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CN104078601B - Organic electroluminescence device and preparation method thereof - Google Patents

Organic electroluminescence device and preparation method thereof Download PDF

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Publication number
CN104078601B
CN104078601B CN201310108759.7A CN201310108759A CN104078601B CN 104078601 B CN104078601 B CN 104078601B CN 201310108759 A CN201310108759 A CN 201310108759A CN 104078601 B CN104078601 B CN 104078601B
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layer
barrier layer
phthalocyanine
mixed
electroluminescent device
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CN104078601A (en
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周明杰
钟铁涛
王平
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention relates to a kind of organic electroluminescence device and preparation method thereof, this organic electroluminescence device is layer structure, this layer structure stacks gradually as anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer, is provided with alternately laminated mixing barrier layer and inorganic barrier layer on described cathode layer surface.The organic electroluminescence device of the present invention; use the Organic substance of doping phthalocyanine thing and fluoride as mixing barrier layer; make film layer heat stability high; flatness is good; be conducive to inorganic matter film forming in the above, external water, the erosion to organic electroluminescence device of the oxygen isoreactivity material can be efficiently reduced, thus the organic functional material and electrode to organic electroluminescence device defines and be effectively protected; meet the requirement of the sealing of encapsulation, the life-span of OLED can be significantly increased.

Description

Organic electroluminescent device and preparation method thereof
Technical Field
The invention relates to the field of photoelectronic devices, in particular to an organic electroluminescent device. The invention also relates to a preparation method of the organic electroluminescent device.
Background
Organic electroluminescent devices (OLEDs) are a class of current-mode semiconductor light-emitting devices based on organic materials. The typical structure is that a luminescent layer with the thickness of dozens of nanometers is made on ITO glass by organic luminescent materials, and a metal electrode with low work function is arranged above the luminescent layer. When a voltage is applied across the electrodes, the light-emitting layer generates light radiation.
The OLED device has the advantages of active light emission, high light emitting efficiency, low power consumption, lightness, thinness, no viewing angle limitation, and the like, and is considered by the industry as a new generation device which is most likely to occupy an dominating position in the future illumination and display device market. As a new lighting and display technology, OLED technology has developed rapidly over the last decade, with great success. As more and more illumination and display manufacturers are increasingly invested in research and development in the world, the industrialization process of the OLED is greatly promoted, so that the growth speed of the OLED industry is remarkable, and the day before large-scale mass production is reached.
Flexible products are the development trend of organic electroluminescent devices, but the problem of short service life generally exists at present, so the service life of the devices is directly influenced by the quality of the packaging technology. The invention mainly aims to provide an organic electroluminescent device and a preparation method thereof, and the packaging technology has the advantages of simple process, strong water and oxygen resistance (WVTR) and obviously prolonged service life of the flexible OLED device.
Disclosure of Invention
The present invention is directed to solve the problems and disadvantages of the prior art, and provides an organic electroluminescent device and a method for fabricating the same, in which an organic material doped with phthalocyanine and fluoride is used as a mixed barrier layer, so that a film layer has high thermal stability and good flatness, which is beneficial for an inorganic material to form a film thereon, and can effectively reduce the erosion of active substances such as external water, oxygen, etc. to the organic electroluminescent device.
The technical scheme provided by the invention aiming at the technical problems is as follows: an organic electroluminescent device, the organic electroluminescent device is a laminated structure, the laminated structure is sequentially laminated as follows: an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer; the surface of the cathode layer is provided with a mixed barrier layer and an inorganic barrier layer which are alternately stacked; wherein,
the mixed barrier layer is made of a mixture consisting of phthalocyanamide, organic matters, fluoride and oxides; the phthalocyanine compound is one of copper phthalocyanine, zinc phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, manganese phthalocyanine and nickel phthalocyanine, and the organic matter is N, N ' -diphenyl-N, N ' -di (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, 4',4' ' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tris (1-phenyl-1H-benzimidazole)-2-yl) benzene, said fluoride being LiF, CeF2、MgF2、AlF3、CaF2Or BaF2Wherein the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2One of (1);
the inorganic barrier layer is made of TiO2、MgO、SiO2、ZrO2ZnO or Al2O3One of (1);
the phthalocyanine accounts for 40-60 mol% of the mixed barrier layer, the fluoride accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 10-20 mol% of the mixed barrier layer, and the organic matter accounts for not more than 40mol% of the mixed barrier layer.
