CN104600209A - Preparation method of organic electroluminescent device - Google Patents

Preparation method of organic electroluminescent device Download PDF

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Publication number
CN104600209A
CN104600209A CN201310530139.2A CN201310530139A CN104600209A CN 104600209 A CN104600209 A CN 104600209A CN 201310530139 A CN201310530139 A CN 201310530139A CN 104600209 A CN104600209 A CN 104600209A
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layer
evaporation
light emitting
preparation
organic electroluminescence
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周明杰
冯小明
钟铁涛
王平
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • 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

Abstract

The invention relates to a preparation method of an organic electroluminescent device. The preparation method of the organic electroluminescent device includes the steps of: providing a conductive anode substrate; performing vacuum evaporation deposition on the conductive anode substrate to form a hole transporting layer; mixing red fluorescent material with light emitting main body material to obtain a mixture of the red fluorescent material and the light emitting main body, heating the mixture of the red fluorescent material and the light emitting main body to form solid solution in the atmosphere of protective gas, performing vacuum evaporation deposition on the solid solution and forming a red light emitting layer on the hole transporting layer; performing vacuum evaporation deposition on the red light emitting layer to form an electronic transporting layer and performing vacuum evaporation deposition on the electronic transporting layer to form a cathode, and thereby obtaining the organic electroluminescent device. According to the preparation method of the organic electroluminescent device, the doping proportion of the red fluorescent material in the red light emitting layer can be accurately controlled, and the organic electroluminescent device with the pre-designed structure can be prepared.

Description

The preparation method of organic electroluminescence device
Technical field
The present invention relates to electroluminescent device preparing technical field, particularly relate to a kind of preparation method of organic electroluminescence device.
Background technology
Organic electroluminescent (Organic Light Emission Diode), hereinafter referred to as OLED, there is the characteristics such as brightness is high, material selection range is wide, driving voltage is low, all solidstate active illuminating, have the advantages such as high definition, wide viewing angle and fast response time simultaneously, a kind of Display Technique and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of current lot of domestic and foreign researcher.
Up to the present, in organic electroluminescence device field, although the scientific research personnel of whole world various countries is by selecting suitable organic material and rational device structure design, made the indices of device performance be greatly improved.
But, in some current luminescent devices, the material of red light luminescent layer is generally that red fluorescence material is doped in the dopant material formed in light emitting host material, red fluorescence material oneself can be caught charge carrier due to it and not need the energy trasfer by other layers in luminescent layer, therefore lower concentration is usually only needed just can to obtain higher luminosity, generally, the mass concentration of red fluorescence material is lower than 1%.Such as Rubrene is entrained in Alq 3time middle, its doping ratio is often lower than 1%.When adopting common co-evaporation method to prepare luminescent layer, the evaporation rate of red fluorescence material is extremely low, need to adopt supply low in calories to evaporation source, thus obtain lower evaporation rate, and be limited to the precision of watch-dog, this technique is more difficult for the control of evaporation source, thus causes the doping ratio of red fluorescence material to be difficult to control.Under the condition requiring doping ratio accurately, need to form the lower doping film of doping ratio, very high to the evaporation rate monitoring requirement of red fluorescence material, this is very high to the requirement of watch-dog, makes the ratio being difficult to accurately control red fluorescence material under existing condition.Therefore, because the doping ratio of red fluorescence material cannot accurately control, the doping content of the doping film therefore obtained is uncontrollable, also just cannot realize the OLED structure preset, thus affects the luminescent properties of device.
Summary of the invention
Based on this, be necessary to provide a kind of preparation method that comparatively accurately can control the organic electroluminescence device of the doping ratio of the red fluorescence material in red light luminescent layer.
