CN111170993A - Organic electronic material containing nitrogen atom heterocycle and preparation method and application thereof - Google Patents
Organic electronic material containing nitrogen atom heterocycle and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an organic electronic material containing nitrogen atom heterocycle and a preparation method and application thereof, relating to the technical field of organic electroluminescence. The invention introduces pyridine, triazine or pyrimidine and other nitrogen atom-containing heterocycles on the main structure of phenanthrene, thereby enhancing the electronegativity of the material, improving the electron transport performance of the compound and improving the heat stability of the compound. The organic electron transport material provided by the invention has the advantages of good thermal stability, high luminous efficiency and high luminous purity. The organic electroluminescent device manufactured by the organic electronic material can reduce the driving voltage, improve the luminous efficiency, has excellent color purity and prolongs the service life of the device.
Description
The technical field is as follows:
the invention relates to the technical field of organic electroluminescence, in particular to an organic electronic material containing nitrogen atom heterocycle and a preparation method and application thereof.
Background art:
along with the development of science and technology and economy, the requirements of people on the quality of life are also increased, and of course, the display and lighting technology which is closely related to the life of people is also included. New display and lighting technologies need to meet not only the color requirements of the human eye, but also health and environmental protection. Organic electroluminescent devices (OLEDs), as a new display technology, can be switched freely for each pixel and emit light actively, resulting in short display response time and high color contrast; the driving voltage is low, and the energy consumption can be reduced; the use of organic materials enables the device to be thinner and lighter and environment-friendly; the diversified selection of the substrate provides possibility for flexible and transparent display, and the substrate is widely applied to the fields of mobile phones, flat panel displays, televisions, lighting, vehicle-mounted display and the like.
The common organic electroluminescent device adopts a sandwich type sandwich structure, namely an organic layer is sandwiched between an anode and a cathode at two sides, and the organic layer is divided into a hole transport layer, an electron transport layer, a luminescent layer, a hole blocking layer, an electron blocking layer and the like according to different photoelectric characteristics of various materials. The light-emitting mechanism of the device is mainly as follows: under the drive of external voltage, holes and electrons overcome energy barriers, are respectively injected into the hole transport layer and the electron transport layer from the anode and the cathode, then are recombined in the light-emitting layer to release energy, and the energy is transferred to the organic light-emitting substance. The light-emitting substance receives energy and is caused to transition from a ground state to an excited state, and when excited molecules transition back to the ground state, a light-emitting phenomenon occurs.
An electron transport material is a material that transports electrons from the cathode to the light emitting layer. Electron transport materials generally require good thermal stability and film-forming properties, high electron mobility, high electron affinity, and high excited state energy levels.
Since most organic electroluminescent materials transport holes faster than electrons. This causes an imbalance in the number of electrons and holes in the light-emitting layer, resulting in a device emitting light away from the light-emitting layer and closer to the electrodes, which requires higher driving voltages and also reduces the efficiency and lifetime of the device. Although recent organic electroluminescent devices have been gradually improved, materials more excellent in light emitting efficiency, driving voltage, lifespan, and the like are required, and thus, development of an electron transport material having good thermal stability and excellent performance is required.
The invention content is as follows:
the invention aims to provide an organic electronic material containing nitrogen atom heterocycle and a preparation method and application thereof. In order to overcome the problems, pyridine, triazine or pyrimidine and other nitrogen atom-containing heterocycles are introduced to the main structure of phenanthrene, so that the electronegativity of the material is enhanced, the electron transport performance of the compound is improved, and the thermal stability of the compound is improved. The present invention provides an organic electroluminescent compound having high thermal stability and film-forming properties, and having high electron mobility. The organic electroluminescent device made of the organic electronic material has excellent luminous efficiency and longer service life.
The invention provides an organic electronic material containing a heterocyclic ring containing nitrogen atoms, which contains a compound shown in the following structural formula (I) or (II):
wherein Py is C5-C30Substituted or unsubstituted pyridine of (a);
r is hydrogen, C1-C4Alkyl radical, C6-C30Substituted or unsubstituted aryl of (a);
Ar1and Ar2Independently selected from the group consisting of C6-C30Substituted or unsubstituted aryl of (a);
Z1、Z2and Z3At least one is N and the others are CH.