The thickness of the mixed barrier layer is 100 nm-200 nm.
The thickness of the inorganic barrier layer is 50 nm-100 nm.
The number of the mixed barrier layers and the inorganic barrier layers which are alternately stacked is 4-6.
The hole injection layer is made of MoO3Doping the mixed material into N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine according to the doping concentration of 30 wt%;
the material of the hole transport layer adopts 4,4',4' ' -tri (carbazole-9-yl) triphenylamine;
the material of the luminescent layer is a doped mixed material formed by doping tris (2-phenylpyridine) iridium into 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) according to the doping concentration of 5 wt%;
the material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline;
the electron injection layer is made of CsN3A mixed material formed by doping 4, 7-diphenyl-1, 10-phenanthroline according to the doping concentration of 30 wt%;
the cathode layer is made of ZnS, Ag and ZnS which are sequentially laminated by adopting a vacuum evaporation method.
The invention also comprises a preparation method of the organic electroluminescent device, which comprises the following steps:
(a) preparing a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode layer in sequence on an anode conducting layer of a cleaned anode conducting substrate by adopting a vacuum evaporation method;
(b) on the cathode layer, firstly, preparing a mixed barrier layer by adopting a vacuum evaporation method; preparing an inorganic barrier layer on the mixed barrier layer by adopting a magnetron sputtering method; then, alternately laminating for a plurality of times in sequence to prepare a mixed barrier layer and an inorganic barrier layer; wherein,
the mixed barrier layer is made of a mixture consisting of phthalocyanamide, organic matters, fluoride and oxides; the phthalocyanine compound is one of copper phthalocyanine, zinc phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, manganese phthalocyanine and nickel phthalocyanine, the organic matter is one of N, N ' -diphenyl-N, N ' -di (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, 4',4' ' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene, and the fluoride is one of LiF and CeF2、MgF2、AlF3、CaF2、BaF2Wherein the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O、MnO2One of (1);
the inorganic barrier layer is made of TiO2、MgO、SiO2、ZrO2ZnO or Al2O3One of (1);
the phthalocyanine accounts for 40-60 mol% of the mixed barrier layer, the fluoride accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 10-20 mol% of the mixed barrier layer, and the organic matter accounts for not more than 40mol% of the mixed barrier layer.
The thickness of the inorganic barrier layer is 100 nm-200 nm; the thickness of the mixed barrier layer is 50 nm-100 nm.
In the step (a), the vacuum degree of the vacuum evaporation of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer and the cathode layer is 1 × 10-5Pa, evaporation rate of
In the step (b), the number of times of alternation of the mixed barrier layer and the inorganic barrier layer is 4-6 times.
In the step (a), the vacuum degree of the vacuum evaporation of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer and the cathode layer is 1 × 10-5Pa; the evaporation rate of the hole injection layer, the hole transport layer and the electron transport layer isThe evaporation rate of the luminescent layer and the electron injection layer isThe cathode layer has an evaporation rate of
Compared with the prior art, the organic electroluminescence device and the preparation method thereof have the following advantages: the organic electroluminescent device of the invention adopts the organic matter doped with phthalocyanine and fluoride as the mixed barrier layer, so that the film has high thermal stability and good flatness, is beneficial to the film formation of the inorganic matter on the mixed barrier layer, and can effectively reduce the erosion of active substances such as external water, oxygen and the like to the organic electroluminescent device, thereby forming effective protection to organic functional materials and electrodes of the organic electroluminescent device, meeting the requirement of the sealing property of encapsulation and obviously prolonging the service life of the OLED device.
Drawings
Fig. 1 is a schematic view of the structure of an organic electroluminescent device of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the following examples.