A preparation method for organic electroluminescence device, comprises the steps:
Conductive anode substrate is provided;
On described conductive anode substrate, vacuum evaporation forms hole transmission layer;
Red fluorescence material and light emitting host material are carried out the mixture being mixed to get red fluorescence material and light emitting host material, in protective gas atmosphere, the mixture of described red fluorescence material and light emitting host material is carried out adding thermosetting solid solution, solid solution described in vacuum evaporation, forms red light luminescent layer on the hole transport layer;
On described red light luminescent layer, vacuum evaporation forms electron transfer layer; And
Vacuum evaporation forms negative electrode on the electron transport layer, obtains described organic electroluminescence device.
Wherein in an embodiment, described in vacuum evaporation during solid solution, before forming the step of red light luminescent layer on the hole transport layer, also comprise the step that vacuum evaporation on the hole transport layer forms blue light-emitting.
Wherein in an embodiment, when the described mixture by described red fluorescence material and light emitting host material carries out the step adding thermosetting solid solution, the mixture of described red fluorescence material and light emitting host material is carried out the temperature of the fusing point 5 ~ 10 DEG C being heated above described light emitting host material, then be cooled to room temperature, obtain described solid solution.
Wherein in an embodiment, the heating rate of described heating is 5 ~ 10 DEG C/min, described in be cooled to room temperature rate of temperature fall be 5 ~ 10 DEG C/min.
Wherein in an embodiment, solid solution described in described vacuum evaporation, is formed in the step of red light luminescent layer on the hole transport layer, and the evaporation rate of described light emitting host material is 0.1 ~ 1nm/s.
Wherein in an embodiment, solid solution described in described vacuum evaporation, is formed in the step of red light luminescent layer on the hole transport layer, and the vacuum degree of vacuum evaporation is 1 × 10 -5~ 1 × 10 -3pa.
Wherein in an embodiment, the mass ratio of described red fluorescence material and light emitting host material is 0.1:100 ~ 1:100.
Wherein in an embodiment, the material of described hole transmission layer is hole mobile material, and described when on described conductive anode substrate, vacuum evaporation forms the step of hole transmission layer, the evaporation rate of described hole mobile material is 0.1 ~ 1nm/s.
Wherein in an embodiment, the material of described electron transfer layer is electron transport material, and described when on described red light luminescent layer, vacuum evaporation forms the step of electron transfer layer, the evaporation rate of described electron transport material is 0.1 ~ 1nm/s.
Wherein in an embodiment, described negative electrode comprises and is laminated in fluoride layer on described electron transfer layer and metal level, the material of described fluoride layer is fluoride, the material of described metal level is metal or alloy, when described vacuum evaporation on the electron transport layer forms the step of negative electrode, the evaporation rate of described fluoride is 0.1 ~ 1nm/s, and the evaporation rate of described metal or alloy is 0.1 ~ 1nm/s.
The preparation method of above-mentioned organic electroluminescence device, first red fluorescence material and light emitting host material premix are added thermosetting solid solution, then this solid solution of vacuum evaporation, the evaporation rate of the technique of this single source evaporation can improve, control than being easier to, more accurately can control the doping ratio of the red fluorescence material in red light luminescent layer, the organic electroluminescence device structure designed in advance prepared.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of the organic electroluminescence device of an execution mode.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with chart.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the organic electroluminescence device of an execution mode, comprises the steps:
Step S110: conductive anode substrate is provided.
Conductive anode substrate is preferably the ITO electro-conductive glass that tin indium oxide (ITO) pellicular cascade is formed on glass substrate.
Preferably, the ITO electro-conductive glass of conductive anode substrate to be square resistance be 5 ~ 100 Ω/.
By clean for conductive anode base-plate cleaning, dry, for subsequent use.
Step S120: vacuum evaporation forms hole transmission layer on conductive anode substrate.
The material of hole transmission layer is hole mobile material.Hole mobile material is preferably N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), N; N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4; 4'-diamines (TPD) or N; N, N', N '-(tetramethoxy phenyl)-benzidine (MeO-TPD).