Preferably, R is independently selected from hydrogen, phenyl, tolyl, biphenyl, or naphthyl;
Ar1and Ar2Independently selected from phenyl, tolyl, biphenyl, naphthyl, phenanthryl, anthracyl, perylenyl, phenylnaphthyl, naphthylphenyl, diphenylphenyl, 9, 9-dimethylfluorenyl, 9, 9-diphenylfluorenyl, 9, 9-spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl or benzophenanthryl.
Further preferably Py is pyridyl, R is phenyl, Ar1And Ar2Independently selected from phenyl, biphenyl or naphthyl.
More preferably, the organic electronic material includes, but is not limited to, any one of the following compounds CQ1-CQ 28.
The present invention also provides a process for the preparation of a compound of formula (I) or (II) as defined above, comprising the steps of:
(A1) synthesis of Compound b: preparing a compound b by using o-bromoiodobenzene and an alkynyl compound through a Sonogashira reaction;
(A2) synthesis of Compound c: preparing a compound c by a Suzuki reaction of the compound b and halogenated phenylboronic acid;
(A3) synthesis of Compound d: reacting the compound c with iodine chloride or bromosuccinimide to prepare a compound d, wherein the used solvent is dichloromethane, chloroform, tetrahydrofuran, 1, 2-dichloroethane, acetonitrile, N-dimethylformamide, N-dimethylacetamide or dioxane;
(A4) synthesis of Compound f: obtaining a compound f through the reaction of the compound d and pyridine boronic acid e or pyridine boric acid ester Suzuki;
(A5) synthesis of compounds of structural formula (I): obtaining a compound with a structural formula (I) by a Suzuki reaction by using a compound j and boric acid ester h;
or;
(B1) synthesis of Compound b: preparing a compound b by using o-bromoiodobenzene and an alkynyl compound through a Sonogashira reaction;
(B2) synthesis of Compound c: preparing a compound c by a Suzuki reaction of the compound b and halogenated phenylboronic acid;
(B3) synthesis of Compound d: thirdly, reacting the compound c with iodine chloride or bromosuccinimide to prepare a compound d, wherein the used solvent is dichloromethane, chloroform, tetrahydrofuran, 1, 2-dichloroethane, acetonitrile, N-dimethylformamide, N-dimethylacetamide or dioxane;
(B4) synthesis of Compound j: carrying out Suzuki reaction on the compound d and boric acid ester h to obtain a compound j;
(B5) synthesis of compounds of structural formula (II): obtaining a compound with a structural formula (II) by a Suzuki reaction of a compound j and pyridine boronic acid e or pyridine boric acid ester;
or;
the raw materials of the compound of the present invention are all available from the market, and in the above reaction formula, R, Py and Ar1、Ar2、Z1、Z2And Z3The definition of (A) is the same as that described above, and X represents chlorine or bromine.
Another aspect of the present invention provides an organic electroluminescent device comprising an anode, a cathode and an organic layer;
the organic layer comprises one or more than one of a luminescent layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer or an electron transport layer;
at least one of the organic layers contains the organic electronic material.
Preferably, the light-emitting layer in the organic layer contains the organic electronic material.
Preferably, the electron transport layer or the electron injection layer in the organic layer contains the organic electronic material.
Preferably, the hole blocking layer in the organic layer contains the organic electronic material.
Preferably, the total thickness of the organic layer is 1 to 1000 nm; further preferably, the total thickness of the organic layer is 50 to 500 nm.
When the compound with the structural formula I or the structural formula II is used in the organic electroluminescent device, other materials such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a blocking layer and the like can be matched to obtain blue light, green light, yellow light, red light or white light.
Each of the organic layers in the organic electroluminescent device of the present invention can be prepared by a vacuum evaporation method, a molecular beam evaporation method, a dip coating method in a solvent, a spin coating method, a bar coating method, an inkjet printing method, or the like. The metal electrode can be prepared by an evaporation method or a sputtering method.
The invention also provides application of the organic electronic material, and the organic electronic material can be used for producing organic electroluminescent devices, organic solar cells, organic thin film transistors, organic photodetectors, organic field effect transistors, organic integrated circuits, organic photoreceptors and the like.
