CN103855310A - Organic electroluminescence device and preparation method thereof - Google Patents
Organic electroluminescence device and preparation method thereof Download PDFInfo
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- CN103855310A CN103855310A CN201210504788.0A CN201210504788A CN103855310A CN 103855310 A CN103855310 A CN 103855310A CN 201210504788 A CN201210504788 A CN 201210504788A CN 103855310 A CN103855310 A CN 103855310A
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- H10K50/00—Organic light-emitting devices
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Abstract
The invention discloses an organic electroluminescence device and a preparation method thereof. The organic electroluminescence device comprises a substrate layer, an anode layer, an organic functional layer and a cathode layer which are laminated and combined in turn. The organic functional layer comprises an electron transmission layer and a light-emitting layer which is driven to emit light by an external power supply. The electron transmission layer is laminated and combined between the cathode layer and the light-emitting layer. Mass percentage of 3.8-28.6% of alkali metal iodide is doped in the electron transmission layer. The preparation method of the organic electroluminescence device comprises steps that a substrate is acquired, the anode layer is prepared, the organic functional layer is prepared and the cathode layer is prepared, etc. The organic electroluminescence device is high in light emission efficiency, low in starting voltage and long in the service life. The preparation method of the organic electroluminescence device is simple in technology, conditions are easy to control and product qualified rate is high so that production efficiency is effectively enhanced, and thus the organic electroluminescence device is suitable for industrialized production.
Description
Technical field
The invention belongs to electric light source technology field, relate to specifically Organnic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode, hereinafter to be referred as OLED) have that brightness is high, material range of choice is wide, driving voltage is low, entirely solidify the characteristics such as active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, be current lot of domestic and foreign researcher's focal point.
Organic electroluminescence device is carrier injection type luminescent device, add after operating voltage at anode and negative electrode, hole is from anode, electronics is injected into respectively the organic material layer of device work from negative electrode, it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and then light sends from electrode one side.
Up to the present, although the scientific research personnel of whole world various countries is by selecting suitable organic material and rational device structure design, make the indices of device performance be greatly improved, but at present owing to driving the electric current of luminescent device larger, luminous efficiency is low, and device lifetime is low, in order to realize the practical of organic electroluminescence device, it is little that people are eager to find a kind of drive current, the luminescent device structure that luminous efficiency is high.
Transport layer doping is more a kind of a kind of method that reduces Organnic electroluminescent device drive current that uses at present, the method can reduce device internal resistance by doped structure, improve the injection efficiency of charge carrier, reduce the raising that starting resistor is conducive to light-emitting device luminous efficiency.But the transport layer obtaining by doping at present doping is inhomogeneous, and interior resistance is still larger, and the efficiency of transmission of charge carrier is lower, and required starting resistor is higher, cause Organnic electroluminescent device luminous efficiency not ideal, and the life-span is short.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of starting resistor low, can effectively improve the Organnic electroluminescent device of the injection efficiency of charge carrier.
Another object of the present invention is to provide a kind of condition easily to control, the Organnic electroluminescent device preparation method that conforming product rate is high.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of Organnic electroluminescent device, comprise the substrate layer, anode layer, organic function layer and the cathode layer that stack gradually combination, it is characterized in that: described organic function layer comprises electron transfer layer and luminous luminescent layer under additional power source drives, described electron transfer layer is stacked to be combined between described cathode layer and luminescent layer, wherein, the alkaline metal iodide that is 3.8～28.6% doped with quality percentage composition in described electron transfer layer.
And a kind of preparation method of above-mentioned Organnic electroluminescent device, between the described luminescent layer of preparation and the step of cathode layer, comprises the step of preparing electron transfer layer:
In coating system, take alkaline metal iodide and electric transmission host material as two independently plating source carry out plated film, form described electron transfer layer, wherein, alkaline metal iodide is (5～30) with the ratio of the evaporation speed of electric transmission host material: 100.
The electron transfer layer of Organnic electroluminescent device of the present invention adopts alkaline metal iodide doping, its conductivity and carrier concentration are effectively improved, improve the efficiency of transmission of electronics, and this electron transfer layer even structure and stable, thereby effectively improve the luminous efficiency of this Organnic electroluminescent device, the starting resistor that has reduced this Organnic electroluminescent device is low, has extended its useful life.