Preferred employing thermal resistance evaporation process forms the hole transmission layer be laminated on conductive anode substrate, and vacuum degree is preferably 1 × 10 -5~ 1 × 10 -3pa, the evaporation rate of hole mobile material is preferably 0.1 ~ 1nm/s, is conducive to forming the higher film of compactness.
The thickness of hole transmission layer is 20 ~ 60nm.
Step S130: red fluorescence material and light emitting host material are carried out the mixture being mixed to get red fluorescence material and light emitting host material; in protective gas atmosphere, the mixture of red fluorescence material and light emitting host material is carried out adding thermosetting solid solution; this solid solution of vacuum evaporation, hole transmission layer forms red light luminescent layer.
Red fluorescence material is preferably 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 4-(dintrile methene)-2-isopropyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTI), 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene) or 4-(dimercapto methylene)-2-methyl-6-(is to dimethylaminostyryl)-4H-pyrans (DCM).
Light emitting host material is preferably oxine aluminium (Alq 3) or N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB).
The mass ratio of red fluorescence material and light emitting host material is preferably 0.1:100 ~ 1:100.
Red fluorescence material and light emitting host material are carried out the mixture being mixed to get red fluorescence material and light emitting host material; in normal pressure and protective gas atmosphere; heated by the mixture of this red fluorescence material and light emitting host material, the mixture of red fluorescence material and light emitting host material forms solid solution.
Protective gas is nitrogen or inert gas.
Preferably, the mixture of this red fluorescence material and light emitting host material is heated above the temperature of the fusing point 5 ~ 10 DEG C of light emitting host material, is then cooled to room temperature, obtains solid solution.Heating makes the temperature of the mixture of red fluorescence material and light emitting host material higher than 5 ~ 10 DEG C of the fusing point of light emitting host material, so that the active force between red fluorescence material and light emitting host material can be overcome, ensure red fluorescence material and the fusing of light emitting host material.
Heat up and rate of temperature fall higher, red fluorescence material in solid solution and light emitting host material mixing more uneven, heat up and rate of temperature fall lower, the red fluorescence material in solid solution and light emitting host material are mixed to get more even, but speed is too low, production efficiency is lower.Take into account mixing uniformity and production efficiency, be preferably heated above the temperature of the fusing point 5 ~ 10 DEG C of light emitting host material with the heating rate of 5 ~ 10 DEG C/min, be cooled to room temperature with the rate of temperature fall of 5 ~ 10 DEG C/min.
Preferably, adopt the above-mentioned solid solution of thermal resistance evaporation process evaporation, make this solid solution be deposited on hole transmission layer, form the red light luminescent layer be laminated on hole transmission layer.
The vacuum degree of evaporation is preferably 1 × 10 -5~ 1 × 10 -3pa, the evaporation rate of light emitting host material is preferably 0.1 ~ 1nm/s, is conducive to forming good, the flawless film of compactness.
The thickness of red light luminescent layer is preferably 2 ~ 10 nanometers.
Preferably, after preparing hole transmission layer, before carrying out step S130, also comprise the step that preparation is laminated in the blue light-emitting on hole transmission layer.
On hole transmission layer, vacuum evaporation forms blue light-emitting.
The material of blue light-emitting is the composite material of blue fluorescent material and blue material of main part, or the composite material of blue phosphor materials and blue material of main part.
Blue fluorescent material is preferably 4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) or 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-.
Blue phosphor materials is preferably two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic and closes iridium (FIrpic), two (4,6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid conjunction iridium (FIr 6), two (4,6-bis-fluoro-5-cyano-phenyl pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic) or two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium (FIrN 4).
Blue material of main part is preferably 4,4'-bis-(9-carbazole) biphenyl (CBP), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) or N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB).
Preferably, the mass ratio of blue fluorescent material and blue material of main part is 10:100 ~ 30:100.The mass ratio of blue phosphor materials and blue material of main part is 10:100 ~ 30:100.
