CN103855311A - Organic electroluminescence device and preparation method thereof - Google Patents

Organic electroluminescence device and preparation method thereof Download PDF

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Publication number
CN103855311A
CN103855311A CN201210504790.8A CN201210504790A CN103855311A CN 103855311 A CN103855311 A CN 103855311A CN 201210504790 A CN201210504790 A CN 201210504790A CN 103855311 A CN103855311 A CN 103855311A
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China
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layer
lithium compound
electroluminescent device
electron injecting
organnic electroluminescent
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周明杰
王平
冯小明
张振华
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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]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • 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 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 injecting layer, an electron transmission layer and a light-emitting layer which are laminated and combined in turn, and the light-emitting layer is driven to emit light by an external power supply. The electron injecting layer and the cathode layer are laminated and combined. The electron injecting layer contains a mixture of inorganic lithium compound and organic lithium compound with mass ratio of 1:0.2-2. 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 electron injecting efficiency so that starting voltage is lowered and light emission efficiency of the organic electroluminescence device is enhanced. 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

Organnic electroluminescent device and preparation method thereof
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, 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.
In order to improve the luminous efficiency of this device, the selected material of electron injecting layer in existing device improves, as independent employing inorganic matter electron injection material or adopt separately organic electronic injection material, but the electron injecting layer existence and stability of this material is not high, higher with the interface potential barrier of electric transmission bed boundary, cause electron injection efficiency lower, thereby caused the luminous efficiency of OLED low, required driving voltage is higher, has reduced its working life.
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 electron injection efficiency.
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, described organic function layer comprises the electron injecting layer, electron transfer layer and the luminous luminescent layer under additional power source drives that stack gradually combination, the stacked combination of described electron injecting layer and cathode layer, wherein, described electron injecting layer contains inorganic lithium compound that mass ratio is 1:0.2～2 and the mixture of organo-lithium compound.
And a kind of preparation method of above-mentioned Organnic electroluminescent device, between the described electron transfer layer of preparation and the step of cathode layer, comprises the step that is prepared as follows described electron injecting layer:
In coating system, carry out plated film as two sources of independently plating at electron transfer layer outer surface taking inorganic lithium compound and organo-lithium compound, form electron injecting layer.
The electron injecting layer of Organnic electroluminescent device of the present invention adopts inorganic lithium compound and the organo-lithium compound formation of adulterating mutually, wherein, inorganic lithium compound can effectively improve the stability of electron injecting layer, organo-lithium compound can effectively reduce the interface potential barrier between electron injecting layer and electron transport material, therefore, adulterate and given the electronic injection effect of this electron injecting layer excellence mutually by inorganic lithium compound and organo-lithium compound, thereby give excellent properties such as luminous efficiency and low starting resistor etc. that Organnic electroluminescent device is high.
Organnic electroluminescent device preparation method of the present invention is two independently to plate source by inorganic lithium compound and organo-lithium compound, by controlling the evaporation speed in two plating sources, prepares even structure and stable doped structure electron injecting layer.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.
Brief description of the drawings
Fig. 1 is the structural representation of embodiment of the present invention Organnic electroluminescent device;
Fig. 2 is embodiment of the present invention Organnic electroluminescent device preparation method's schematic flow sheet;
Fig. 3 is the current-voltage relation curve figure of the Organnic electroluminescent device of the embodiment of the present invention 1 and comparative example 1,2 preparations.
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 electron injection efficiency.As shown in Figure 1, it comprises the substrate layer 1, anode layer 2, organic function layer 3 and the cathode layer 4 that stack gradually to this Organnic electroluminescent device structure.
Wherein, organic function layer 3 comprises the hole injection layer 31, hole transmission layer 32, luminescent layer 33, electron transfer layer 34, the electron injecting 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 injecting layer 35 and cathode layer 4, its structure is as shown in Figure 1.
In this organic function layer 3, the selected material of hole injection layer 31 is preferably CuPc (CuPc), CuPc (ZnPc), (4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 4; 4 ', 4 " at least one in tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA).Certainly, the selected 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 selected material of above-mentioned hole transmission layer 32 is preferably 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, in addition, 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.
