CN103050636B - Top emission organic electroluminescence diode and preparation method thereof - Google Patents
Top emission organic electroluminescence diode and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to field of optoelectronic devices, it discloses a kind of top emission organic electroluminescence diode and preparation method thereof; This top emission organic electroluminescence diode comprises the substrate, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually; Wherein, material be metal-doped metal fluoride composition mixture, in described mixture, mass percent shared by metal is 60 ~ 90%.Top emission organic electroluminescence diode provided by the invention, the material of cathode layer adopts the mixture of metal and metal fluoride composition, and the visible light transmissivity of its cathode layer can reach 60-80%, thus improves the light emission rate on cathode layer surface; Meanwhile, metal fluoride has good electron injection effect, when it is entrained in inside metallic cathode, when it contacts with the electron injecting layer of lower floor, can also reduce further two-layer between interracial contact potential barrier, be therefore conducive to the injection of electronics, reduce driving voltage.
Description
Technical field
The present invention relates to field of optoelectronic devices, particularly relate to a kind of top emission organic electroluminescence diode.The invention still further relates to the preparation method of this top emission organic electroluminescence diode.
Background technology
Organic electroluminescent (OrganicLightEmissionDiode, be called for short OLED) diode, there is brightness high, material selection range is wide, driving voltage is low, the characteristics such as all solidstate active illuminating, have high definition simultaneously, wide viewing angle, and can the advantage such as high-speed response of smooth and easy display animation, and OLED can be made into flexible structure, folded bent can be carried out, a kind of flat panel display and planar light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, quite popular research fields of nearest more than ten years.
Organic electroluminescent LED has a kind of structure of similar sandwich, it is negative electrode and anode up and down respectively, the organic material functional layer of single or multiple lift different materials kind and different structure is clipped between two electrodes, be followed successively by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer.Organic electroluminescent LED is carrier injection type luminescent device, after anode and negative electrode add operating voltage, hole is from anode, electronics is injected into the organic material layer of device work respectively from negative electrode, two kinds of charge carriers form hole-electron to luminescence in luminous organic material, and then light sends from electrode side.
But organic electroluminescent LED develops into now, its structure is bottom-emission formula mostly, and cathode layer is that transparence is to obtain bright dipping.Transparent cathode conventional is at present generally the metal level of ITO or thin layer, as Ag, Mg:Ag alloy etc.But ITO processing procedure is all use the mode of sputter to prepare, and its manufacturing process is comparatively large to the destruction of organic layer, and easily causes short circuit; And use hot evaporation to prepare transparent sheet metal electrode layer, and if electrode layer is too thin, then conductivity is too poor, if electrode layer is too thick, then light transmission rate is low.
Summary of the invention
A kind of technique is the object of the present invention is to provide to prepare simple, conductivity better and the higher top emission organic electroluminescence diode of visible light transmissivity.
A kind of top emission organic electroluminescence diode, comprises the substrate, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually; Wherein, the material of described cathode layer is the mixture of metal and metal fluoride composition, and in described mixture, mass percent shared by metal is 60 ~ 90%.
In above-mentioned top emission organic electroluminescence diode, described metal is aluminium or silver; Described metal fluoride is magnesium fluoride, calcirm-fluoride, lithium fluoride, cesium fluoride, lead fluoride, barium fluoride, thorium fluoride or neodymium fluoride; And the thickness of described cathode layer is 20 ~ 40nm.
Top emission organic electroluminescence diode provided by the invention, its backing material adopted is thin polymer film, e.g., PETG, polyether sulfone, PEN, clear polyimides, cyclic olefine copolymer or Merlon.
The material that the hole injection layer of this top emission organic electroluminescence diode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer material therefor commonly uses by this area, such as:
The material selection 4,4 ', 4 of hole injection layer "-three (N-3-methylphenyl-N-phenyl-amino)-triphenylamine;
The material selection N of hole transmission layer, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines;
The material selection 4 of luminescent layer, 4 '-N, N-bis-carbazyls-biphenyl doping two (4,6-difluorophenyl pyridinato-N, C
2') pyridinecarboxylic closes the dopant mixture of iridium composition;
Material selection oxine-the aluminium of electron transfer layer;
The material selection magnesium fluoride of electron injecting layer, calcirm-fluoride, lithium fluoride or cesium fluoride.