The thickness of blue light-emitting is preferably 5 ~ 30 nanometers.
Prepare blue light-emitting and preferably adopt thermal resistance evaporation process, the vacuum degree of blue material of main part evaporation is preferably 1 × 10 -5~ 1 × 10 -3pa, the speed of evaporation is preferably 0.1 ~ 1nm/s.
Step S140: vacuum evaporation forms electron transfer layer on red light luminescent layer.
The material of electron transfer layer is electron transport material.Electron transport material is preferably oxine aluminium (Alq 3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP).
Preferred employing thermal resistance evaporation process forms electron transfer layer, and vacuum degree is preferably 1 × 10 -5~ 1 × 10 -3pa, the evaporation rate of electron transport material is preferably 0.1 ~ 1nm/s, to form good, the flawless film of compactness.
The thickness of electron transfer layer is preferably 20 ~ 60nm.
Step S150: vacuum evaporation forms negative electrode on the electron transport layer.
Negative electrode comprises the fluoride layer and metal level that stack gradually on electron transfer layer.The thickness of fluoride layer is preferably 0.5 ~ 2 nanometer.The thickness of metal level is preferably 70 ~ 200 nanometers.
First vacuum evaporation forms fluoride layer on the electron transport layer, then carries out vacuum evaporation form metal level on fluoride layer.
The material of fluoride layer is fluoride.Fluoride is preferably cesium fluoride (CsF) or lithium fluoride (LiF).The material of metal level is metal or alloy.Metal is preferably silver (Ag), aluminium (Al) or magnesium (Mg).Alloy is preferably magnesium-aluminium (Mg-Al) alloy or magnesium-Yin (Mg-Ag) alloy.
Preferred employing thermal resistance evaporation forms the negative electrode be laminated on electron transfer layer, and vacuum degree is preferably 1 × 10 -5~ 1 × 10 -3pa, the evaporation rate of fluoride is preferably 0.1 ~ 1nm/s, and the evaporation rate of metal or alloy is preferably 0.1 ~ 1nm/s, to improve the compactness of film.
The conductive anode substrate, hole transmission layer, blue light-emitting, red light luminescent layer, electron transfer layer and the negative electrode that stack gradually are formed with organic electroluminescence devices.
The preparation method of above-mentioned organic electroluminescence device, first red fluorescence material and light emitting host material premix are added thermosetting solid solution, then this solid solution of vacuum evaporation, the evaporation rate of the technique of this single source evaporation can improve, be easier to control, more accurately can control the doping ratio of the red fluorescence material in red light luminescent layer, the organic electroluminescence device structure designed in advance prepared.
Further, because evaporation rate can improve, improve preparation efficiency.Adopt solid solution to carry out vacuum evaporation and prepare red light luminescent layer, with lower to the requirement of watch-dog, be convenient to production application, reduce preparation cost.
Set forth further below by way of specific embodiment.