The invention has the beneficial effects that:
the invention provides an organic electronic material containing nitrogen atom heterocycle, a preparation method and application thereof. The organic electroluminescent device manufactured by the organic electroluminescent compound can reduce the driving voltage, improve the luminous efficiency, has excellent color purity and prolong the service life of the device.
Description of the drawings:
FIG. 1 is a hydrogen nuclear magnetic spectrum of compound CQ 2.
FIG. 2 is a hydrogen nuclear magnetic spectrum of compound CQ 21.
FIG. 3 is a schematic view of an organic electroluminescent device according to the present invention
Wherein 110 represents a glass substrate, 120 represents an anode, 130 represents a hole injection layer, 140 represents a hole transport layer, 150 represents a blocking layer, 160 represents a light emitting layer, 170 represents an electron transport layer, 180 represents an electron injection layer, and 190 represents a cathode.
Fig. 4 is a graph of current density versus current efficiency for a device.
Fig. 5 is a graph of current density versus power efficiency and external quantum efficiency for devices prepared from compound CQ 1.
FIG. 6 shows the results of example 7 at 20mA/cm2Current density of (a).
Detailed Description
The present invention will be further described with reference to the accompanying drawings and detailed description, but the following embodiments are only preferred embodiments of the present invention, and not all embodiments. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention.
Example 1
An organic electronic material containing nitrogen atom heterocycle, the organic electronic material contains compound CQ1, the synthetic route of compound CQ1 is as follows:
the synthesis method of the intermediate CQ1-1 comprises the following steps:
o-bromoiodobenzene (52.2g, 184.5mmol), phenylacetylene (18.85g, 184.5mmol) and triethylamine (260mL) were added to a flask, under nitrogen, cuprous iodide (0.35g, 1.84mmol) and triphenylphosphine palladium chloride (0.5g, 0.7mmol) were added, the reaction was stopped after stirring at room temperature for 0.5h, and triethylamine was concentrated off by filtration to give 46.8g of a yellow oily liquid in 98% yield.
1H NMR(400MHz,CDCl3,δ):7.62-7.64(m,2H),7.57(dd,J＝7.2,1.2Hz,1H),7.51(dd,J＝5.2,1.2Hz,1H),7.32-7.40(m,5H).
The synthesis method of the intermediate CQ1-2 comprises the following steps:
the flask was charged with intermediate CQ1-1(13.4g, 52.1mmol), p-chlorobenzeneboronic acid (8.5g, 54.4mmol) and potassium carbonate (14.4g, 104.2mmol), then added with toluene (80mL), tetrahydrofuran (40mL) and deionized water (40mL), and added with triphenylphosphine palladium chloride (0.27g, 0.38mmol) under nitrogen protection, after refluxing for 3h to stop the reaction, cooled, separated, washed with water to neutral, and concentrated to dryness to give 16g of a yellow oily liquid.
1H NMR(400MHz,CDCl3,δ):7.60-7.66(m,3H),7.30-7.44(m,10H).
The synthesis method of the intermediate CQ1-3 comprises the following steps:
intermediate CQ1-2(15g, 51.9mmol) and dichloromethane (225mL) are added into a flask, the temperature is reduced to 0-5 ℃, iodine chloride (10g, 61.6mmol) is dissolved in dichloromethane (75mL) and is added into the solution dropwise, after the addition, the solution is stirred for 0.5h, 200mL 5% aqueous sodium sulfite solution is added to quench the reaction until the solution is neutral, and then the solution is separated, dried, concentrated and dried, and passes through a column to obtain 13g of light yellow solid with the yield of 60%.
1H NMR(400MHz,CDCl3,δ):8.61-8.67(m,2H),8.45-8.48(m,1H),7.68-7.75(m,2H),7.53-7.62(m,4H),7.37(d,J＝2.0Hz,1H),7.26-7.29(m,2H).
The synthesis method of the intermediate CQ1-4 comprises the following steps:
the flask was charged with intermediate CQ1-3(13.6g, 32.8mmol), pinacol 3-pyridineborate (10g, 48.8mmol) and potassium carbonate (13.6g, 98.4mmol), then toluene (81mL), ethanol (27mL) and deionized water (27mL) were added, triphenylphosphine palladium chloride (0.68g, 0.97mmol) was added under nitrogen protection, the reaction was refluxed for 6h, the solution was cooled, the organic phase was washed with water, part of the solvent was concentrated off, a solid precipitated, filtered, the cake was recrystallized once with toluene and dried to give 9.7g of product in 81% yield.