The organic electroluminescent device of the present invention has a layered structure, and as shown in fig. 1, the layered structure includes an anode conductive substrate 101, a hole injection layer 102, a hole transport layer 103, a light emitting layer 104, an electron transport layer 105, an electron injection layer 106, a cathode layer 107, a mixed barrier layer 108, and an inorganic barrier layer 109, which are sequentially stacked.
In the organic electroluminescent device, a plurality of mixed barrier layers and inorganic barrier layers which are alternately laminated are arranged on the surface of the cathode layer. The number of the mixed barrier layers and the inorganic barrier layers which are alternately stacked is 4-6.
The material of the mixed barrier layer is a mixture consisting of phthalocyanamide, organic matters, fluoride and oxide; the phthalocyanine compound is one of copper phthalocyanine, zinc phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, manganese phthalocyanine and nickel phthalocyanine, the organic matter is one of N, N ' -diphenyl-N, N ' -di (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, 4',4' ' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene, and the fluoride is one of LiF and CeF2、MgF2、AlF3、CaF2Or BaF2Wherein the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2One of (1);
the inorganic barrier layer is made of TiO2、MgO、SiO2、ZrO2ZnO or Al2O3One of (1);
the phthalocyanine accounts for 40-60 mol% of the mixed barrier layer, the fluoride accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 10-20 mol% of the mixed barrier layer, and the organic matter accounts for not more than 40mol% of the mixed barrier layer.
The thickness of the mixed barrier layer is 100 nm-200 nm, and the thickness of the inorganic barrier layer is 50 nm-100 nm.
In the organic electroluminescent device, the anode conductive substrate 101 includes an anode conductive layer and a substrate, the substrate may be a glass substrate or an organic thin film substrate, the anode conductive layer may be made of conductive oxides, such as Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO) or fluorine-doped zinc oxide (FTO), and the conductive oxides are prepared on the glass substrate, which are abbreviated as ITO glass, AZO glass, IZO glass, and FTO glass. The anode conductive substrate may be made by itself or may be commercially available. In practical applications, other suitable materials can be selected as the anode conductive substrate 101 according to requirements. In practical applications, a desired anode pattern of the organic electroluminescent device can be prepared on the anode conductive substrate 101. The anode conductive substrate 101 is conventional and will not be described herein.
In the organic electroluminescent device, the materials and thicknesses of other functional layers are as follows:
the hole injection layer is made of MoO3Doping the mixed material into N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine according to the doping concentration of 30 wt%; the thickness is 10 nm;
the material of the hole transport layer adopts 4,4',4' -tri (carbazole-9-yl) triphenylamine; thickness of 30nm
The material of the luminescent layer is a doped mixed material formed by doping tris (2-phenylpyridine) iridium into 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) according to the doping concentration of 5 wt%; the thickness is 20 nm;
the material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline; the thickness is 10 nm;
the electron injection layer is made of CsN3A mixed material formed by doping 4, 7-diphenyl-1, 10-phenanthroline according to the doping concentration of 30 wt%; the thickness is 20 nm.
The cathode layer is made of ZnS, Ag and ZnS which are sequentially laminated, and the thickness of the cathode layer is 30 nm.
The preparation method of the organic electroluminescent device comprises the following steps:
(a) preparing a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode layer in sequence on an anode conducting layer of a cleaned anode conducting substrate by adopting a vacuum evaporation method;
the vacuum degree of the hole injection layer, the hole transport layer, the luminescent layer, the electron transport layer, the electron injection layer and the cathode layer is 1 × 10 during vacuum evaporation preparation-5Pa; the evaporation rates of the hole injection layer, the hole transport layer and the electron transport layer areThe light emitting layer and the electron injection layer have evaporation rates ofThe evaporation rate of the cathode layer is
(b) On the cathode layer, firstly, preparing a mixed barrier layer by adopting a vacuum evaporation method; then preparing an inorganic barrier layer on the mixed barrier layer by adopting a magnetron sputtering method; then, alternately laminating the prepared mixed barrier layer and the inorganic barrier layer for a plurality of times in sequence; the number of times of alternating the mixed barrier layer and the inorganic barrier layer is 4-6.