Organnic electroluminescent device preparation method of the present invention is two independently to plate source by alkaline metal iodide and electric transmission host material, by controlling the evaporation speed in two plating sources, prepare even structure and stable electron transfer layer doped structure, effectively reduce the interior resistance of electron transfer layer, improve electron transfer layer to electric transmission efficiency, thereby given excellent properties such as luminous efficiency and low starting resistor etc. that Organnic electroluminescent device is high.In addition, the method technique is simple, and condition is easily controlled, and conforming product rate is high, has effectively improved production efficiency, is suitable for industrialization and produces.
Accompanying drawing explanation
Fig. 1 is the structural representation of embodiment of the present invention Organnic electroluminescent device;
Fig. 2 is the another kind of structural representation of embodiment of the present invention Organnic electroluminescent device;
Fig. 3 is embodiment of the present invention Organnic electroluminescent device preparation method's schematic flow sheet;
The current-voltage characteristic curve figure of Fig. 4 Organnic electroluminescent device that to be the embodiment of the present invention 1 prepare with comparative example 1.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of starting resistor low, can effectively improve the Organnic electroluminescent device of the injection efficiency of charge carrier, and its structure is as shown in Fig. 1 to 2.This Organnic electroluminescent device comprises the substrate layer 1, anode layer 2, organic function layer 3 and the cathode layer 4 that stack gradually.
Wherein, organic function layer 3 comprises the hole injection layer 31, hole transmission layer 32, luminescent layer 33, hole blocking layer 34, the electron transfer layer 35 that stack gradually combination.Wherein, the stacked combination in the relative surface of face that combines with substrate layer 1 of hole injection layer 31 and anode layer 2, a surperficial stacked combination of electron transfer layer 35 and cathode layer 4, its structure is as shown in Figure 1.
In organic function layer 3, the material of hole injection layer 31 is preferably CuPc (CuPc), Phthalocyanine Zinc (ZnPc), (4,4', 4 " at least one in tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA).Certainly, the material of this hole injection layer 31 can also adopt other known hole-injecting materials of this area, and its thickness also can arrange according to the thickness of this area routine.This hole injection layer 31 the ohmic contact that can effectively strengthen between anode layer 2 and hole injection layer 31 is set, strengthened electric conductivity, further improve the hole injectability of anode layer 2 ends.Certainly,, if do not consider the hole injectability of embodiment of the present invention Organnic electroluminescent device anode tap, also can in this position, hole injection layer 31 be set.
The material of hole transmission layer 32 can be selected from 4,4', 4 " tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA); N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), 4,4', 4 " at least one in tri-(carbazole-9-yl) triphenylamine (TCTA).Certainly, the material of this hole transmission layer 32 can also adopt other known hole mobile materials of this area, and its thickness also can arrange according to the thickness of this area routine.In order further to improve the efficiency of this hole transmission layer 32 to hole transport, as the preferred embodiment of the present invention, this hole transmission layer 32 is hole mobile material and the hole dopant doped layer structure of doping mutually.Wherein hole dopant preferably but be not only 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-tetra-cyanogen quinone-bismethanes (F4-TCNQ), 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is composite to one or both in naphthoquinones (F6-TNAP).
In luminescent layer 33, luminescent material can be selected flexibly according to actual demand (as requirements such as glow colors).As selected NPB:Ir (MDQ)
2(acac), wherein, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) is material of main part, two (2-methyl-diphenyl [f, h] quinoxaline (acetylacetone,2,4-pentanedione) (Ir (MDQ)
2(acac)) be guest materials, and main, object doping mass ratio is 5:100.Certainly, luminescent material also can be selected the other materials of this area, as two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes that iridium (FIrpic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) closes iridium (Ir (MDQ) 2 (acac)), three (2-phenylpyridines) close iridium (Ir (ppy)
3) at least one.The thickness of this luminescent layer 33 can be set to 25nm, certainly, and also other thickness ranges of this area routine of its thickness.