1H NMR(400MHz,CDCl3,δ):8.73-8.77(m,2H),8.42-8.46(m,2H),7.63-7.73(m,2H),7.45-7.56(m,4H),7.09-7.29(m,6H).
Method for synthesizing compound CQ 1:
the intermediate CQ1-4(2g, 5.5mmol), 2, 4-diphenyl-6- (4-phenylboronic acid pinacol ester) pyrimidine (2.5g, 5.7mmol) and potassium carbonate (2.3g, 16.6mmol) are added into a flask, then toluene (20mL), ethanol (10mL) and deionized water (10mL) are added, palladium acetate (0.06g, 0.27mmol) and x-phos (0.12g, 0.54mmol) are added under the protection of nitrogen, reflux reaction is carried out for 2h, a large amount of solid is separated out, cooling is carried out, filtration is carried out, a filter cake is washed to be neutral by water, then washed by ethanol and dried. Then recrystallized once with toluene and dried to obtain 2.5g of product with yield of 71%.
1H NMR(400MHz,CDCl3,δ):8.86(d,1H),8.64-8.73(m,3H),8.34-8.36(m,2H),8.05-8.15(m,5H),7.95-7.98(m,1H),7.89-7.92(m,1H),7.78-7.81(m,2H),7.64-7.67(m,2H),7.36-7.60(m,14H).MS(ESI,m/z):[M+H]+:638.74.
Example 2
An organic electronic material containing nitrogen atom heterocycle, the organic electronic material contains compound CQ2, the synthetic route of compound CQ2 is as follows:
synthesis method of compound CQ2
The flask was charged with intermediate CQ1-4(2g, 5.5mmol), 2, 4-diphenyl-6- (4-phenylboronic acid pinacol) -1,3, 5-triazine (2.5g, 5.7mmol) and potassium carbonate (2.3g, 16.6mmol), toluene (20mL), ethanol (10mL) and deionized water (10mL) was added, palladium acetate (0.06g, 0.27mmol) and x-phos (0.12g, 0.54mmol) were added under nitrogen, the reaction was refluxed for 2h, a large amount of solid precipitated, cooled, filtered, the cake washed with water to neutrality, washed with ethanol and dried. Then recrystallizing with toluene once, drying to obtain 2.2g product with yield 63%, the product is compound CQ2, and its hydrogen nuclear magnetic spectrum is shown in figure 1.
1H NMR:(400MHz,CDCl3)δ8.77-8.95(m,8H),8.47-8.48(m,2H),8.05-8.08(m,1H),7.90(d,1H),7.72-7.77(m,3H),7.50-7.62(m,9H),7.27-7.32(m,3H),7.19-7.23(m,3H).MS(ESI,m/z):[M+H]+:639.52.
Example 3
An organic electronic material containing nitrogen atom heterocycle, the organic electronic material contains compound CQ5, the synthetic route of compound CQ5 is as follows:
synthesis method of compound CQ5
The flask was charged with intermediate CQ1-4(8g, 21.9mmol), 2, 4-diphenyl-6- (3-phenylboronic acid pinacol) -1,3, 5-triazine (10g, 23.0mmol) and potassium carbonate (9.1g, 65.8mmol), toluene (80mL), ethanol (40mL) and deionized water (40mL) were added, under nitrogen, palladium acetate (0.24g, 1.1mmol) and x-phos (0.48g, 2.2mmol) were added, the reaction was refluxed for 2h, a large amount of solid precipitated, cooled, filtered, the filter cake washed with water to neutrality, washed with ethanol and dried. Then recrystallized once by toluene and dried to obtain 4.6g of product with the yield of 33 percent.
1H NMR(400MHz,CDCl3,δ):8.88-8.98(m,3H),8.74-8.78(m,5H),8.47-8.49(m,2H),8.10-8.13(m,1H),7.94(s,1H),7.73-7.81(m,2H),7.51-7.64(m,10H),7.21-7.30(m,6H)。MS(ESI,m/z):[M+H]+:639.34.