When the mixed barrier layer is prepared by vacuum evaporation, the vacuumThe vacuum degree of evaporation is 1 × 10-5Pa～1×10-3Pa, the evaporation rate of the vacuum evaporation isWhen the magnetron sputtering is used for preparing the inorganic barrier layer, the vacuum degree is 1 × 10-5Pa～1×10-3Pa。
Wherein the material of the mixed barrier layer is a mixture consisting of phthalocyanamide, organic matters, fluoride and oxide; the phthalocyanine compound is one of copper phthalocyanine, zinc phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, manganese phthalocyanine and nickel phthalocyanine, the organic matter is one of N, N ' -diphenyl-N, N ' -di (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, 4',4' ' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene, and the fluoride is one of LiF and CeF2、MgF2、AlF3、CaF2、BaF2Wherein the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O、MnO2One of (1);
the inorganic barrier layer is made of TiO2、MgO、SiO2、ZrO2ZnO or Al2O3One of (1);
the phthalocyanine accounts for 40-60 mol% of the mixed barrier layer, the fluoride accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 10-20 mol% of the mixed barrier layer, and the organic matter accounts for not more than 40mol% of the mixed barrier layer.
The thickness of the mixed barrier layer is 100 nm-200 nm, and the thickness of the inorganic barrier layer is 50 nm-100 nm.
The organic electroluminescent device and the production steps thereof of the present invention are specifically described in examples 1 to 6 below:
example 1
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, CuPc-TAPC-LiF-MoO3Layer, TiO2And (3) a layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
The organic electroluminescent device is prepared by adopting the following steps:
a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparing a hole transport layer by adopting 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) as a hole transport material and ensuring that the vacuum degree is 1 × 10-5Pa, evaporation rateThe evaporation thickness is 30 nm;
d) light-emitting layer: using 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl)) Benzene (TPBI) is used as a host material, and tris (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration 5% and degree of vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 1 × 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing cathode layer from ZnS/Ag/ZnS with a thickness of 100nm and a vacuum degree of 1 × 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by adopting a vacuum evaporation mode, wherein the mixed barrier layer is prepared by doping and co-evaporating four substances, namely CuPc (copper phthalocyanine), TAPC (organic substance), LiF (LiF), MoO (MoO), and the like3Wherein the CuPc accounts for 50mol%, the LiF accounts for 30mol%, and the MoO accounts for316mol% and 4mol% of organic TAPC, degree of vacuum of the mixed barrier layer 1 × 10-5Pa, evaporation rateThe thickness is 200 nm;
i) manufacturing an inorganic barrier layer: adopts a magnetron sputtering method to prepare TiO2Background vacuum degree of film, inorganic Barrier layer 1 × 10-5Pa and the thickness is 100 nm. During preparation, the flow of Ar is introduced at 10sccm and CH4Flow rate of 20 sccm;
j) repeating the steps h) and i)6 times alternately.
Example 2
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS layer, ZnPc-NPB-CeF2-V2O5Layer, MgO layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
The organic electroluminescent device is prepared by adopting the following steps:
a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparing a hole transport layer by adopting 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) as a hole transport material and ensuring that the vacuum degree is 1 × 10-5Pa, evaporation rateThe evaporation thickness is 30 nm;
d) light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration 5% and degree of vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 1 × 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing cathode layer from ZnS/Ag/ZnS with a thickness of 100nm and a vacuum degree of 1 × 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: by means of a vacuum chamberPreparing a mixed barrier layer on the cathode layer by air evaporation, wherein the mixed barrier layer is prepared by doping and co-evaporating four substances, one is ZnPc (zinc phthalocyanine), the other is NPB (zinc phthalocyanine), and the third is CeF2The fourth is V2O5ZnPc in 40mol%, NPB in 35mol%, CeF2In a proportion of 15mol%, V2O5The proportion is 10mol%, and the vacuum degree of the mixed barrier layer is 5 × 10-5Pa, evaporation rateThe thickness is 150 nm;
i) the preparation of the inorganic barrier layer comprises preparing MgO film by magnetron sputtering method, wherein the background vacuum degree of the inorganic barrier layer is 1 × 10-5Pa and the thickness is 50 nm. During preparation, the flow rate of Ar introduced is 5sccm and CH415 sccm;
j) repeating the steps h) and i)5 times alternately.