Embodiment 1
Prepare organic electroluminescence device
1, provide square resistance be the ITO electro-conductive glass of 5 Ω/ as conductive anode substrate, conductive anode base-plate cleaning is clean, for subsequent use after dry;
2, be 1 × 10 in vacuum degree -5in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the hole transmission layer be laminated on conductive anode substrate with the evaporation rate evaporation hole mobile material of 0.1nm/s.Hole mobile material is N, N, N', N '-(tetramethoxy phenyl)-benzidine (MeO-TPD), the thickness of hole transmission layer is 20nm;
3, be 1 × 10 in vacuum degree -5in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the blue light-emitting be laminated on hole transmission layer.The material of blue light-emitting is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) and two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes the composite material of iridium (FIrpic), the mass ratio of FIrpic and TPBi is 10:100, and wherein the evaporation rate of FIrpic is the evaporation rate of 0.1nm/s, NPB is 1nm/s.The thickness of blue light-emitting is 30nm;
4, be that 0.1:100 is by red fluorescence material 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene) and light emitting host material 8-hydroxy quinoline aluminium (Alq in mass ratio 3) carry out being mixed to get 5,6, the mixture of 11,12-tetraphenyl naphthonaphthalene and oxine aluminium, in nitrogen atmosphere, under normal pressure, by this 5, the mixture of 6,11,12-tetraphenyl naphthonaphthalene and oxine aluminium is heated to 350 DEG C according to the heating rate of 10 DEG C/min, then be down to room temperature with the rate of temperature fall of 10 DEG C/min, form solid solution.Being positioned in the evaporation boat of vacuum coating equipment by this solid solution, is 1 × 10 in vacuum degree -5in the vacuum coating system of Pa, adopting thermal resistance evaporation technology, take evaporation rate as the above-mentioned solid solution of 1nm/s evaporation, and form the red light luminescent layer be laminated on blue light-emitting, the thickness of red light luminescent layer is 10nm;
5, be 1 × 10 in vacuum degree -5in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, with the evaporation rate evaporation electron transport material of 0.1nm/s, prepare the electron transfer layer be laminated on red light luminescent layer, electron transport material is 4,7-diphenyl-o-phenanthroline (Bphen), the thickness of electron transfer layer is 20nm;
6, be 1 × 10 in vacuum degree -5in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the fluoride layer be laminated on electron transfer layer with the evaporation rate evaporation fluoride of 0.1nm/s, fluoride is cesium fluoride, and the thickness of fluoride layer is 1 nanometer; Be laminated in the metal level on fluoride layer with the evaporation rate evaporation reasonable offer of 1nm/s, alloy is magnesium-aluminum alloy, and the thickness of metal level is 100 nanometers, and metal level is laminated on fluoride layer, obtains the negative electrode be laminated on electron transfer layer.
The conductive anode substrate, hole transmission layer, blue light-emitting, red light luminescent layer, electron transfer layer and the negative electrode that stack gradually are formed with organic electroluminescence devices.
Embodiment 2
Prepare organic electroluminescence device
1, provide square resistance be the ITO electro-conductive glass of 100 Ω/ as conductive anode substrate, conductive anode base-plate cleaning is clean, for subsequent use after dry;
2, be 1 × 10 in vacuum degree -3in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the hole transmission layer be laminated on conductive anode substrate with the evaporation rate evaporation hole mobile material of 1nm/s.Hole mobile material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), and the thickness of hole transmission layer is 60nm;
3, be that 1:100 is by red fluorescence material 4-(dintrile methyl in mass ratio)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB) and light emitting host material N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB) carries out being mixed to get 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, the mixture of 4'-diamines, in nitrogen atmosphere, under normal pressure, by this 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, the mixture of 4'-diamines is heated to 320 DEG C according to the heating rate of 5 DEG C/min, then room temperature is down to the rate of temperature fall of 5 DEG C/min, form solid solution.Being positioned in the evaporation boat of vacuum coating equipment by this solid solution, is 1 × 10 in vacuum degree -3in the vacuum coating system of Pa, adopting thermal resistance evaporation technology, take evaporation rate as the above-mentioned solid solution of 0.1nm/s evaporation, and form the red light luminescent layer be laminated on hole transmission layer, the thickness of red light luminescent layer is 2nm;
4, be 1 × 10 in vacuum degree -3in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, with the evaporation rate evaporation electron transport material of 1nm/s, prepare the electron transfer layer be laminated on red light luminescent layer, electron transport material is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), the thickness of electron transfer layer is 60nm;
5, be 1 × 10 in vacuum degree -3in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the fluoride layer be laminated on electron transfer layer with the evaporation rate evaporation fluoride of 0.1nm/s, fluoride is cesium fluoride, and the thickness of fluoride layer is 2 nanometers; Prepare the metal level be laminated on fluoride layer with the evaporation rate evaporation metal of 0.2nm/s, metal is aluminium, and the thickness of metal level is 200 nanometers, and metal level is laminated on fluoride layer, obtains the negative electrode be laminated on electron transfer layer.