Example 4
An organic electronic material containing nitrogen atom heterocycle, the organic electronic material contains compound CQ7, the synthetic route of compound CQ7 is as follows:
synthesis method of compound CQ7
The flask was charged with intermediate CQ1-4(2g, 5.5mmol), 2-phenyl 4-biphenyl-6- (3-phenylboronic acid pinacol) -1,3, 5-triazine (2.9g, 5.7mmol) and potassium carbonate (2.3g, 16.6mmol), toluene (20mL), ethanol (10mL) and deionized water (10mL) were added, palladium acetate (0.06g, 0.27mmol) and x-phos (0.12g, 0.54mmol) were added under nitrogen, the reaction was refluxed for 3h, a large amount of solid precipitated, cooled, filtered, the cake was washed with water to neutrality, washed with ethanol and dried. Then recrystallized once by toluene and dried to obtain 2.9g of product with the yield of 74 percent.
1H NMR(400MHz,CDCl3,δ):8.92(d,J＝2.0Hz,1H),8.86(d,1H),8.68-8.73(m,2H),8.64-8.66(m,1H),8.39-8.43(m,2H),8.12-8.14(m,1H),8.06-8.09(m,1H),7.99-8.05(m,2H),7.95-7.98(m,2H),7.89-7.92(m,1H),7.64-7.72(m,3H),7.42-7.61(m,15H),7.35-7.40(m,2H).MS(ESI,m/z):[M+H]+:715.48.
Example 5
An organic electronic material containing nitrogen atom heterocycle, the organic electronic material contains compound CQ10, the synthetic route of compound CQ10 is as follows:
the synthesis method of the intermediate CQ10-1 comprises the following steps:
the flask was charged with intermediate CQ1-1(15g, 58.3mmol), o-chlorobenzoic acid (10g, 63.9mmol) and potassium carbonate (20g, 144.7mmol), then toluene (90mL), tetrahydrofuran (45mL) and deionized water (45mL) were added, triphenylphosphine palladium chloride (0.3g, 0.43mmol) was added under nitrogen protection, the reaction was stopped after 4h of reflux reaction, cooled, separated, the organic phase washed neutral with water and concentrated to dryness to give 11.5g yellow oily liquid with a yield of 68%.
1H NMR(400MHz,CDCl3,δ):7.67-7.70(m,1H),7.61-7.64(m,2H),7.51-7.56(m,3H),7.45-7.49(m,1H),7.38-7.44(m,3H),7.34-7.37(m,3H).
The synthesis method of the intermediate CQ10-2 comprises the following steps:
intermediate CQ1-1(9.5g, 32.9mmol) and dichloromethane (150mL) are added into a flask, the temperature is reduced to 0-5 ℃, iodine chloride (6.4g, 39.4mmol) is dissolved in dichloromethane (50mL) and is added into the solution dropwise, after the dropwise addition, the solution is stirred for 0.5h, 150mL of 5% sodium sulfite aqueous solution is added dropwise to quench the reaction to neutrality, the solution is separated, dried, concentrated and dried, and petroleum ether passes through a column, so that 13.9g of light yellow oily liquid is obtained.
1H NMR(400MHz,CDCl3,δ):9.77-9.80(m,1H),8.52-8.54(m,1H),7.71-7.74(m,3H),7.54-7.56(m,3H),7.35-7.36(m,1H),7.25-7.30(m,3H).
The synthesis method of the intermediate CQ10-3 comprises the following steps:
the intermediate CQ10-2(12g, 28.9mmol), pinacol 3-pyridineborate (8.9g, 43.4mmol) and potassium carbonate (12g, 86.8mmol) were added to the flask, toluene (120mL), ethanol (60mL) and deionized water (60mL) were added, palladium triphenylphosphine chloride (0.6g, 0.85mmol) was added under nitrogen protection, the reaction was refluxed for 6h, the organic phase was cooled and separated, washed with water, part of the solvent was concentrated off, a solid was precipitated, filtered, the filter cake was recrystallized once with toluene and dried to obtain 7.9g of product with a yield of 75%.
1H NMR(400MHz,CDCl3,δ):9.76(d,1H),8.41-8.46(m,2H),7.66-7.79(m,2H),7.43-7.57(m,4H),7.34-7.38(m,1H),7.07-7.29(m,6H).
