of the present invention include: metals such as vanadium, chromium, copper, zinc, gold, etc., or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO A1 or SnO 2 Metal such as Sb and oxygenA combination of chemical compounds; and conductive polymers such as polypyrrole and polyaniline.
The hole injection layer is preferably a p-doped hole injection layer, by which is meant 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 transport layer material is a material capable of receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer, and has high hole mobility. The hole transport layer material may be selected from arylamine derivatives, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like.
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 compound shown in the formula I prepared by the embodiment of the invention can be used as a luminescent auxiliary layer material.
The light-emitting substance of the light-emitting layer is a substance capable of receiving and binding holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, to emit light in the visible light region, and is preferably a substance having high quantum efficiency for fluorescence or phosphorescence.
In particular, the light emitting layer may comprise a host material and a doping material; the mass ratio of the host material to the doping material is 90-99.5:0.5-10.
The main material can be aromatic condensed ring derivative or heterocyclic compound. 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, pyrimidine derivatives, and the like.
The doping material can be fluorescent doping material or phosphorescent doping material, and specifically can be aromatic amine derivative, styrylamine compound, boron complex, fluoranthene compound or metal complex, etc.
The electron transport layer may function to facilitate electron transport. The electron transport layer material is a material that advantageously receives electrons from the cathode and transports the electrons to the light emitting layer, preferably a material having high electron mobility. The electron transport layer may include at least one of an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and preferably at least one of an electron transport layer and an electron injection layer.
The electron injection layer may function to promote electron injection, have an ability to transport electrons, and 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, 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 generally preferably a material having a small work function so that electrons are smoothly injected into the organic material layer, which has a layer thickness of 0.5 to 5nm. The cathode material is generally preferably a material having a small work function in order to facilitate injection of electrons 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, or alloys thereof, multilayer structural materials such as LiF/A1 or LiO2/A1, mg/Ag, and the like.
It should be noted that, other layer materials in the organic electroluminescent device are not particularly limited except that the light-emitting auxiliary layer disclosed in the embodiment of the present invention includes the compound represented by formula I, and materials disclosed in the prior art may be used.
The organic electroluminescent device provided by the embodiment of the invention is specifically described below with reference to specific application examples.
Application example 1
The application example provides a preparation method of an organic electroluminescent device, which comprises the following steps:
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, repeatedly washing with distilled water for 2 times, washing with ultrasonic waves for 10min, transferring into a spin dryer after washing, removing distilled water on the glass substrate, baking with a vacuum oven at 220 ℃ for 2 hours, and cooling after baking. 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): the hole injection layer materials HT and P-dopant were vacuum evaporated at an evaporation rate of 1 Å/s, the chemical formulas of which are shown below. The evaporation rate ratio of HT to P-dock is 97:3, the thickness is 10nm;
c. HTL (hole transport layer): vacuum evaporating HT of 120nm on the hole injection layer as a hole transport layer at an evaporation rate of 1.5 Å/s;
d. prime (light-emitting auxiliary layer): vacuum-evaporating the compound 1 provided in the above example as a light-emitting auxiliary layer over the hole transport layer at an evaporation rate of 0.5 Å/s of 10nm;
e. EML (light emitting layer): then, a Host material (Host) and a Dopant material (Dopant) having a thickness of 25nm were vacuum-deposited as light-emitting layers on the above light-emitting auxiliary layer at a deposition rate of 1 Å/s, and the chemical formulas of Host and Dopant are as follows. Wherein the evaporation rate ratio of Host to Dopant is 97:3.
f. HB (hole blocking layer): a hole blocking layer having a thickness of 5.0nm was vacuum deposited at a deposition rate of 0.5. 0.5 Å/s.
g. ETL (electron transport layer): ET and Liq with a thickness of 35nm were vacuum-evaporated as electron transport layers at an evaporation rate of 1 Å/s, and the chemical formula of ET is shown below. Wherein the evaporation rate ratio of ET to Liq is 50:50.
h. EIL (electron injection layer): an electron injection layer was formed by vapor deposition of 1.0nm on a Yb film layer at a vapor deposition rate of 0.5. 0.5 Å/s.
i. And (3) cathode: and evaporating magnesium and silver at 18nm at an evaporation rate ratio of 1 Å/s, wherein the evaporation rate ratio is 1:9, so as to obtain the OLED device.
j. Light extraction layer: CPL with a thickness of 70nm was vacuum deposited as a light extraction layer on the cathode at a deposition rate of 1 Å/s.
k. And packaging the substrate subjected to evaporation to obtain the organic electroluminescent device. Specifically, firstly, a gluing device is used for carrying out a coating process on a cleaned cover plate by using UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to evaporation coating 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, UV glue illumination curing is completed.