Above-mentioned luminescent layer 33 can be luminous under additional power source drives, and its selected luminescent material can be selected flexibly according to actual demand (as requirements such as glow colors).As selected 4,4 '-bis-(9-carbazole) biphenyl (CBP), two (4,6-difluorophenyl pyridine-N, C2) pyridine carboxylic acid closes iridium (FIrPic), N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) (Ir (MDQ) 2(acac)), 4,4 ', 4 "-tri-(carbazole-9-yl)-triphenylamines (TCTA), three (2-phenylpyridine) close iridium (Ir (ppy) 3), 4, 4 '-bis-(2, 2-diphenylethyllene)-1, 1 '-biphenyl (DPBVi), 4-4-dicyano methylene-2-the tert-butyl group-6-(1, 1, 7, 7-tetramethyl-julolidine-9-vinyl)-4H-pyrans (DCJTB), 4, 4 '-bis-(9-carbazole) biphenyl and two (4, 6-difluorophenyl pyridine-N, C2) pyridine carboxylic acid closes the dopant mixture (CBP:FIrPic) of iridium, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamines and two (2-methyl-diphenyl [f, h] quinoxaline) dopant mixture (NPB:Ir (MDQ) of (acetylacetone,2,4-pentanedione) 2(acac)), 4,4 ', 4 "-tri-(carbazole-9-yl)-triphenylamines and three (2-phenylpyridine) close the dopant mixture (TCTA:Ir (ppy) of iridium 3), the 4-4-dicyano methylene-2-tert-butyl group-6-(1,1,7,7-tetramethyl-julolidine-9-vinyl)-4H-pyrans and oxine) any in the dopant mixture (DCJTB:Alq3) of-aluminium.Wherein, CBP:FIrPic, NPB:Ir (MDQ) 2(acac), TCTA:Ir (ppy) 3according to the mixing of adulterating of existing ratio, as NPB:Ir (MDQ) 2(acac), wherein, NPB is material of main part, Ir (MDQ) 2(acac) be guest materials, and main, object doping mass ratio is 5:100.The thickness of this luminescent layer 33 can be set to 10nm, 20nm, certainly, and also other thickness ranges of this area routine of its thickness.
The selected material of above-mentioned electron transfer layer 34 is preferably (oxine)-aluminium (Alq 3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (TAZ), two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) at least one in aluminium (BAlq).Electron transfer layer 34 even structure of this material, stable, interior resistance is little, can further improve the efficiency of transmission of electronics.The thickness of this electron transfer layer 34 can be set to 40nm, 50nm, certainly, and also other thickness ranges of this area routine of its thickness.
The selected material of above-mentioned electron transfer layer 35 contains inorganic lithium compound that mass ratio is 1:0.2～2 and the mixture of organo-lithium compound.Wherein, this inorganic lithium compound is preferably Li 3n, LiN 3, LiCoO 2, LiPO 4in at least one, organo-lithium compound is preferably Liq and/or CH 3cO 2li.Inorganic lithium compound in this electron transfer layer 35 can effectively improve the stability of electron injecting layer, organo-lithium compound can effectively reduce the interface potential barrier between electron injecting layer and electron transport material, and both adulterate mutually and have given the electronic injection effect of these electron injecting layer 35 excellences.In order to make the electronic injection effect of this electron transfer layer 35 more excellent, the thickness of electron injecting layer 35 is preferably controlled at 0.2～5nm.
Certainly, on the basis of Organnic electroluminescent device structure as shown in Figure 1, above-mentioned organic function layer 3 can also comprise electronic barrier layer and hole blocking layer (electronic barrier layer and hole blocking layer Fig. 1 do not show), this electronic barrier layer is stacked to be combined between hole transmission layer 32 and luminescent layer 33, and this hole blocking layer is stacked to be combined between electron transfer layer 34 and luminescent layer 33.
Wherein, the selected material of this electronic barrier layer can be conventional material known in this field, and its thickness can be also the thickness of this area routine.The setting of electronic barrier layer is for cathode layer 4 injected electrons are trapped in luminescent layer 33 as much as possible, to improve 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.