Method for synthesizing compound CQ 10:
the flask was charged with intermediate CQ1-4(2g, 5.5mmol), 2, 4-diphenyl-6- (3-phenylboronic acid pinacol) -1,3, 5-triazine (2.5g, 5.7mmol) and potassium carbonate (2.3g, 16.6mmol), toluene (20mL), ethanol (10mL) and deionized water (10mL) were added, palladium acetate (0.06g, 0.27mmol) and x-phos (0.12g, 0.54mmol) were added under nitrogen, refluxed for 2h, cooled, filtered, the cake washed with water to neutrality, washed with ethanol and dried. Then recrystallizing once with toluene and drying to obtain 2.8g of product with yield of 80%.
1H NMR(400MHz,CDCl3,δ):9.00-9.01(d,1H),8.88-8.89(m,1H),8.76-8.79(m,4H),8.45-8.49(m,2H),8.02-8.04(m,1H),7.42-7.68(m,13H),7.01-7.33(m,8H).MS(ESI,m/z):[M+H]+:639.39.
Example 6
An organic electronic material containing nitrogen atom heterocycle, the organic electronic material contains compound CQ21, the synthetic route of compound CQ21 is as follows:
the synthesis method of the intermediate CQ21-1 comprises the following steps:
the flask was charged with intermediate CQ1-3(6g, 14.5mmol), 2, 4-diphenyl-6- (3-phenylboronic acid pinacol) -1,3, 5-triazine (6.6g, 15.2mmol) and potassium carbonate (6g, 43.4mmol), toluene (36mL), ethanol (18mL) and deionized water (18mL) were added, triphenylphosphine palladium chloride (0.18g, 0.28mmol) was added under nitrogen, the reaction was refluxed for 3h, the organic phase was cooled, separated, washed with water, some of the solvent was concentrated, a solid precipitated, filtered, the filter cake was recrystallized once with toluene and dried to give 7.6g of product in 88% yield.
1H NMR(400MHz,CDCl3,δ):8.60-8.81(m,8H)，7.39-7.74(m,13H),7.27-7.29(m,2H),7.16-7.22(m,3H).:
The synthesis method of the intermediate CQ21 comprises the following steps:
the flask was charged with intermediate CQ21-1(4.7g, 7.9mmol), pinacol 3-pyridineborate (2.5g, 5.7mmol) and potassium carbonate (3.3g, 23.9mmol), then toluene (30mL), dioxane (30mL) and deionized water (15mL) was added, palladium acetate (0.14g, 0.63mmol) and x-phos (0.28g, 1.3mmol) were added under nitrogen, the reaction was refluxed for 5h, cooled, filtered, the filter cake was washed to neutral with water, washed with ethanol and dried. Then recrystallizing with toluene once, drying to obtain 4.2g product with yield of 84%, and obtaining the product CQ21, wherein the hydrogen nuclear magnetic spectrum is shown in figure 2.
1H NMR(400MHz,CDCl3,δ):8.96-8.98(d,1H),8.84-8.91(m,2H),8.72-8.74(m,4H),8.57-8.67(m,3H),7.94-7.96(m,1H),7.83-7.88(m,2H),7.68-7.76(m,2H),7.42-7.59(m,9H),7.32-7.36(m,2H),7.15-7.22(m,4H).MS(ESI,m/z):[M+H]+:639.28.
The effects of the compounds of the present invention are described in detail below by way of examples.
The preparation of the organic electroluminescent device and the structural schematic diagram are shown in fig. 3, and the specific device structure is as follows: glass/anode (ITO)/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/Electron Blocking Layer (EBL)/light emitting layer (host material GH: green light emitting material GD)/Electron Transport Layer (ETL)/electron injection Layer (LiF)/cathode (Al).
Example 7
Preparation of an OLED Using the Compound CQ1 of example 1
(1) The transparent conductive ITO glass substrate 110 (with the anode 120 on top) (south glass group ltd, china) was sonicated in a commercial detergent, rinsed in deionized water, sequentially washed with ethanol, acetone and deionized water, baked in a clean environment to completely remove moisture, cleaned with ultraviolet photosynthetic ozone, and treated with oxygen plasma for 30 seconds.