Example 3
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, FePc-Alq3-MgF2-WO3Layer of SiO2And (3) a layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
The organic electroluminescent device is prepared by adopting the following steps:
a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparing a hole transport layer by adopting 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) as a hole transport material and ensuring that the vacuum degree is 1 × 10-5Pa, evaporation rateThe evaporation thickness is 30 nm;
d) light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration 5% and degree of vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 1 × 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Incorporation into Bphen, dopingConcentration 30wt% and vacuum degree 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing cathode layer from ZnS/Ag/ZnS with a thickness of 100nm and a vacuum degree of 1 × 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by adopting a vacuum evaporation mode, wherein the mixed barrier layer is prepared by doping and co-evaporating four substances, one is FePc (iron phthalocyanine), and the other is Alq3And the third is MgF2The fourth is WO3The proportion of FePc is 60mol%, Alq3The proportion of MgF is 10mol percent2In a proportion of 10mol%, WO320mol% of the vacuum degree of 1 × 10-5Pa, evaporation rateThe thickness is 200 nm;
i) manufacturing an inorganic barrier layer: the SiO is prepared by adopting a magnetron sputtering method2Background vacuum degree of film, inorganic Barrier layer 1 × 10-5Pa, thickness 70 nm. During preparation, the flow rate of Ar introduced is 7sccm and CH4Flow rate of 10 sccm;
j) repeating the steps h) and i)6 times alternately.
Example 4
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, CoPc-m-MTDATA-AlF3-Cs2O layer, ZrO2And (3) a layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
The organic electroluminescent device is prepared by adopting the following steps:
a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparing a hole transport layer by adopting 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) as a hole transport material and ensuring that the vacuum degree is 1 × 10-5Pa, evaporation rateThe evaporation thickness is 30 nm;
d) light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration 5% and degree of vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 1 × 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing cathode layer from ZnS/Ag/ZnS with a thickness of 100nm and a vacuum degree of 1 × 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by adopting a vacuum evaporation mode, wherein the mixed barrier layer is prepared by doping and co-evaporating four substances, one is CoPc (cobalt phthalocyanine), the other is m-MTDATA, and the third is AlF3And the fourth is Cs250mol% of O and CoPc, 15mol% of m-MTDATA, and AlF3The proportion of Cs is 20mol percent2The proportion of O is 15mol percent, and the vacuum degree of the mixed barrier layer is 5 × 10-5Pa, evaporation rateThe thickness is 150 nm;
i) manufacturing an inorganic barrier layer: ZrO prepared by adopting magnetron sputtering method2Background vacuum degree of film, inorganic Barrier 5 × 10-5Pa, thickness 100nm, when preparing, Ar flow 10sccm, CH4The flow rate is 20 sccm;
j) repeating the steps h) and i) for 4 times alternately.
Example 5
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, MnPc-BCP-CaF2-Ni2An O layer and a ZnO layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
The organic electroluminescent device is prepared by adopting the following steps:
a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparation of hole transport layer: the use of 4,4',4' ' -tris (carbazol-9-yl) triphenylamine (TCTA) as hole transport materialDegree of vacuum 1 × 10-5Pa, evaporation rateThe evaporation thickness is 30 nm;
d) light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration 5% and degree of vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 1 × 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing cathode layer from ZnS/Ag/ZnS with a thickness of 100nm and a vacuum degree of 1 × 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by adopting a vacuum evaporation mode, wherein the mixed barrier layer is prepared by doping and co-evaporating four substances, namely MnPc (manganese phthalocyanine), BCP (BCP), and CaF (calcium phthalocyanine)2The fourth is Ni2The proportion of O and MnPc is 55mol percent, the proportion of BCP is 15mol percent of CaF2In a proportion of 15mol%, Ni2The proportion of O is 15mol%, the thickness of the mixed barrier layer is 150nm, and the vacuum degree is 5 × 10-5Pa, evaporation rate
i) Preparing an inorganic barrier layer, namely preparing a ZnO film by adopting a magnetron sputtering method, wherein the background vacuum degree of the inorganic barrier layer is 5 × 10-5Pa and the thickness is 80 nm. During preparation, the flow rate of Ar introduced is 5sccm and CH4Flow rate of 20 sccm;
j) repeating the steps h) and i)6 times alternately.