The material of described anode layer is silver, aluminium or gold.
The present invention also provides a kind of manufacture method of above-mentioned top emission organic electroluminescence diode, and it comprises the following steps:
Step S1, cleaning, drying substrates;
Step S2, utilize the method for vacuum coating, at described substrate surface evaporation one deck anode layer;
Step S3, utilize the method for vacuum coating, stack gradually evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer on described anode layer surface;
Step S4, surperficial evaporation cathode layer at described electron injecting layer, the material of this cathode layer is the mixture of metal-doped metal fluoride composition, and in described mixture, mass percent shared by metal is 60 ~ 90%;
After above-mentioned preparation technology completes, obtain top emission organic electroluminescence diode.
Top emission organic electroluminescence diode provided by the invention, the material of cathode layer adopts the mixture of metal and metal fluoride composition, and the visible light transmissivity of its cathode layer can reach 60-80%, thus improves the light emission rate on cathode layer surface; Meanwhile, metal fluoride has good electron injection effect, time inside the cathode layer that it is entrained in metal material, when it contacts with the electron injecting layer of lower floor, can also reduce further two-layer between interracial contact potential barrier, be therefore conducive to the injection of electronics, reduce driving voltage.
Top emission organic electroluminescence diode prepared by the present invention, its preparation technology is simple, and when making anode layer, less to the destructiveness of thin polymer film substrate in manufacturing process, and short circuit phenomenon can be avoided to occur.
Accompanying drawing explanation
Fig. 1 is the structural representation of top emission organic electroluminescence diode of the present invention;
Fig. 2 is preparation technology's flow chart of top emission organic electroluminescence diode of the present invention;
Fig. 3 is the Current density-voltage performance diagram of the organic electroluminescent LED of embodiment 1, comparative example 1 and comparative example 2.
Embodiment
A kind of top emission organic electroluminescence diode provided by the invention, as shown in Figure 1, the substrate 101, anode layer 102, hole injection layer 103, hole transmission layer 104, luminescent layer 105, electron transfer layer 106, electron injecting layer 107 and the cathode layer 108 that stack gradually is comprised; Wherein, the material of described cathode layer 108 is the mixture of metal-doped metal fluoride composition, and in described mixture, mass percent shared by metal is 60 ~ 90%; Described metal is material of main part, and described metal fluoride is guest materials or dopant material.
In the described mixed film layer of this top emission organic electroluminescence diode, the metal in cathode layer can be metallic aluminium (Al) or silver (Ag); Described metal fluoride is selected from magnesium fluoride (MgF
2), calcirm-fluoride (CaF
2), lithium fluoride (LiF), cesium fluoride (CsF), lead fluoride (PbF
2), barium fluoride (BaF
2), thorium fluoride (ThF
4) or neodymium fluoride (NdF
2) etc. material, the transparent wave band of described metal fluoride is the visible light wave range comprising 380-780nm.
The thickness of described negative electrode is between 20-40nm, the preparation process of described negative electrode is that metal and metal fluoride are placed in two evaporation boats respectively, evaporates by hot evaporation the mixture film that bi-material (i.e. metal and metal fluoride) obtains simultaneously.By regulating the evaporation rate of material, controlling the ratio of material in cathode film layer, so just can obtain the cathode layer that visible light transmissivity can reach 65-80%.Meanwhile, described metal fluoride has good electron injection effect, when it is entrained in inside metallic cathode, when it contacts with the electron injecting layer of lower floor, can also reduce further two-layer between interracial contact potential barrier, be therefore conducive to the injection of electronics, reduce driving voltage.In addition, described metal fluoride doping in the cathode, can improve the optical band gap of negative electrode, thus improve the visible light transmissivity of negative electrode.
This top emission organic electroluminescence diode, its backing material adopted is thin polymer film, as, PETG (PET), polyether sulfone (PES), PEN (PEN), clear polyimides (PI), cyclic olefine copolymer (COC) or Merlon (PC); In view of this top emission organic electroluminescence diode is top emission OLED device, therefore the polymeric film surface of its backing material has to pass through smooth stiffened process, makes case hardness up to 2H-3H (pencil hardness).