The structure of the organic electroluminescent device is as follows:
ITO/Ag/ITO/HT: P-dose (10 nm, 3%)/HT (120 nm)/Compound 1 (10 nm)/Host: dose (25 nm, 3%)/HB (5 nm)/ET: liq (30 nm, 50%)/Yb (1 nm)/Mg: ag (18 nm, 1:9)/CPL (70 nm).
In addition, the structural formula of part of the materials used in the preparation method is as follows:
application examples 2 to 41
The organic electroluminescent devices of application examples 2 to 41 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 corresponding compound 4, 5, 6, 7, 8, 11, 14, 15, 18, 22, 23, 25, 30, 31, 32, 33, 36, 40, 44, 49, 51, 52, 54, 55, 58, 61, 67, 74, 80, 82, 85, 88, 93, 100, 102, 109, 112, 113, 116, 119, 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.
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 in application example 1 was replaced with comparative compound 2.
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 in application example 1 was replaced with comparative compound 3.
Comparative example 4
An organic electroluminescent device was prepared according to the above-described method for preparing an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 4.
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.
Comparative example 6
An organic electroluminescent device was prepared according to the above-described method for preparing an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 6.
Wherein, the structural formulas of the comparative compounds 1, 2, 3, 4, 5 and 6 are as follows:
performance test:
the organic electroluminescent devices obtained in the above application examples 1 to 41 and comparative examples 1 to 6 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 3 below:
as known to those skilled in the art, the blue-light organic electroluminescent device is affected by the microcavity effect, and the luminous efficiency is greatly affected by chromaticity, so that a BI value is introduced as the basis of the efficiency of the blue-light luminescent material, bi=luminous efficiency/CIEy. And the problems of short lifetime and low efficiency of blue light devices have been one of the problems that those skilled in the art are urgent to solve in the art.
As can be seen from table 3, the organic electroluminescent device application examples 1 to 41 prepared by using the luminescent auxiliary material provided by the embodiment of the invention have the technical effects of high luminous efficiency, long service life and improvement of driving voltage compared with the existing organic electroluminescent devices provided by comparative examples 1 to 6.
The fluorescence decay pattern of the device (application example 25) prepared from the compound 55 is shown in FIG. 3. Fig. 3 shows that the time taken for the luminance of the organic electroluminescent device prepared by the compound 55 to decay to 95% is 200h. The T95 life of the compounds of the invention is generally between 200 and 230 hours.
Compared with the comparative compound 1, the compound 33 provided by the embodiment of the invention has the advantages that the aromatic amine derivative is directly connected with the benzene ring on the naphthobenzofuran, and the comparative compound 1 has a bridging group phenylene, so that the influence of furan on the triplet state energy level of the compound is weakened, and the light-emitting auxiliary layer and the light-emitting layer are influencedIs a function of the energy level matching of the first and second energy sources. The device results show that the luminous efficiency of the device obtained by using the compound 33 is relatively improved by about 5%, the service life is prolonged by about 25%, the driving voltage is obviously improved, and the voltage is reduced by 0.13V.
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Compared with the comparative compound 2, the compound 51 provided by the embodiment of the invention is distinguished in that substituent groups exist on dibenzofuran on aromatic amine, and the substituent groups on the dibenzofuran can further distort the structure of the compound, so that the compound is not easy to crystallize in the evaporation process, and the service life of a device is prolonged. The device results showed that the luminous efficiency of the device obtained by using the compound 51 was relatively improved by about 6%, the lifetime was prolonged by about 29%, and the driving voltage was also significantly improved.
Compared with the comparative compound 4, the compound 82 provided by the embodiment of the invention has the advantages that the mother nucleus is changed from dibenzofuran to naphthobenzofuran, the compound 82 has about 5% improvement on luminous efficiency, the service life of the device is prolonged by 69h, and the driving voltage is reduced by 0.1V; compared with the comparative compound 5, the compound 67 provided by the embodiment of the invention has the advantages that the substitution position of the aromatic amine is changed, the luminous efficiency of the compound 67 is improved by about 6%, the service life of the device is prolonged by 62 hours, the driving voltage is reduced by 0.12V, and the device performance is obviously improved.