Example 6
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, NiPc-TPBi-BaF2-MnO2Layer of Al2O3And (3) a layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
The organic electroluminescent device is prepared by adopting the following steps:
a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparing a hole transport layer by adopting 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) as a hole transport material and ensuring that the vacuum degree is 1 × 10-5Pa, evaporation rateThe evaporation thickness is 30 nm;
d) light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration 5% and degree of vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 1 × 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 1 × 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing a cathode layer: cathode is made ofZnS/Ag/ZnS, thickness of 100nm, vacuum degree of 1 × 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by vacuum evaporation, wherein the mixed barrier layer is prepared by doping and co-evaporating four substances, namely NiPc (nickel phthalocyanine), TPBi and BaF2The fourth is MnO2The proportion of NiPc is 60mol%, the proportion of TPBi is 19mol%, and BaF2In a proportion of 16mol%, MnO2The proportion is 15mol%, and the vacuum degree of the mixed barrier layer is 1 × 10-3Pa, evaporation rateThe thickness is 150 nm;
i) manufacturing an inorganic barrier layer: al is prepared by adopting a magnetron sputtering method2O3Background vacuum degree of film, inorganic Barrier layer 1 × 10-3Pa, thickness 70 nm. During preparation, the flow rate of Ar introduced is 7sccm, and the flow rate of CH4 is 13 sccm;
j) repeating the steps h) and i)6 times alternately.
Performance testing
The organic electroluminescent devices according to the present invention of examples 1 to 6 above were subjected to the water oxygen resistance (WVTR) and transmittance test, and as can be seen from table 1 below, the water oxygen resistance reached 10－4g/m2The performance of the OLED is higher than day, and the service life of the OLED light-emitting device manufactured by the OLED light-emitting device is longer than 4800 hours on average.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
WVTR(g/m2/day) 6.0E-4 6.3E-4 6.7E-4 7.2E-4 7.5E-4 8.2E-4
Light transmittance 63％ 64％ 65％ 67％ 68％ 69％
Life (hours) 4945 4910 4883 4845 4820 4800
Therefore, the organic electroluminescent device and the preparation method thereof have the following advantages:
1. the organic electroluminescent device of the invention adopts the organic matter doped with phthalocyanine and fluoride as the mixed barrier layer, so that the film has high thermal stability and good flatness, is beneficial to the film formation of the inorganic matter on the mixed barrier layer, and can effectively reduce the erosion of active substances such as external water, oxygen and the like to the organic electroluminescent device, thereby forming effective protection to organic functional materials and electrodes of the organic electroluminescent device, meeting the requirement of the sealing property of encapsulation and obviously prolonging the service life of the OLED device. The water and oxygen resistance of the paint reaches 10－4g/m2And/day, the service life of the OLED luminescent device manufactured by the method is more than 4800 hours on average, and the light transmittance of the packaging surface is more than 63%.
2. The preparation method of the organic electroluminescent device is simple in preparation process and easy for large-area preparation, is particularly suitable for application of the flexible OLED device, solves the packaging problem of the flexible OLED, and promotes the development of flexible OLED products.
The above-mentioned embodiments are merely preferred examples of the present invention, and not intended to limit the present invention, and those skilled in the art can easily make various changes and modifications according to the main concept and spirit of the present invention, so that the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. An organic electroluminescent device, the organic electroluminescent device is a laminated structure, the laminated structure is sequentially laminated as follows: an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer; the cathode layer is characterized in that mixed barrier layers and inorganic barrier layers which are alternately stacked are arranged on the surface of the cathode layer; wherein,
the material of the mixed barrier layer is a mixture consisting of phthalocyanine, organic matters, fluoride and oxide; the phthalocyanine is copper phthalocyanine, zinc phthalocyanine, iron phthalocyanine or phthalocyanineCobalt, manganese phthalocyanine or nickel phthalocyanine, the organic matter is one of N, N ' -diphenyl-N, N ' -di (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene, and the fluoride is one of LiF and CeF2、MgF2、AlF3、CaF2Or BaF2Wherein the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2One of (1);
the inorganic barrier layer is made of TiO2、MgO、SiO2、ZrO2ZnO or Al2O3One of (1);
the phthalocyanine accounts for 40-60 mol% of the mixed barrier layer, the fluoride accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 10-20 mol% of the mixed barrier layer, and the organic matter accounts for not more than 40mol% of the mixed barrier layer.