The material that the hole injection layer of this top emission organic electroluminescence diode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer material therefor commonly uses by this area, such as:
The material selection 4,4 ', 4 of hole injection layer "-three (N-3-methylphenyl-N-phenyl-amino)-triphenylamine (m-MTDATA);
The material selection N of hole transmission layer, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB);
The material selection 4 of luminescent layer, 4 '-N, N-bis-carbazyls-biphenyl (CBP) doping two (4,6-difluorophenyl pyridinato-N, C
2') pyridinecarboxylic closes the dopant mixture that iridium (FIrPic) forms; Two (4,6-difluorophenyl pyridinato-N, C
2the doping mass percent that ') pyridinecarboxylic closes iridium is 8%, and namely FirPic is guest materials or dopant material, and CBP is material of main part;
Material selection oxine-aluminium (the Alq of electron transfer layer
3);
Material selection magnesium fluoride (the MgF of electron injecting layer
2), calcirm-fluoride (CaF
2), lithium fluoride (LiF) or cesium fluoride (CsF); The thickness of described electron injecting layer is 0.5-1nm.
The material of described anode layer is silver (Ag), aluminium (Al) or gold (Au); Described anode layer thickness is 60-150nm.
The manufacture method of above-mentioned top emission organic electroluminescence diode, as shown in Figure 2, it comprises the following steps:
Step S1, be placed on substrate (e.g., thin polymer film) containing washing agent deionized water in carry out ultrasonic cleaning, use isopropyl alcohol successively after clean by washed with de-ionized water, acetone processes in ultrasonic wave, then drying up with nitrogen, for subsequent use; Wherein, thin polymer film is selected from PETG (PET), polyether sulfone (PES), PEN (PEN), clear polyimides (PI), cyclic olefine copolymer (COC) or Merlon (PC);
Step S2, utilize the method for vacuum coating, the substrate surface evaporation one deck anode layer cleaned, the thickness 60-150nm of this anode layer;
Step S3, by the method for vacuum coating, evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer successively on anode layer surface; The thickness of described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer is respectively 25 ~ 35nm, 45 ~ 55nm, 15 ~ 25nm, 35 ~ 45nm and 0.5 ~ 1nm;
Step S4, be the cathode layer of 20-40nm at the surperficial evaporation thickness of described electron injecting layer, the material of this cathode layer is the mixture of metal-doped metal fluoride composition, and in described mixture, mass percent shared by metal is 60 ~ 90%;
Above-mentioned preparation technology complete after, obtain top emission organic electroluminescence diode.
In above-mentioned steps S2, also comprise the surface treatment step to described anode layer:
After described anode layer preparation, need be placed in plasma treatment instrument and carry out plasma treatment; Like this, through the anode layer of plasma treatment, the injection barrier in hole can be reduced.
In above-mentioned steps S4, the preparation of cathode layer also comprises the steps:
Metal and metal fluoride are placed in two evaporation boats respectively, evaporate by hot evaporation the cathode layer that bi-material obtains mixture composition simultaneously; And by regulating the evaporation rate of metal and metal fluoride, control metal and the ratio of metal fluoride in cathode layer.
Top emission organic electroluminescence diode provided by the invention, the material of cathode layer adopts the mixture of metal and metal fluoride composition, and the visible light transmissivity of its cathode layer can reach 60-80%, thus improves the light emission rate on cathode layer surface; Meanwhile, metal fluoride has good electron injection effect, when it is entrained in inside metallic cathode, when it contacts with the electron injecting layer of lower floor, can also reduce further two-layer between interracial contact potential barrier, be therefore conducive to the injection of electronics, reduce driving voltage.
Top emission organic electroluminescence diode prepared by the present invention, its preparation technology is simple, and when making anode layer, less to the destructiveness of thin polymer film substrate in manufacturing process, and short circuit phenomenon can be avoided to occur.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The top emission organic electroluminescence diode structure of the present embodiment 1 is: PET/Ag/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ MgF
2/ (Ag:MgF
2).
The preparation technology of this top emission organic electroluminescence diode is as follows:
Be placed on by PET film substrate in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, PET film surface deposition thickness be the Ag of 60nm as anode layer, then by anode layer oxygen plasma treatment 2 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 30nm, thickness is 50nm, thickness be the luminescent layer FIrPic:CBP of 20nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 40nm
3, thickness is the electron injecting layer MgF of 0.5nm
2.
The cathode layer of to be then evaporation thickness be 20nm, structure is Ag:MgF
2; Wherein, Ag is at Ag:MgF
2in mass percent be 60.1%.