The selected material of this hole blocking layer can be conventional material known in this field, and its thickness can be also the thickness of this area routine.This hole blocking layer and electronic barrier layer arrange simultaneously, synergy, can make to be trapped in as much as possible luminescent layer 33 from anode layer 4 injected holes, and make this hole and electronics meeting rate in luminescent layer 33, to improve both exciton amounts compound and that form, to reach the object of the luminous intensity that strengthens luminescent layer 33.Certainly, this hole blocking layer and electronic barrier layer also can be selected a setting.
In the Organnic electroluminescent device shown in Fig. 1, substrate layer 1 can be selected the conventional material in this area and conventional thickness.Can select substrate of glass material etc. as its material.
The material of anode layer 2 can be selected indium doped stannum oxide film (ITO), indium-zinc oxide (IZO) or aluminium zinc oxide (AZO), at least one in gallium zinc oxide (GZO).Its thickness can be 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 selected material of cathode layer 4 can be aluminium (Al), and its thickness can be set to 70～200nm.Certainly, the selected material of cathode layer 4 can also be argent (Ag), silver-colored magnesium alloy (Ag-Mg) or magnadure (Al-Mg), and thickness also can arrange other conventional thickness.
From the above, the electron injecting layer 35 of above-described embodiment Organnic electroluminescent device adopts inorganic lithium compound and the organo-lithium compound formation of adulterating mutually, wherein, inorganic lithium compound can effectively improve the stability of electron injecting layer 35, organo-lithium compound can effectively reduce the interface potential barrier between electron injecting layer 35 and electron transport material 34, therefore, adulterate mutually and given the electronic injection effect of these electron injecting layer 35 excellences by inorganic lithium compound and organo-lithium compound, thereby give excellent properties such as luminous efficiency and low starting resistor etc. that Organnic electroluminescent device is high, extend its useful life.By the setting to other each layer of structure, selected material and the adjustment of thickness, synergy with this electron injecting layer 35, to reach the injection efficiency and the concentration that improve charge carrier in Organnic electroluminescent device, further to significantly improve the luminous efficiency of this Organnic electroluminescent device, reduce the effect of the starting resistor of this 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 2, refers to Fig. 1 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;
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, electron transfer layer 34, when electron injecting 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, electron transfer layer 34, the functional layers such as electron injecting layer 35, in the time of each layer of evaporation, material taking equivalent layer is prepared each layer as plating source, wherein, plating hole injection layer 31, hole transmission layer 32, luminescent layer 33, electron transfer layer 34, the plating source that electron injecting layer 35 is each layer as described above, in order to save length, do not repeat them here.Wherein, in the time of plating electron injecting layer 35, inorganic lithium compound and organo-lithium compound are placed in respectively in two evaporation sources of vacuum coating system, prepare the electron injecting layer 35 of doped structure by the method for codope.In the time of this electron injecting layer 35 of plating, inorganic lithium compound is or/and the evaporation speed in organo-lithium compound plating source is preferably 0.01 ~ 0.1nm/s, and wherein, inorganic lithium compound is preferably 1:(0.2-2 with the ratio of the evaporation speed of organo-lithium compound).In the time preparing electron injecting layer 35, by controlling the evaporation speed in each plating source, to realize evenly mixing between corresponding plating source, and control the ratio that mix in corresponding plating source, to obtain even structure and stable electron injecting layer 35.In addition, by the control to evaporation time and evaporation speed, realize each functional layer in organic function layer 3 as the control of electron injecting layer 35 and other each layer thicknesses.
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 taking cathode material, form cathode layer 4.Its evaporation condition adopts the process conditions of this area routine.If its evaporation rate is 0.5nm/s, by controlling the thickness of evaporation time with control cathode layer 4.
From the above, above-mentioned Organnic electroluminescent device preparation method is two independently to plate source by inorganic lithium compound and organo-lithium compound, by controlling the evaporation speed in two plating sources, prepare even structure and stable doped structure electron injecting layer, effectively reduce the interface potential barrier between electron injecting layer and electron transport material, improve the electronic injection effect of electron injecting layer, 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.
Now, in conjunction with instantiation, structure to embodiment of the present invention Organnic electroluminescent device and preparation method thereof is further elaborated.