The conductive anode substrate, hole transmission layer, red light luminescent layer, electron transfer layer and the negative electrode that stack gradually are formed with organic electroluminescence devices.
Embodiment 3
Prepare organic electroluminescence device
1, provide square resistance be the ITO electro-conductive glass of 50 Ω/ as conductive anode substrate, conductive anode base-plate cleaning is clean, for subsequent use after dry;
2, be 1 × 10 in vacuum degree -4in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the hole transmission layer be laminated on conductive anode substrate with the evaporation rate evaporation hole mobile material of 1nm/s.Hole mobile material is N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), and the thickness of hole transmission layer is 50nm;
3, be 1 × 10 in vacuum degree -4in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the blue light-emitting be laminated on hole transmission layer.The material of blue light-emitting is for closing iridium (FIr for 4,4'-bis-(9-carbazole) biphenyl (CBP) and two (4,6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid 6) composite material, CBP and FIr 6mass ratio be 15:100, wherein the evaporation rate of CBP is 1nm/s, FIr 6evaporation rate be 0.15nm/s.The thickness of blue light-emitting is 15nm;
4, be that 0.5:100 is by red fluorescence material 4-(dimercapto methylene in mass ratio)-2-methyl-6-(is to dimethylaminostyryl)-4H-pyrans (DCM) and light emitting host material 8-hydroxy quinoline aluminium (Alq 3) carry out being mixed to get 4-(dimercapto methylene)-2-methyl-6-(is to dimethylaminostyryl) mixture of-4H-pyrans and oxine aluminium, in nitrogen atmosphere, under normal pressure, by this 4-(dimercapto methylene)-2-methyl-6-(is to dimethylaminostyryl) mixture of-4H-pyrans and oxine aluminium is heated to 350 DEG C according to the heating rate of 8 DEG C/min, then be down to room temperature with the rate of temperature fall of 8 DEG C/min, form solid solution.Being positioned in the evaporation boat of vacuum coating equipment by this solid solution, is 1 × 10 in vacuum degree -4in the vacuum coating system of Pa, adopting thermal resistance evaporation technology, take evaporation rate as the above-mentioned solid solution of 0.2nm/s evaporation, and form the red light luminescent layer be laminated on blue light-emitting, the thickness of red light luminescent layer is 5nm;
5, be 1 × 10 in vacuum degree -4in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, with the evaporation rate evaporation electron transport material of 0.5nm/s, prepare the electron transfer layer be laminated on red light luminescent layer, electron transport material is 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), the thickness of electron transfer layer is 40nm;
6, be 1 × 10 in vacuum degree -4in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the fluoride layer be laminated on electron transfer layer with the evaporation rate evaporation fluoride of 0.01nm/s, fluoride is lithium fluoride, and the thickness of fluoride layer is 0.5 nanometer; Prepare the metal level be laminated on fluoride layer with the evaporation rate evaporation metal of 2nm/s, metal is silver, and the thickness of metal level is 70 nanometers, and metal level is laminated on fluoride layer, obtains the negative electrode be laminated on electron transfer layer.
The conductive anode substrate, hole transmission layer, blue light-emitting, red light luminescent layer, electron transfer layer and the negative electrode that stack gradually are formed with organic electroluminescence devices.