2. The organic electroluminescent device according to claim 1, wherein the thickness of the hybrid barrier layer is 100nm to 200 nm.
3. The organic electroluminescent device according to claim 1, wherein the inorganic barrier layer has a thickness of 50nm to 100 nm.
4. The organic electroluminescent device according to claim 1, wherein: the number of the mixed barrier layers and the inorganic barrier layers which are alternately stacked is 4-6.
5. The organic electroluminescent device according to claim 1, wherein:
the hole injection layer is made of MoO3Doping N, N '-diphenyl-N, N' -di (1-naphthalene) according to the doping concentration of 30wt%1,1 '-biphenyl-4, 4' -diamine;
the hole transport layer is made of 4,4' -tris (carbazole-9-yl) triphenylamine;
the material of the luminescent layer is a doped mixed material formed by doping tris (2-phenylpyridine) iridium into 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) according to the doping concentration of 5 wt%;
the material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline;
the electron injection layer is made of CsN3A mixed material formed by doping 4, 7-diphenyl-1, 10-phenanthroline according to the doping concentration of 30 wt%;
the cathode layer is made of ZnS, Ag and ZnS which are sequentially laminated by adopting a vacuum evaporation method.
6. A preparation method of an organic electroluminescent device comprises the following steps:
(a) preparing a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode layer in sequence on an anode conducting layer of a cleaned anode conducting substrate by adopting a vacuum evaporation method;
(b) on the cathode layer, firstly, preparing a mixed barrier layer by adopting a vacuum evaporation method; preparing an inorganic barrier layer on the mixed barrier layer by adopting a magnetron sputtering method; then, alternately stacking the mixed barrier layer and the inorganic barrier layer for a plurality of times in sequence; wherein,
the material of the mixed barrier layer is a mixture consisting of phthalocyanine, organic matters, fluoride and oxide; the phthalocyanine is one of copper phthalocyanine, zinc phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, manganese phthalocyanine and nickel phthalocyanine, the organic matter is one of N, N ' -diphenyl-N, N ' -di (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene, and the fluoride is one of LiF and CeF2、MgF2、AlF3、CaF2Or BaF2Wherein the oxide isMoO3、V2O5、WO3、Cs2O、Ni2O or MnO2One of (1);
the inorganic barrier layer is made of TiO2、MgO、SiO2、ZrO2ZnO or Al2O3One of (1);
the phthalocyanine accounts for 40-60 mol% of the mixed barrier layer, the fluoride accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 10-20 mol% of the mixed barrier layer, and the organic matter accounts for not more than 40mol% of the mixed barrier layer.
7. The method according to claim 6, wherein the thickness of the mixed barrier layer is 100nm to 200 nm; the thickness of the inorganic barrier layer is 50 nm-100 nm.
8. The method according to claim 6, wherein in the step (a), the vacuum degree of the vacuum evaporation for preparing the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, the electron injection layer and the cathode layer is 1 × 10-5Pa; the evaporation rate of the hole injection layer, the hole transport layer and the electron transport layer isThe evaporation rate of the luminescent layer and the electron injection layer isThe cathode layer has an evaporation rate of
9. The method according to claim 6, wherein in the step (b), the number of times of alternation of the mixed barrier layer and the inorganic barrier layer is 4 to 6.
10. The method according to claim 6, wherein in the step (b), the vacuum evaporation is performed to obtain the mixed barrier layer under a vacuum degree of 1 × 10-5Pa～1×10-3Pa, the evaporation rate of the vacuum evaporation isWhen the inorganic barrier layer is prepared by magnetron sputtering, the vacuum degree is 1 × 10-5Pa～1×10-3Pa。
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