The setting of hole blocking layer 34 is to be trapped in as much as possible luminescent layer 33 from anode layer 2 injected holes in order to make, and make this hole and electronics meeting rate in luminescent layer 33, to improve both exciton amounts compound and that form, and exciton energy is passed to luminescent material, thereby the electronics of excitation light-emitting material is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, discharge luminous energy, to reach the object of the luminous intensity that strengthens luminescent layer 33.This hole blocking layer 34 can be selected hole barrier materials well known in the art, and as TPBi, Bphen, BAlq, its thickness also can be selected the thickness of this area routine, as 10nm.Certainly,, if do not consider the luminous intensity of embodiment of the present invention Organnic electroluminescent device, also can in this position, hole blocking layer 34 be set.
Further preferably, as embodiments of the invention, on the basis of Organnic electroluminescent device structure as shown in Figure 1, above-mentioned organic function layer 3 also comprises electron injecting layer 36, this electron injecting layer 36 is stacked to be combined between electron transfer layer 35 and cathode layer 4, and its structure as shown in Figure 2.Wherein, the material of electron injecting layer 36 is preferably alkali-metal halide, is preferably halide iodide.Particularly, this alkaline metal iodide is at least one in lithium iodide, KI, sodium iodide, cesium iodide, rubidium iodide.The thickness of electron injecting layer 36 is preferably 0.2～2nm.The setting of this electron injecting layer 36, can effectively strengthen the ohmic contact between itself and cathode layer 4, strengthen electric conductivity, further improve the electronic injection ability of cathode layer 4 ends, to realize further equilibrium carrier, control recombination region, in luminescent layer 33, increase exciton amount, obtained desirable luminosity and luminous efficiency.
Wherein, the alkaline metal iodide of electron injecting layer 36 can be identical or not identical with the kind of the dopant alkaline metal iodide in electron transfer layer 35 mentioned above.But, inventor finds in further studying, when identical the kind of the kind selected alkaline metal iodide of electron injecting layer 36 and the dopant alkaline metal iodide in electron transfer layer 35, the injection efficiency of electronics can be improved more significantly, mechanical strength and the ohmic contact of electron injecting layer 36 and cathode layer 4, electron transfer layer 35 combinations can also be strengthened simultaneously.
The material of anode layer 2 can be selected indium doped stannum oxide film (ITO), and thickness is 100nm.Certainly, the material of this anode layer 2 can also be selected other positive electrode of this area, as metal simple-substance or metal alloy etc., and other thickness that the thick end also can setup cost field routine.
The material of cathode layer 4 is preferably argent (Ag), aluminium (Al), silver-colored magnesium alloy (Ag-Mg) or magnadure (Al-Mg), and its thickness is 100nm.Certainly, the material of this cathode layer 4 can also be selected other negative material of this area, as other metal simple-substances or metal alloy etc., and other thickness that the thick end also can setup cost field routine.
From the above, Organnic electroluminescent device of the present invention is provided with alkaline metal iodide and the electric transmission host material electron transfer layer 35 of doping mutually, these electron transfer layer 35 even structure and stable, its conductivity and carrier concentration are effectively improved, improve the efficiency of transmission of electronics, thereby effectively improved the luminous efficiency of this Organnic electroluminescent device, the starting resistor that has reduced this Organnic electroluminescent device is low, has extended its useful life.In addition, between electron transfer layer 35 and cathode layer 4, be provided with electron injecting layer 36, can effectively strengthen the ohmic contact between itself and cathode layer 4, strengthen electric conductivity, reduced the injection barrier of electronics, improved the electronic injection ability of cathode layer 4 ends, to realize further equilibrium carrier, control recombination region, in luminescent layer 33, increase exciton amount, improve luminous intensity and the luminous efficiency of Organnic electroluminescent device.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method about Organnic electroluminescent device mentioned above.This preparation method's flow process as shown in Figure 3, please be mixed and see Fig. 1,2 simultaneously, comprises the steps:
S01. obtain substrate: obtain according to actual needs the substrate of required size, as substrate layer 1;
S02. prepare anode layer 2: at a plated surface anode layer 2 of substrate layer 1;
S03. prepare organic function layer 3: the anode layer 2 of preparing at step S02 with the substrate layer 1 relative plated surface organic function layer 3 of face that combines, wherein, this organic function layer 3 comprises electron transfer layer 35 and luminous luminescent layer 33 under additional power source drives, electron transfer layer 35 is stacked to be combined between cathode layer and 4 luminescent layers 33, and the alkaline metal iodide that is 3.8～28.6% doped with quality percentage composition in electron transfer layer;
S04. prepare cathode layer 4: the organic function layer 3 of preparing at step S03 with the anode layer 2 relative plated surface cathode layer 4 of face that combines, obtain Organnic electroluminescent device.