Comparative example 1
Prepare organic electroluminescence device
1, provide square resistance be the ITO electro-conductive glass of 5 Ω/ as conductive anode substrate, conductive anode base-plate cleaning is clean, for subsequent use after dry;
2, be 1 × 10 in vacuum degree -5in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the hole transmission layer be laminated on conductive anode substrate with the evaporation rate evaporation hole mobile material of 0.1nm/s.Hole mobile material is N, N, N', N '-(tetramethoxy phenyl)-benzidine (MeO-TPD), the thickness of hole transmission layer is 20nm;
3, be 1 × 10 in vacuum degree -5in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the blue light-emitting be laminated on hole transmission layer.The material of blue light-emitting is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) and two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes the composite material of iridium (FIrpic), the mass ratio of FIrpic and TPBi is 10:100, and wherein the evaporation rate of FIrpic is the evaporation rate of 0.1nm/s, NPB is 1nm/s.The thickness of blue light-emitting is 30nm;
4, by red fluorescence material Rubrene and light emitting host materials A lq 3be placed in two evaporation boats respectively, adopt double source to steam technique altogether and prepare red light luminescent layer.The dopant ratio of design is 0.1:100, but in actual mechanical process, the evaporation rate of Rubrene is minimum can only be controlled as 0.01nm/s, and it is higher to there is inaccuracy, and simultaneously Alq 3evaporation rate must reach the evaporation rate of 10nm/s, but this evaporation rate needs higher heat supply, causes luminescent material easily to decompose, and is difficult to the thin layer realizing thickness 2nm;
5, be 1 × 10 in vacuum degree -5in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, with the evaporation rate evaporation electron transport material of 0.1nm/s, prepare the electron transfer layer be laminated on red light luminescent layer, electron transport material is 4,7-diphenyl-o-phenanthroline (Bphen), the thickness of electron transfer layer is 20nm;
6, be 1 × 10 in vacuum degree -5in the vacuum coating system of Pa, adopt thermal resistance evaporation technology, prepare the fluoride layer be laminated on electron transfer layer with the evaporation rate evaporation fluoride of 0.1nm/s, fluoride is cesium fluoride, and the thickness of fluoride layer is 1 nanometer; Be laminated in the metal level on fluoride layer with the evaporation rate evaporation reasonable offer of 1nm/s, the material of metal level is magnesium-aluminum alloy, and the thickness of metal level is 100 nanometers, and metal level is laminated on fluoride layer, obtains the negative electrode be laminated on electron transfer layer.
The conductive anode substrate, hole transmission layer, blue light-emitting, red light luminescent layer, electron transfer layer and the negative electrode that stack gradually are formed with organic electroluminescence devices.
Test and Preparation equipment are high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), U.S. marine optics Ocean Optics USB4000 fiber spectrometer testing electroluminescent spectrum, Keithley company of U.S. Keithley2400 tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company.
The luminosity of the organic electroluminescence device prepared of testing example 1 ~ 3 and comparative example 1 under the driving voltage of 6V and luminous efficiency, test result is in table 1.
The luminosity of organic electroluminescence device prepared by table 1 embodiment 1 ~ 3 and comparative example 1 and luminous efficiency
Luminosity (cd/m 2） Luminous efficiency (lm/W) CIE
Embodiment 1 5124 12.5 0.35,0.38
Embodiment 2 4285 11.1 0.58,0.32
Embodiment 3 4125 10.8 0.29,0.35
Comparative example 1 3545 8.9 0.15,0.32
As can be seen from Table 1, organic electroluminescence device prepared by embodiment 1 and embodiment 3 is white light organic electroluminescent device, its CIE coordinate is also in white-light emitting region, and luminous efficiency is higher, therefore illustrate that red light luminescent layer can be effectively luminous, prepared by embodiment 2 is a red light-emitting organic electroluminescence device, and its CIE coordinate is also in red light-emitting region, illustrates that the organic electroluminescence device that embodiment 2 makes effectively achieves red emission.Although and white light organic electroluminescent device is prepared in comparative example 1 design, what obtain only has blue emission, illustrate and adopt two mode of steaming altogether cannot realize concentration lower than the doping of 0.1%, so there is no the transmitting of ruddiness.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Conductive anode substrate is provided;
On described conductive anode substrate, vacuum evaporation forms hole transmission layer;
Red fluorescence material and light emitting host material are carried out the mixture being mixed to get red fluorescence material and light emitting host material, in protective gas atmosphere, the mixture of described red fluorescence material and light emitting host material is carried out adding thermosetting solid solution, solid solution described in vacuum evaporation, forms red light luminescent layer on the hole transport layer;
On described red light luminescent layer, vacuum evaporation forms electron transfer layer; And
Vacuum evaporation forms negative electrode on the electron transport layer, obtains described organic electroluminescence device.