。
The comparison compound 3 is different from the compound shown in the formula I in terms of the substitution positions of the aromatic amine and has no substituent on dibenzofuran on the aromatic amine, the comparison compound 6 is different from the compound shown in the formula I in terms of biphenyl on the aromatic amine, no substituted dibenzofuran group is contained in the compound, the device performance result shows that the luminous efficiency of the comparison compound 3 is about 146cd/A/CIEy, the device service life is about 148h, the luminous efficiency of the comparison compound 6 is about 152-156cd/A/CIEy, the device service life is generally 200-230h, and the compounds provided by the embodiment of the invention all show excellent device performance.
It can be seen that the present invention, although similar in structure to the prior art compounds, only compounds according to formula I of the present invention, when used as blue light emitting auxiliary layers, exhibit significant device performance improvements.
The luminescent auxiliary material provided by the invention is based on aromatic ring benzofurans, substituent groups exist on the aromatic ring, the aromatic ring benzofurans are directly connected with aromatic amine, one of the substituent groups on the aromatic amine is dibenzofuran, and the substituent groups exist on the benzene ring where the dibenzofuran is connected with the aromatic amine. The organic electroluminescent device prepared by the luminescent auxiliary material provided by the embodiment of the invention has the technical effects of high luminous efficiency, long service life and improvement of driving voltage.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description.
Claims (9)
1. The luminous auxiliary material is characterized by having a structural general formula as shown in a chemical formula I:
wherein n is 1; m is selected from 0 or 1;
Ar 1 selected from phenyl or naphthyl; ar (Ar) 2 Is phenyl; ar (Ar) 3 Selected from one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, said substituted group being selected from at least one of deuterium, halogen group, cyano, hydroxy, carbonyl, ester group, silyl, boron group, C1-C30 alkyl, C3-C30 cycloalkyl, alkoxy, C6-C30 aryl, 3-to 30-membered heteroarylOne of the two; r is phenyl;
ar is condensed with an adjacent benzene ring; ar is phenyl.
2. The light-emitting auxiliary material according to claim 1, wherein the light-emitting auxiliary material has a structural general formula of any one of chemical formulas I-a, I-b, and I-c:
3. the light-emitting auxiliary material according to claim 1, wherein Ar 3 Any one selected from phenyl, naphthyl, phenanthryl, methylphenyl, ethylphenyl, cyanophenyl, methoxyphenyl, phenylpyridyl, phenylpyrimidinyl, biphenyl, terphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-phenyl-9H-carbazolyl, diphenylfluorenyl and dimethylfluorenyl.
4. A light-emitting auxiliary material according to claim 3, wherein Ar 3 Any one selected from phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-phenyl-9H-carbazolyl, dimethylfluorenyl and diphenylfluorenyl.
5. The light-emitting auxiliary material according to claim 1, wherein the structural formula of the light-emitting auxiliary material is any one of the following structural formulas:
6. a method of preparing a luminescent auxiliary material as claimed in any one of claims 1 to 5, characterized in that the synthetic route of the luminescent auxiliary material is as follows:
wherein Hal is selected from Cl, br or I; r' is
Ar 1 、Ar 2 、Ar 3 Ar and R are the same as the ranges; the preparation method of the luminescent auxiliary material comprises the following steps:
when R' is
When it is desired to add reactants A-I, reactant B-I, cu (OAc) 2 Reacting myristic acid with 2,6-lutidine to obtain an intermediate C-I; alternatively, when R' is +.>
When it is desired to add reactants A-I, reactant B-I, cu (OAc) 2 Dissolving triethylamine in a mixed solvent of acetonitrile and EtOH after drying, heating to react to obtain the intermediateAn intermediate C-I;
and (3) dissolving the intermediate C-I and 1.0-1.3eq of reactant D-I in a solvent, then placing in a protective atmosphere, adding a palladium catalyst, a phosphine ligand and alkali, and heating to react to obtain the luminescent auxiliary material shown in the formula I.
7. Use of a light-emitting auxiliary material according to any one of claims 1-5 for the preparation of a light-emitting device and/or a display device.
8. A light-emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the light-emitting auxiliary material according to any one of claims 1 to 5.
9. The light-emitting device according to claim 8, wherein the organic layer includes at least a hole-transporting layer, a light-emitting layer, and a light-emitting auxiliary layer provided between the hole-transporting layer and the light-emitting layer; the light-emitting auxiliary layer contains the light-emitting auxiliary material partially or entirely.
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