Particularly, the selected substrate in above-mentioned steps S01 as described above, can be selected the backing material of this area routine, as glass.
Preferably, before carrying out following step S02, also comprise the preliminary treatment that this substrate layer 1 is cleaned:
Substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up for subsequent use with nitrogen.
In above-mentioned steps S02, substrate is placed in to magnetic control sputtering system at substrate surface spatter film forming, forms anode layer 2.Its sputtering condition adopts the process conditions of this area routine.
Preferably, before carrying out following step S03, also comprise the anode layer 2 in step S02 is carried out to plasma treatment: this substrate that is coated with anode layer 2 is placed in to stool ion processing chamber, carries out plasma treatment.This plasma treatment condition adopts the process conditions of this area routine.After plasma treatment, anode layer 2 can effectively improve anode work function, reduces the injection barrier in hole.
In above-mentioned steps S03, preparing the method for organic function layer 3 adjusts according to its structure, as the structure when organic function layer 3 comprises the hole injection layer 31 that stacks gradually combination as shown in Figure 1, hole transmission layer 32, luminescent layer 33, hole blocking layer 34, when electron transfer layer 35, the substrate that contains anode layer 2 after step S02 processes is placed in to vacuum coating system, plate successively hole injection layer 31 at these anode layer 2 outer surfaces, hole transmission layer 32, luminescent layer 33, hole blocking layer 34, the functional layers such as electron transfer layer 35, in the time of each layer of evaporation, material take equivalent layer is prepared each layer as plating source, wherein, plating hole injection layer 31, hole transmission layer 32, luminescent layer 33, hole blocking layer 34, the plating source that electron transfer layer 35 is each layer as described above, in order to save length, do not repeat them here.Wherein, as in the time plating electron transfer layer 35, alkaline metal iodide, electric transmission host material are placed in respectively in two evaporation sources of vacuum coating system, the electron transfer layer 35 adulterating by the method preparation of codope, wherein, alkaline metal iodide is preferably (5～30) with the ratio of the evaporation speed of electric transmission host material: 100.Plate the evaporation speed in source by controlling both, to realize both Uniform Dopeds, and control the ratio of both doping, to obtain even structure and stable electron transfer layer 35.
Further, as the preferred embodiment of the present invention, in the time that this organic function layer 3 also comprises electron injecting layer 36, after plating electron transfer layer 35 and before carrying out lower step S04, also comprise the step of plating electron injecting layer 36:
In vacuum coating system, at electron transfer layer 35 outer surface plated films, form electron injecting layer 36 take alkaline metal iodide as plating source.
Wherein, the plating source of plating electron injecting layer 36 alkaline metal iodide as described above.Preferably, the concrete kind of this alkaline metal iodide is identical with the kind of the electric transmission dopant alkaline metal iodide in electron transfer layer 35, and the evaporation speed of this alkaline metal iodide is 0.02～0.5nm/s.This preferred evaporation condition, can obtain even structure, and has good ohmic contact with electron transfer layer 35.
In the time of plating hole injection layer 36, the substrate that is coated with hole transmission layer 35 is placed in to coating system, material take plating hole injection layer 36 carries out plated film as plating source at hole transmission layer 35 outer surfaces, forms hole injection layer 36, and evaporation condition can adopt the condition of this area routine.
Particularly, in above-mentioned steps S04, the substrate that is coated with organic function layer 3 is placed in to coating system, carries out plated film as plating source at organic function layer 3 outer surfaces take cathode material, form cathode layer 4.Its plated film condition evaporation rate is preferably 0.5nm/s, and by controlling the evaporation time, the thickness that preferably makes cathode layer 4 is 100nm.