Embodiment 2
The top emission organic electroluminescence diode structure of the present embodiment 2 is: PC/Au/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ LiF/ (Ag:PbF
2).
The preparation technology of this top emission organic electroluminescence diode is as follows:
PC film-substrate be placed in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, PC film surface deposit thickness be the Au of 80nm as anode layer, then by anode layer oxygen plasma treatment 5 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 35nm, thickness is 50nm, thickness be the luminescent layer FIrPic:CBP of 15nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 45nm
3, thickness is the electron injecting layer LiF of 1nm.
The cathode layer of to be then evaporation thickness be 25nm, structure is Ag:PbF
2; Wherein, Ag is at Ag:MgF
2in mass percent be 65.3%.
Embodiment 3
The top emission organic electroluminescence diode structure of the present embodiment 3 is: PI/Al/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ CaF
2/ (Ag:CaF
2).
The preparation technology of this top emission organic electroluminescence diode is as follows:
PI film-substrate be placed in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, PI film surface deposit thickness be the Al of 100nm as anode layer, then by anode layer oxygen plasma treatment 2 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 30nm, thickness is 45nm, thickness be the luminescent layer FIrPic:CBP of 25nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 40nm
3, thickness is the electron injecting layer CaF of 1nm
2.
The cathode layer of to be then evaporation thickness be 35nm, structure is Ag:CaF
2; Wherein, Al is at Ag:CaF
2in mass percent be 71.4%.
Embodiment 4
The top emission organic electroluminescence diode structure of the present embodiment 4 is: PEN/Ag/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ LiF/ (Ag:BaF
2).
The preparation technology of this top emission organic electroluminescence diode is as follows:
PEN film-substrate be placed in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, PEN film surface deposit thickness be the Ag of 120nm as anode layer, then by anode layer oxygen plasma treatment 2 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 30nm, thickness is 50nm, thickness be the luminescent layer FIrPic:CBP of 20nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 40nm
3, thickness is the electron injecting layer LiF of 1nm.
The cathode layer of to be then evaporation thickness be 40nm, structure is Ag:BaF
2; Wherein, Al is at Ag:BaF
2in mass percent be 78.1%.
Embodiment 5
The top emission organic electroluminescence diode structure of the present embodiment 5 is: COC/Al/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ CsF/ (Ag:CaF
2).
The preparation technology of this top emission organic electroluminescence diode is as follows:
COC film-substrate be placed in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, COC film surface deposit thickness be the Al of 150nm as anode layer, then by anode layer oxygen plasma treatment 2 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 30nm, thickness is 50nm, thickness be the luminescent layer FIrPic:CBP of 20nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 35nm
3, thickness is the electron injecting layer CsF of 1nm.
The cathode layer of to be then evaporation thickness be 35nm, structure is Ag:CaF
2; Wherein, Ag is at Ag:CaF
2in mass percent be 79.2%.
Embodiment 6
The top emission organic electroluminescence diode structure of the present embodiment 6 is: PES/Ag/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ LiF/ (Al:LiF).
The preparation technology of this top emission organic electroluminescence diode is as follows:
PES film-substrate be placed in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, PES film surface deposit thickness be the Ag of 120nm as anode layer, then by anode layer oxygen plasma treatment 2 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 25nm, thickness is 50nm, thickness be the luminescent layer FIrPic:CBP of 25nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 40nm
3, thickness is the electron injecting layer LiF of 1nm.
The cathode layer of to be then evaporation thickness be 20nm, structure is Al:LiF; Wherein, the mass percent of Al in Al:LiF is 89.3%.
Embodiment 7
The top emission organic electroluminescence diode structure of the present embodiment 7 is: PET/Al/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ MgF
2/ (Al:ThF
4).
The preparation technology of this top emission organic electroluminescence diode is as follows:
Be placed on by PET film substrate in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, PET film surface deposition thickness be the Al of 100nm as anode layer, then by anode layer oxygen plasma treatment 2 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 30nm, thickness is 50nm, thickness be the luminescent layer FIrPic:CBP of 15nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 45nm
3, thickness is the electron injecting layer MgF of 0.5nm
2.
The cathode layer of to be then evaporation thickness be 30nm, structure is Al:ThF
4; Wherein, Al is at Al:ThF
4in mass percent be 81.5%.