2. the preparation method of organic electroluminescence device according to claim 1, it is characterized in that, described in vacuum evaporation during solid solution, before forming the step of red light luminescent layer on the hole transport layer, also comprise the step that vacuum evaporation on the hole transport layer forms blue light-emitting.
3. the preparation method of organic electroluminescence device according to claim 1, it is characterized in that, when the described mixture by described red fluorescence material and light emitting host material carries out the step adding thermosetting solid solution, the mixture of described red fluorescence material and light emitting host material is carried out the temperature of the fusing point 5 ~ 10 DEG C being heated above described light emitting host material, then be cooled to room temperature, obtain described solid solution.
4. the preparation method of organic electroluminescence device according to claim 3, is characterized in that, the heating rate of described heating is 5 ~ 10 DEG C/min, described in be cooled to room temperature rate of temperature fall be 5 ~ 10 DEG C/min.
5. the preparation method of organic electroluminescence device according to claim 1, it is characterized in that, solid solution described in described vacuum evaporation, is formed in the step of red light luminescent layer on the hole transport layer, and the evaporation rate of described light emitting host material is 0.1 ~ 1nm/s.
6. the preparation method of organic electroluminescence device according to claim 1, is characterized in that, solid solution described in described vacuum evaporation, is formed on the hole transport layer in the step of red light luminescent layer, and the vacuum degree of vacuum evaporation is 1 × 10 -5~ 1 × 10 -3pa.
7. the preparation method of organic electroluminescence device according to claim 1, is characterized in that, the mass ratio of described red fluorescence material and light emitting host material is 0.1:100 ~ 1:100.
8. the preparation method of organic electroluminescence device according to claim 1, it is characterized in that, the material of described hole transmission layer is hole mobile material, described when on described conductive anode substrate, vacuum evaporation forms the step of hole transmission layer, the evaporation rate of described hole mobile material is 0.1 ~ 1nm/s.
9. the preparation method of organic electroluminescence device according to claim 1, it is characterized in that, the material of described electron transfer layer is electron transport material, described when on described red light luminescent layer, vacuum evaporation forms the step of electron transfer layer, the evaporation rate of described electron transport material is 0.1 ~ 1nm/s.
10. the preparation method of organic electroluminescence device according to claim 1, it is characterized in that, described negative electrode comprises and is laminated in fluoride layer on described electron transfer layer and metal level, the material of described fluoride layer is fluoride, the material of described metal level is metal or alloy, when described vacuum evaporation on the electron transport layer forms the step of negative electrode, the evaporation rate of described fluoride is 0.1 ~ 1nm/s, and the evaporation rate of described metal or alloy is 0.1 ~ 1nm/s.
CN201310530139.2A 2013-10-30 2013-10-30 Preparation method of organic electroluminescent device Pending CN104600209A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112928220A (en) * 2021-01-25 2021-06-08 中国科学院长春应用化学研究所 Organic light-emitting diode containing crystalline solid solution as light-emitting layer and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112928220A (en) * 2021-01-25 2021-06-08 中国科学院长春应用化学研究所 Organic light-emitting diode containing crystalline solid solution as light-emitting layer and application
CN112928220B (en) * 2021-01-25 2023-08-08 中国科学院长春应用化学研究所 Organic electroluminescent diode containing crystalline solid solution as light-emitting layer and application thereof

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