From the above, above-mentioned Organnic electroluminescent device preparation method is plating source the evaporation speed of controlling two plating sources by dopant and electric transmission host material, evaporation makes electric transmission doped layer structure, this electric transmission doped layer even structure and stable, the low electric transmission efficiency of interior resistance is high, thereby gives excellent properties such as luminous efficiency and low starting resistor etc. that this Organnic electroluminescent device is high.In addition, the method technique is simple, and condition is easily controlled, and conforming product rate is high, has effectively improved production efficiency, is suitable for industrialization and produces.
Now, in conjunction with instantiation, structure to embodiment of the present invention Organnic electroluminescent device and preparation method thereof is further elaborated.
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm)/CuPc (20nm)/NPB (30nm)/NPB:Ir (MDQ)
2(acac) (25nm)/TPBi (10nm)/KI:TPBi (30nm)/KI (0.5nm)/Ag (100nm); Wherein, electron transfer layer is the mixture layer of the mutual doping of KI and TPBi, and wherein, the mass ratio of KI and TPBi is 1:10.
This Organnic electroluminescent device preparation method comprises following step:
Step S11. provides glass substrate: glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up for subsequent use with nitrogen;
Step S12., in magnetic control sputtering system, prepares ito anode layer in the glass substrate in step S11, and antianode layer carries out plasma treatment as described above;
Step S13. is in vacuum coating system, and the ito anode layer outer surface of preparing in step S12 be evaporation hole injection layer CuPc, hole transmission layer NPB, luminescent layer NPB:Ir (MDQ) successively
2(acac), hole blocking layer TPBi;
Step S14: in vacuum coating system, adulterant metallic compound dopant KI and organic electronic are transmitted to host material TPBi respectively as in two evaporation sources, by regulating firing rate and heat to supply with, carry out while evaporation, make electron transfer layer; Particularly, the evaporation rate of KI is at 0.05nm/s, and the evaporation rate of TPBi is 0.5nm/s;
Step S15: in vacuum coating system, KI is placed in to evaporation source, at electron transfer layer outer surface plated film, forms electron injecting layer;
Step S16: in vacuum coating system, at electron injecting layer outer surface evaporation anode A g layer, form negative electrode, obtain Organnic electroluminescent device.
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm)/ZnPc (20nm)/TCTA (40nm)/NPB:Ir (MDQ)
2(acac) (25nm)/BAlq (10nm)/NaI:Alq
3(40nm)/NaI (0.2nm) Al (100nm); Wherein, electron transfer layer is NaI and Alq
3the mixture layer of mutual doping, wherein, NaI and Alq
3mass ratio be 1:5.
This Organnic electroluminescent device preparation method comprises following step:
Step S21. provides glass substrate: glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up for subsequent use with nitrogen;
Step S22., in magnetic control sputtering system, prepares ito anode layer in the glass substrate in step S21, and antianode layer carries out plasma treatment as described above;
Step S23. is in vacuum coating system, and the ito anode layer outer surface of preparing in step S22 be evaporation hole injection layer ZnPc, hole transmission layer TCTA, luminescent layer NPB:Ir (MDQ) successively
2(acac), hole blocking layer BAlq;
Step S24: in vacuum coating system, adulterant metallic compound dopant NaI and organic electronic transmission host material Alq
3as in two evaporation sources, by regulating firing rate and heat to supply with, carry out while evaporation respectively, make electron transfer layer; Particularly, the evaporation rate of NaI is at 0.02nm/s, Alq
3evaporation rate be 0.1nm/s;
Step S25: in vacuum coating system, NaI is placed in to evaporation source, at electron transfer layer outer surface plated film, forms electron injecting layer;
Step S26: in vacuum coating system, at electron injecting layer outer surface evaporation anode A l layer, form negative electrode, obtain Organnic electroluminescent device.
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm)/m-MTDATA (20nm)/TPD (40nm)/NPB:Ir (MDQ)
2(acac) (25nm)/BAlq (10nm)/LiI:BAlq (60nm)/LiI (2nm)/Al-Mg (100nm); Wherein, electron transfer layer is the mixture layer of the mutual doping of LiI and BAlq, and wherein, the mass ratio of LiI and BAlq is 1:20.