Embodiment 8
The top emission organic electroluminescence diode structure of the present embodiment 8 is: PEN/Ag/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ MgF
2/ (Al:NdF
2).
The preparation technology of this top emission organic electroluminescence diode is as follows:
PEN film-substrate be placed in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, PEN film surface deposit thickness be the Ag of 120nm as anode layer, then by anode layer oxygen plasma treatment 2 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 25nm, thickness is 55nm, thickness be the luminescent layer FIrPic:CBP of 20nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 40nm
3, thickness is the electron injecting layer MgF of 0.5nm
2.
The cathode layer of to be then evaporation thickness be 40nm, structure is Al:NdF
2; Wherein, Al is at Al:NdF
2in mass percent be 83.9%.
Comparative example 1
The organic electroluminescent LED structure of this comparative example 1 is: PET/Ag/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ LiF/Ag.
The preparation technology of this top emission organic electroluminescence diode is as follows:
Be placed on by PET film substrate in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, PET film surface deposition thickness be the Ag of 60nm as anode layer, then by anode layer oxygen plasma treatment 2 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 30nm, thickness is 50nm, thickness be the luminescent layer FIrPic:CBP of 20nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 40nm
3, thickness is the electron injecting layer LiF of 0.5nm.
The cathode layer of to be then evaporation thickness be 20nm, material is Ag.
Comparative example 2
The organic electroluminescent LED structure of this comparative example 2 is: PET/Ag/m-MTDATA/NPB/ (FIrPic:CBP)/Alq
3/ LiF/ITO.
The preparation technology of this top emission organic electroluminescence diode is as follows:
Be placed on by PET film substrate in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
In vacuum evaporation system, PET film surface deposition thickness be the Ag of 60nm as anode layer, then by anode layer oxygen plasma treatment 2 minutes.
After being disposed, the hole transmission layer NPB that continuing on anode layer surface successively evaporation thickness is the hole injection layer m-MTDATA of 30nm, thickness is 50nm, thickness be the luminescent layer FIrPic:CBP of 20nm (wherein, FIrPic is guest materials, CBP is material of main part, and guest materials doping mass percentage content is 8%), thickness is the electron transfer layer Alq of 40nm
3, thickness is the electron injecting layer LiF of 0.5nm.
Then be adopt low frequency sputtering technology to make the ITO of 50nm as cathode layer.
Tested by the organic electroluminescent LED that top emission organic electroluminescence diode obtained for embodiment 1 to 8 and comparative example 1 and 2 obtain, result is as shown in table 1.Light transmission rate as can be seen from table 1, the mixing negative electrode of metal-doped metal fluoride composition has higher light transmission rate, a little less than the light transmission rate of ITO electrode layer than common metal A g electrode layer; Therefore, in top emission organic electroluminescence diode, the cathode layer structure of metal-doped metal fluoride composition can improve the light emission rate on cathode layer surface, the twice of the chances are common metal A g electrode layer and ITO electrode layer.
Luminescent properties contrast in table 1, includes the luminosity of organic electroluminescent LED under the driving voltage of 8V and the maximum luminous efficiency of device.Can learn from table 1, because metal-doped metal fluoride mixing negative electrode had both improve the light transmittance of cathode layer, in turn ensure that the conductivity of cathode layer, electron injection performance is also due to common sheet metal Ag and ITO electrode in addition, and therefore every luminescent properties data are all better.