(2) The glass substrate with the anode is placed in a vacuum chamber, vacuum pumping is carried out, HIL (60nm) is evaporated on ITO to be used as a hole injection layer 130, and the evaporation rate is 0.1 nm/s.
(3) A compound NPB was deposited on the hole injection layer to form a hole transport layer 140 having a thickness of 10nm, a deposition rate of 0.1nm/s, and a TCTA was deposited to form an electron blocking layer 150 having a thickness of 5 nm. The evaporation rate was 0.1 nm/s.
(4) A light-emitting layer 160 with a thickness of 20nm was deposited on the hole-blocking layer, wherein CBP was the host light-emitting material and Ir (ppy)3 in an amount of 5 wt% was the phosphorescent dopant guest material, and the deposition rate was 0.1 nm/s.
(5) A compound CQ1 was deposited on the light-emitting layer to a thickness of 30nm as an electron transport layer 170. The evaporation rate is 0.1nm/s, and 1nm LiF is evaporated to form the electron injection layer 180 and 80nmAl is used as the cathode 190 of the device.
Example 8
The only difference from example 7 is that compound CQ2 was evaporated on the light-emitting layer in step (5) to a thickness of 30nm as an electron transport layer 170.
Example 9
The only difference from example 7 is that compound CQ5 was evaporated on the light-emitting layer in step (5) to a thickness of 30nm as an electron transport layer 170.
Example 10
The only difference from example 7 is that compound CQ7 was evaporated on the light-emitting layer in step (5) to a thickness of 30nm as an electron transport layer 170.
Example 11
The only difference from example 7 is that compound CQ10 was evaporated on the light-emitting layer in step (5) to a thickness of 30nm as an electron transport layer 170.
Example 12
The only difference from example 7 is that compound CQ21 was evaporated on the light-emitting layer in step (5) to a thickness of 30nm as an electron transport layer 170.
Comparative example 1
The only difference from example 7 is that compound CQ1 used in step (5) was replaced by compound 8 (i.e., ET1) described in manufacturing example 8 disclosed in Chinese patent CN 107445910A.
Comparative example 2
The only difference from example 7 is that compound 37 (i.e. ET2) described in example 5 disclosed in Chinese patent CN108299388A is used in place of compound CQ1 used in step (5).
Comparative example 3
The only difference from example 7 is that compound Alq3 was used in place of compound CQ1 used in step (5).
Experimental example 1:
the prepared device is measured by a Photo Research PR650 spectrometer at 20mA/cm2And measuring the time (T90) at which the luminance becomes 90% of the initial luminance at the current density.
Specifically, as shown in Table 1, FIG. 4 is a graph of current density versus current efficiency for the devices prepared, FIG. 5 is a graph of current density versus power efficiency versus external quantum efficiency for the devices prepared from CQ1, and FIG. 6 is a graph of current density versus power efficiency versus external quantum efficiency for the devices prepared from CQ1 at 20mA/cm2Current density of (a).
TABLE 1
As can be seen from the experimental data of table 1, fig. 4 and fig. 5, the nitrogen atom-containing heterocyclic compound of the present invention represented by chemical formula I or II can be applied to an organic electroluminescent device as an electron transport material.
The organic electroluminescent device prepared from the nitrogen atom-containing heterocyclic organic electronic material has lower working voltage than that of comparative examples 1-3 in the prior art, high brightness, and improved current efficiency, power efficiency and external quantum efficiency under the same current density. Meanwhile, under the same current density, the service life of the device prepared by the compound is greatly prolonged compared with that of the comparative example in the prior art. This is because, under the same current density, the invention has better electron transmission capability, lower working voltage, lower power consumption of the device and longer service life of the device.
The excellent performances are mainly that the nitrogen atom-containing heterocyclic organic electronic material prepared by introducing pyridine and pyrimidine or triazine at different positions of phenanthryl can effectively reduce the HOMO energy level and LUMO energy level of the material, increase the electron injection and transmission capability, reduce the working voltage of the device and improve the efficiency. Meanwhile, asymmetric groups are introduced at different positions of phenanthrene, so that the mutual influence of different groups can be reduced, the thermal stability of the material can be improved, an amorphous film can be prepared, the efficiency of a device can be improved, and the service life of the device can be prolonged.