This Organnic electroluminescent device preparation method comprises following step:
Step S31. provides glass substrate: glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up for subsequent use with nitrogen;
Step S32., in magnetic control sputtering system, prepares ito anode layer in the glass substrate in step S31, and antianode layer carries out plasma treatment as described above;
Step S33. is in vacuum coating system, and the ito anode layer outer surface of preparing in step S32 be evaporation hole injection layer m-MTDATA, hole transmission layer TPD, luminescent layer NPB:Ir (MDQ) successively
2(acac), hole blocking layer BAlq;
Step S34: in vacuum coating system, adulterant metallic compound Dopant Li I and organic electronic are transmitted to host material BAlq respectively as in two evaporation sources, by regulating firing rate and heat to supply with, carry out while evaporation, make electron transfer layer; Particularly, the evaporation rate of LiI is at 0.02nm/s, and the evaporation rate of BAlq is 0.4nm/s;
Step S35: in vacuum coating system, LiI is placed in to evaporation source, at electron transfer layer outer surface plated film, forms electron injecting layer;
Step S36: in vacuum coating system, at electron injecting layer outer surface evaporation anode A l-Mg layer, form negative electrode, obtain Organnic electroluminescent device.
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm) //m-MTDATA (40nm)/2-TNATA/ (20nm)/CBP:FIrPic (10nm)/Bphen (10nm)/CsI:Bphen (60nm)/CsI (0.5nm)/Ag-Mg (100nm); Wherein, electron transfer layer is the mixture layer of the mutual doping of CsI and Bphen, and wherein, the mass ratio of CsI and Bphen is 3:10.
This Organnic electroluminescent device preparation method comprises following step:
Step S41. provides glass substrate: glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up for subsequent use with nitrogen;
Step S42., in magnetic control sputtering system, prepares ito anode layer in the glass substrate in step S41, and antianode layer carries out plasma treatment as described above;
Step S43. in vacuum coating system, the ito anode layer outer surface of preparing in step S42 evaporation hole injection layer m-MTDATA, hole transmission layer 2-TNATA, luminescent layer CBP:FIrPic, hole blocking layer Bphen successively;
Step S44: in vacuum coating system, adulterant metallic compound dopant CsI and organic electronic are transmitted to host material Bphen respectively as in two evaporation sources, by regulating firing rate and heat to supply with, carry out while evaporation, make electron transfer layer; Particularly, the evaporation rate of CsI is at 0.1nm/s, and the evaporation rate of Bphen is 0.3nm/s;
Step S45: in vacuum coating system, CsI is placed in to evaporation source, at electron transfer layer outer surface plated film, forms electron injecting layer;
Step S46: in vacuum coating system, at electron injecting layer outer surface evaporation anode A g-Mg layer, form negative electrode, obtain Organnic electroluminescent device.
Embodiment 5
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm) //m-MTDATA (40nm)/2-TNATA/ (20nm)/CBP:FIrPic (10nm)/Bphen (10nm)/RbI:TAZ (80nm)/Ag-Mg (100nm); Wherein, electron transfer layer is the mixture layer of the mutual doping of RbI and TAZ, and wherein, the mass ratio of RbI and TAZ is 1:5.
This Organnic electroluminescent device preparation method comprises following step:
Step S51. provides glass substrate: glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up for subsequent use with nitrogen;
Step S52., in magnetic control sputtering system, prepares ito anode layer in the glass substrate in step S51, and antianode layer carries out plasma treatment as described above;
Step S53. in vacuum coating system, the ito anode layer outer surface of preparing in step S52 evaporation hole injection layer m-MTDATA, hole transmission layer 2-TNATA, luminescent layer CBP:FIrPic, hole blocking layer Bphen successively;
Step S54: in vacuum coating system, adulterant metallic compound dopant RbI and organic electronic are transmitted to host material TAZ respectively as in two evaporation sources, by regulating firing rate and heat to supply with, carry out while evaporation, make electron transfer layer; Particularly, the evaporation rate of RbI is at 0.04nm/s, and the evaporation rate of TAZ is 0.2nm/s;
Step S55: in vacuum coating system, RbI is placed in to evaporation source, at electron transfer layer outer surface plated film, forms electron injecting layer;
Step S56: in vacuum coating system, at electron injecting layer outer surface evaporation anode A g-Mg layer, form negative electrode, obtain Organnic electroluminescent device.