Table 1
| Cathode thin film resistance (Ω/) | Transmitance | Starting resistor (V) | Brightness (cd/m during 8V 2) | Luminous efficiency (cd/A) | |
| Embodiment 1 | 0.84 | 79.1％ | 3.1 | 4123 | 22.5 |
| Embodiment 2 | 0.81 | 71.5％ | 3.2 | 3971 | 21.6 |
| Embodiment 3 | 0.60 | 68.2％ | 3.4 | 3621 | 17.5 |
| Embodiment 4 | 0.54 | 67.2％ | 3.2 | 4012 | 21.7 |
| Embodiment 5 | 0.44 | 68.4％ | 3.5 | 3554 | 17.1 |
| Embodiment 6 | 0.41 | 65.2％ | 3.2 | 3821 | 19.2 |
| Embodiment 7 | 0.54 | 60.7％ | 3.4 | 3456 | 17.1 |
| Embodiment 8 | 0.35 | 61.3％ | 3.4 | 3275 | 16.2 |
| Comparative example 1 | 0.29 | 55.6％ | 3.9 | 1875 | 9.6 |
| Comparative example 2 | 15.2 | 79.8％ | 4.3 | 1812 | 8.5 |
Fig. 3 is the Current density-voltage performance diagram of the organic electroluminescent LED of embodiment 1, comparative example 1 and comparative example 2.As can be seen from curve, the metal-doped metal fluoride mixing negative electrode that the present embodiment 1 provides has better electron injection effect, and cause under same drive voltage, organic electroluminescent LED can obtain higher current density.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (6)
1. a top emission organic electroluminescence diode, this top emission organic electroluminescence diode comprises the substrate, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually; It is characterized in that, the material of described cathode layer is the mixture of metal-doped metal fluoride composition, and in described mixture, mass percent shared by metal is 60 ~ 90%;
Described metal is aluminium or silver; Described metal fluoride is magnesium fluoride, calcirm-fluoride, lithium fluoride, cesium fluoride, lead fluoride, barium fluoride, thorium fluoride or neodymium fluoride; The material of electron injecting layer is magnesium fluoride, calcirm-fluoride, lithium fluoride or cesium fluoride;
The thickness of described cathode layer is 20 ~ 40nm;
The thickness of described electron injecting layer is 0.5-1nm.
2. top emission organic electroluminescence diode according to claim 1, it is characterized in that, the material of described substrate is PETG, polyether sulfone, PEN, clear polyimides, cyclic olefine copolymer or Merlon; The material of described hole injection layer is 4,4', 4 "-three (N-3-methylphenyl-N-phenyl-amino)-triphenylamines; The material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines; The material of described luminescent layer is 4,4'-N, N-bis-carbazyls-biphenyl doping two (4,6-difluorophenyl pyridinato-N, C
2 ') pyridinecarboxylic close iridium composition dopant mixture; The material of described electron transfer layer is oxine-aluminium.
3. according to the arbitrary described top emission organic electroluminescence diode of claim 1 to 2, it is characterized in that, the material of described anode layer is silver, aluminium or gold.
4. a preparation method for top emission organic electroluminescence diode, comprises the steps:
Step S1, cleaning, drying substrates;
Step S2, at surperficial evaporation one deck anode layer of described substrate;
Step S3, stacks gradually evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer on described anode layer surface;
Step S4, at the surperficial evaporation cathode layer of described electron injecting layer, the material of this cathode layer is the mixture of metal and metal fluoride composition, and in described mixture, mass percent shared by metal is 60 ~ 90%;
After above-mentioned preparation technology is complete, obtained described top emission organic electroluminescence diode;
Described metal is aluminium or silver; Described metal fluoride is magnesium fluoride, calcirm-fluoride, lithium fluoride, cesium fluoride, lead fluoride, barium fluoride, thorium fluoride or neodymium fluoride; The material of electron injecting layer is magnesium fluoride, calcirm-fluoride, lithium fluoride or cesium fluoride;
The thickness of described cathode layer is 20 ~ 40nm;
The thickness of described electron injecting layer is 0.5-1nm.
5. the preparation method of top emission organic electroluminescence diode according to claim 4, it is characterized in that, the material of described substrate is PETG, polyether sulfone, PEN, clear polyimides, cyclic olefine copolymer or Merlon; The material of described hole injection layer is 4,4', 4 "-three (N-3-methylphenyl-N-phenyl-amino)-triphenylamines; The material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines; The material of described luminescent layer is 4,4'-N, N-bis-carbazyls-biphenyl doping two (4,6-difluorophenyl pyridinato-N, C
2 ') pyridinecarboxylic close iridium composition dopant mixture; The material of described electron transfer layer is oxine-aluminium.
6. according to the preparation method of the arbitrary described top emission organic electroluminescence diode of claim 4 to 5, it is characterized in that, the material of described anode layer is silver, aluminium or gold.
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| TWI662730B (en) * | 2018-03-09 | 2019-06-11 | 謙華科技股份有限公司 | Thermal transfer film for preparing organic light emitting diode and preparation method thereof |
| CN114023912A (en) * | 2021-11-08 | 2022-02-08 | 江苏联视控股集团有限公司 | Photoelectronic device based on rare earth oxide |
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