Embodiment 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)/Li 3n:Liq (1: 1,0.2nm)/Al (70nm).Wherein, hole injection layer is CuPc, and hole transmission layer is NPB, and luminescent layer is NPB:Ir (MDQ) 2(acac), electron transfer layer is TPBi, and electron injecting layer is Li 3the doping mixed structure layer of N:Liq.
This Organnic electroluminescent device is preparation method comprise the following steps:
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 5 × 10 in vacuum -4in the coating system of Pa, the ito anode layer outer surface evaporation cave implanted layer successively of preparing in step S12, hole transmission layer, luminescent layer, electron transfer layer, the evaporation rate of each layer is 0.2nm/s;
Step S14. is 5 × 10 in vacuum degree -4in the Vacuum Heat coating system of Pa, adulterant Li 3n and Liq, respectively as in two evaporation sources, by regulating firing rate and heat to supply with, carry out while evaporation, make electron injecting layer; Particularly, Li 3the evaporation rate of N is at 0.01nm/s, and the evaporation rate of Liq is 0.01nm/s;
Step S15: in vacuum coating system, at electron injecting layer outer surface evaporation anode A l layer, form negative electrode, obtain Organnic electroluminescent device.
Embodiment 2
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm)/ZnPc (20nm)/TCTA (40nm)/TCTA:Ir (ppy) 3(15nm)/BAlq (50nm)/LiCoO 2: CH 3cO 2li (1:0.2,5nm)/Al (100nm).Wherein, hole injection layer is ZnPc, and hole transmission layer is TCTA, and luminescent layer is TCTA:Ir (ppy) 3, electron transfer layer is BAlq, electron injecting layer is LiCoO 2: CH 3cO 2the doping mixed structure layer of Li.
This Organnic electroluminescent device is preparation method comprise the following steps:
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 5 × 10 in vacuum -4in the coating system of Pa, the ito anode layer outer surface evaporation cave implanted layer successively of preparing in step S22, hole transmission layer, luminescent layer, electron transfer layer, the evaporation rate of each layer is 0.2nm/s;
Step S24. is 5 × 10 in vacuum degree -4in the Vacuum Heat coating system of Pa, adulterant LiCoO 2and CH 3cO 2li, respectively as in two evaporation sources, by regulating firing rate and heat to supply with, carries out while evaporation, makes electron injecting layer; Particularly, LiCoO 2evaporation rate at 0.2nm/s, CH 3cO 2the evaporation rate of Li is 0.04nm/s;
Step S25: in vacuum coating system, at electron injecting layer outer surface evaporation anode A l layer, form negative electrode, obtain Organnic electroluminescent device.
Embodiment 3
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm)/m-MTDATA (20nm)/TPD (40nm)/DPBVi (20nm)/BCP (50nm)/LiN 3: Liq (1:2,1nm)/Al (120nm).Wherein, hole injection layer is m-MTDATA, and hole transmission layer is TPD, and luminescent layer is DPBVi, and electron transfer layer is BCP, and electron injecting layer is LiN 3: the doping mixed structure layer of Liq.
This Organnic electroluminescent device is preparation method comprise the following steps:
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 5 × 10 in vacuum -4in the coating system of Pa, the ito anode layer outer surface evaporation cave implanted layer successively of preparing in step S32, hole transmission layer, luminescent layer, electron transfer layer, the evaporation rate of each layer is 0.2nm/s;
Step S34. is 5 × 10 in vacuum degree -4in the Vacuum Heat coating system of Pa, adulterant LiN 3respectively as in two evaporation sources, by regulating firing rate and heat to supply with, carry out while evaporation with Liq, make electron injecting layer; LiN particularly 3evaporation rate at 0.05nm/s, the evaporation rate of Liq is 0.1nm/s;
Step S35: in vacuum coating system, at electron injecting layer outer surface evaporation anode A l layer, form negative electrode, obtain Organnic electroluminescent device.