Comparative example 1
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm)/CuPc (20nm)/NPB (30nm)/NPB:Ir (MDQ)
2(acac) (20nm)/TPBi (40nm)/Ag (100nm); Compare embodiment 1, the Organnic electroluminescent device in this comparative example 1 does not adopt the electron transfer layer structure of doping, there is no electron injecting layer structure yet.
Comparative example 2
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm)/CuPc (20nm)/NPB (30nm)/NPB:Ir (MDQ)
2(acac) (20nm)/TPBi (40nm)/LiF (1nm)/Ag (100nm); Compare embodiment 1, the Organnic electroluminescent device in this comparative example 2 does not adopt the electron transfer layer structure of doping, but adopts LiF as electron injecting layer structure
Organnic electroluminescent device carries out luminescent properties test
Organnic electroluminescent device prepared by above-described embodiment 1 and comparative example 1 carries out current-voltage characteristic curve test, and test result as shown in Figure 4.Can obviously be found out by Fig. 4, adopt the electron transfer layer of doping, in the electron transfer layer that makes to contain doping and the Organnic electroluminescent device of electron injecting layer, electronic injection performance is improved significantly.
Organnic electroluminescent device prepared by above-described embodiment 1 to embodiment 5 and comparative example 1 and comparative example 2 carries out luminescent properties test, and test result is as following table 1:
Table 1
Can find out in conjunction with Fig. 1 and table 1, the Organnic electroluminescent device of the electron transfer layer with doping prepared by above-described embodiment is because electronic injection performance is improved, its starting resistor is starkly lower than common luminescent device, in luminous efficiency, be better than common Organnic electroluminescent device with the light efficiency of Organnic electroluminescent device of the electron transfer layer of doping.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an Organnic electroluminescent device, comprise the substrate layer, anode layer, organic function layer and the cathode layer that stack gradually combination, it is characterized in that: described organic function layer comprises electron transfer layer and luminous luminescent layer under additional power source drives, described electron transfer layer is stacked to be combined between described cathode layer and luminescent layer, wherein, the alkaline metal iodide that is 3.8～28.6% doped with quality percentage composition in described electron transfer layer.
2. Organnic electroluminescent device according to claim 1, it is characterized in that: described organic function layer also comprises electron injecting layer, surface thereof is combined with described cathode layer, be combined with electron transfer layer in another relative surface, wherein, the material of described electron injecting layer is alkali-metal halide.
3. Organnic electroluminescent device according to claim 2, is characterized in that: described alkali-metal halide is alkaline metal iodide.
4. Organnic electroluminescent device according to claim 3, is characterized in that: the material alkaline metal iodide kind of described electron injecting layer is identical with the alkaline metal iodide kind of adulterating in electron transfer layer.
5. Organnic electroluminescent device according to claim 2, is characterized in that: the thickness of described electron injecting layer is 0.2～2nm.
6. according to the Organnic electroluminescent device described in claim 1～5 any one, it is characterized in that: described alkaline metal iodide is at least one in lithium iodide, KI, sodium iodide, cesium iodide, rubidium iodide.
7. according to the Organnic electroluminescent device described in claim 1～5 any one, it is characterized in that: the thickness of described electron transfer layer is 30～100nm.
8. the Organnic electroluminescent device preparation method as described in claim 1～7 any one, between the described luminescent layer of preparation and the step of cathode layer, comprises the step of preparing described electron transfer layer:
In coating system, take alkaline metal iodide and electric transmission host material as two independently plating source carry out plated film, form described electron transfer layer, wherein, alkaline metal iodide is (5～30) with the ratio of the evaporation speed of electric transmission host material: 100.
9. Organnic electroluminescent device preparation method as claimed in claim 8, it is characterized in that, after the step of the described electron transfer layer of preparation, also comprise the step of preparing electron injecting layer: at described electron transfer layer outer surface plated film, form electron injecting layer take alkaline metal iodide as plating source.
10. Organnic electroluminescent device preparation method as claimed in claim 9, is characterized in that, in the step of the described electron injecting layer of preparation, the evaporation speed of described alkaline metal iodide is 0.02～05nm/s.
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