The structural formula in the device is as follows:
the organic materials are all known materials and are obtained by market purchase.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. An organic electronic material containing a heterocyclic ring containing a nitrogen atom, wherein the organic electronic material contains a compound of the following structural formula (I) or (II):
wherein Py is C5-C30Substituted or unsubstituted pyridine of (a);
r is hydrogen, C1-C4Alkyl radical, C6-C30Substituted or unsubstituted aryl of (a);
Ar1and Ar2Independently selected from the group consisting of C6-C30Substituted or unsubstituted aryl of (a);
Z1、Z2and Z3At least one is N and the others are CH.
2. The organic electronic material of claim 1, wherein R is independently selected from hydrogen, phenyl, tolyl, biphenyl, or naphthyl;
Ar1and Ar2Independently selected from phenyl, tolyl, biphenyl, naphthyl, phenanthryl, anthracyl, perylenyl, phenylnaphthyl, naphthylphenyl, diphenylphenyl, 9, 9-dimethylfluorenyl, 9, 9-diphenylfluorenyl, 9, 9-spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl or benzophenanthryl.
3. The organic electronic material according to claim 1, wherein Py is pyridyl, R is phenyl, Ar is Ar1And Ar2Independently selected from phenyl, biphenyl or naphthyl.
4. The organic electronic material according to claim 1, wherein the organic electronic material comprises any one of the following compounds CQ1-CQ 28;
5. the organic electronic material of claim 1, wherein the preparation method of the compound of formula (I) or (II) comprises the following steps:
(A1) synthesis of Compound b: preparing a compound b by using o-bromoiodobenzene and an alkynyl compound through a Sonogashira reaction;
(A2) synthesis of Compound c: preparing a compound c by a Suzuki reaction of the compound b and halogenated phenylboronic acid;
(A3) synthesis of Compound d: reacting the compound c with iodine chloride or bromosuccinimide to prepare a compound d, wherein the used solvent is dichloromethane, chloroform, tetrahydrofuran, 1, 2-dichloroethane, acetonitrile, N-dimethylformamide, N-dimethylacetamide or dioxane;
(A4) synthesis of Compound f: obtaining a compound f through the reaction of the compound d and pyridine boronic acid e or pyridine boric acid ester Suzuki;
(A5) synthesis of compounds of structural formula (I): obtaining a compound with a structural formula (I) by a Suzuki reaction by using a compound j and boric acid ester h;
or;
(B1) synthesis of Compound b: preparing a compound b by using o-bromoiodobenzene and an alkynyl compound through a Sonogashira reaction;
(B2) synthesis of Compound c: preparing a compound c by a Suzuki reaction of the compound b and halogenated phenylboronic acid;
(B3) synthesis of Compound d: thirdly, reacting the compound c with iodine chloride or bromosuccinimide to prepare a compound d, wherein the used solvent is dichloromethane, chloroform, tetrahydrofuran, 1, 2-dichloroethane, acetonitrile, N-dimethylformamide, N-dimethylacetamide or dioxane;
(B4) synthesis of Compound j: carrying out Suzuki reaction on the compound d and boric acid ester h to obtain a compound j;
(B5) synthesis of compounds of structural formula (II): obtaining a compound with a structural formula (II) by a Suzuki reaction of a compound j and pyridine boronic acid e or pyridine boric acid ester;
or;
6. an organic electroluminescent device, comprising an anode, a cathode, and an organic layer;
the organic layer comprises one or more than one of a luminescent layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer or an electron transport layer;
at least one of said organic layers comprising the organic electronic material of any one of claims 1-5.
7. The organic electroluminescent device according to claim 6, wherein the organic layer contains the organic electronic material according to any one of claims 1 to 5 in a light-emitting layer.
8. The organic electroluminescent device according to claim 6, wherein the electron transport layer or the electron injection layer of the organic layer comprises the organic electronic material according to any one of claims 1 to 5.
9. The organic electroluminescent device according to claim 6, wherein the hole blocking layer in the organic layer comprises the organic electronic material according to any one of claims 1 to 5.
10. The use of the organic electronic material according to any one of claims 1 to 5, wherein the organic electronic material can be used for producing organic electroluminescent devices, organic solar cells, organic thin film transistors, organic photodetectors, organic field effect transistors, organic integrated circuits and organic photoreceptors.
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