Embodiment 4
A kind of Organnic electroluminescent device, its structure is glass substrate/ITO (100nm)/2-TNATA (20nm)/TPD (30nm)/CBP:FIrPic (10nm)/Bphen (40nm)/Li 3pO 4: Liq (1:0.5,5nm)/Al (150nm).Wherein, hole injection layer is 2-TNATA, and hole transmission layer is TPD, and luminescent layer is CBP:FIrPic, and electron transfer layer is Bphen, and electron injecting layer is Li 3pO 4: the doping mixed structure layer of Liq.
This Organnic electroluminescent device is preparation method comprise the following steps:
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. is 5 × 10 in vacuum -4in the coating system of Pa, the ito anode layer outer surface evaporation cave implanted layer successively of preparing in step S42, hole transmission layer, luminescent layer, electron transfer layer, the evaporation rate of each layer is 0.2nm/s;
Step S44. is 5 × 10 in vacuum degree -4in the Vacuum Heat coating system of Pa, adulterant Li 3pO 4respectively as in two evaporation sources, by regulating firing rate and heat to supply with, carry out while evaporation with Liq, make electron injecting layer; Li particularly 3pO 4evaporation rate at 0.1nm/s, the evaporation rate of Liq is 0.05nm/s;
Step S45: in vacuum coating system, at electron injecting layer outer surface evaporation anode A l layer, form negative electrode, obtain Organnic electroluminescent device.
Embodiment 5
A kind of Organnic electroluminescent device, its structure is glass substrate/GZO (100nm) //m-MTDATA (40nm)/NPB (20nm)/DCJTB:Alq3 (20nm)/Alq3 (40nm)/LiN 3: CH 3cO 2li (1:1.5,0.5nm)/Al (200nm).Wherein, hole injection layer is m-MTDATA, and hole transmission layer is NPB, and luminescent layer is DCJTB:Alq3, and electron transfer layer is Alq3, and electron injecting layer is LiN 3: CH 3cO 2the doping mixed structure layer of Li.
This Organnic electroluminescent device is preparation method comprise the following steps:
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, prepare GZO anode layer, and antianode layer carries out plasma treatment as described above in the glass substrate in step S51;
Step S53. is 5 × 10 in vacuum -4in the coating system of Pa, the GZO anode layer outer surface evaporation cave implanted layer successively of preparing in step S52, hole transmission layer, luminescent layer, electron transfer layer, the evaporation rate of each layer is 0.2nm/s;
Step S54. is 5 × 10 in vacuum degree -4in the Vacuum Heat coating system of Pa, adulterant LiN 3and CH 3cO 2li, respectively as in two evaporation sources, by regulating firing rate and heat to supply with, carries out while evaporation, makes electron injecting layer; LiN particularly 3evaporation rate at 0.02nm/s, CH 3cO 2the evaporation rate of Li is 0.03nm/s;
Step S55: in vacuum coating system, at electron injecting layer outer surface evaporation anode A l layer, form negative electrode, obtain Organnic electroluminescent device.
Comparative example 1
With reference to embodiment 1, making device architecture is glass substrate/ITO (100nm)/CuPc (20nm)/NPB (30nm)/NPB:Ir (MDQ) 2(acac) (20nm)/TPBi (40nm)/LiN 3(0.2nm)/Al (70nm); Compare embodiment 1,1 of comparative example adopts inorganic material as electron injecting layer.
Comparative example 2
With reference to embodiment 1, making device architecture is glass substrate/ITO (100nm)/CuPc (20nm)/NPB (30nm)/NPB:Ir (MDQ) 2(acac) (20nm)/TPBi (40nm)/Liq (0.2nm)/Al (70nm); Compare embodiment 1,2 employing organic materials of comparative example are as electron injecting layer.
Organnic electroluminescent device carries out luminescent properties test
Above-described embodiment 1 and the Organnic electroluminescent device of comparative example 1,2 preparations are carried out to current-voltage relation analysis, and analysis result as shown in Figure 3.Can obviously be found out by Fig. 3, it is electron injecting layer that the Organnic electroluminescent device of preparing due to embodiment has adopted the mixture of inorganic lithium compound and organo-lithium compound doping.Inorganic lithium compound in electron injecting layer can effectively improve the stability of electron injecting layer, and organo-lithium compound can effectively reduce the interface potential barrier between electron injecting layer and electron transport material.Therefore, by the synergy of inorganic lithium compound and organo-lithium compound, make the stability of electron injecting layer be better than existing common organic electron injecting layer, thereby what make that electronics can stability and high efficiency is injected into electron transfer layer from negative electrode, and effectively reduce the interface potential barrier between electron injecting layer and electron transfer layer, thereby under lower starting resistor, can obtain larger drive current, extend the useful life of this Organnic electroluminescent device.
The Organnic electroluminescent device of above-described embodiment 1 to embodiment 5 and comparative example 1,2 preparations is carried out to luminescent properties test, and test result is as following table 1:
Table 1
Figure BDA00002503183400131
Can find out in conjunction with Fig. 1 and table 1, the Organnic electroluminescent device of above-described embodiment 1～5 preparation is compared with common luminescent device, embodiment 1～5 prepares Organnic electroluminescent device because electronic injection performance is improved, its starting resistor is starkly lower than the luminescent device of comparative example 1 and 2, in luminous efficiency, the obvious efficiency of OLED device provided by the invention is higher.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments 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 (9)

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 the electron injecting layer, electron transfer layer and the luminous luminescent layer under additional power source drives that stack gradually combination, the stacked combination of described electron injecting layer and cathode layer, wherein, described electron injecting layer contains inorganic lithium compound that mass ratio is 1:0.2～2 and the mixture of organo-lithium compound.
2. Organnic electroluminescent device according to claim 1, is characterized in that: described inorganic lithium compound is Li 3n, LiN 3, LiCoO 2, LiPO 4in at least one.
3. Organnic electroluminescent device according to claim 1, is characterized in that: described organo-lithium compound is Liq and/or CH 3cO 2li.
4. according to the arbitrary described Organnic electroluminescent device of claim 1～3, it is characterized in that: the thickness of described electron injecting layer is 0.2～5nm.
5. according to the arbitrary described Organnic electroluminescent device of claim 1～3, it is characterized in that: the selected material of described electron transfer layer is (oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2, in 4-triazole derivative, two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) aluminium at least any.
6. Organnic electroluminescent device according to claim 1, it is characterized in that: the selected material of described luminescent layer is 4, 4 '-bis-(9-carbazole) biphenyl, two (4, 6-difluorophenyl pyridine-N, C2) pyridine carboxylic acid closes iridium, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamines, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione), 4, 4 ', 4 "-tri-(carbazole-9-yl)-triphenylamine, three (2-phenylpyridines) close iridium, 4, 4 '-bis-(2, 2-diphenylethyllene)-1, 1 '-biphenyl, 4-4-dicyano methylene-2-the tert-butyl group-6-(1, 1, 7, 7-tetramethyl-julolidine-9-vinyl)-4H-pyrans, 4, 4 '-bis-(9-carbazole) biphenyl and two (4, 6-difluorophenyl pyridine-N, C2) pyridine carboxylic acid closes the dopant mixture of iridium, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamines and two (2-methyl-diphenyl [f, h] quinoxaline) dopant mixture of (acetylacetone,2,4-pentanedione), 4, 4 ', 4 " dopant mixture that-tri-(carbazole-9-yl)-triphenylamines and three (2-phenylpyridine) close iridium, 4-4-dicyano methylene-2-the tert-butyl group-6-(1, 1, 7, 7-tetramethyl-julolidine-9-vinyl)-4H-pyrans and oxine) any in the dopant mixture of-aluminium.
7. the Organnic electroluminescent device preparation method as described in claim 1～6 any one, between the described electron transfer layer of preparation and the step of cathode layer, comprises the step that is prepared as follows described electron injecting layer:
In coating system, carry out plated film as two sources of independently plating at electron transfer layer outer surface taking inorganic lithium compound and organo-lithium compound, form electron injecting layer.
8. Organnic electroluminescent device preparation method as claimed in claim 7, is characterized in that: described inorganic lithium compound is or/and the evaporation speed of organo-lithium compound is 0.01～0.1nm/s.
9. Organnic electroluminescent device preparation method as claimed in claim 7 or 8, is characterized in that: described inorganic lithium compound is 1:(0.2～2 with the ratio of the evaporation speed of organo-lithium compound).
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Application publication date: 20140611