CN102842682A - Stacked organic electroluminescence device and manufacturing method thereof - Google Patents
Stacked organic electroluminescence device and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a stacked organic electroluminescence device. The stacked organic electroluminescence device comprises an anode, a cathode, two organic electroluminescence layers positioned between the anode and the cathode, and a charge generation layer positioned between the two organic electroluminescence layers, wherein the charge generation layer comprises an n-type layer, a metal layer, an interface layer and a p-type layer, which are stacked in sequence; and the n-type layer is closer to the anode than the p-type layer. According to the stacked organic electroluminescence device, the metal layer and the interface layer are arranged between the n-type layer and the p-type layer, so that mutual diffusion of the n-type layer and the p-type layer is effectively prevented; and the metal layer is in direct contact with the n-type layer at the same time, so that electrons are conveniently transmitted. Relative to the conventional stacked organic electroluminescence device utilizing the n-type layer and the p-type layer as the charge generation layers, the current efficiency is higher. The invention further provides a manufacturing method for the stacked organic electroluminescence device.
Description
[technical field]
The present invention relates to the electroluminescence field, relate in particular to a kind of lamination organic electroluminescence device and preparation method thereof.
[background technology]
1987, the C.W.Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in the organic electroluminescent research.Utilize the ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).In this double-deck device, brightness reaches 1000cd/m under the 10V
2, luminous efficiency is that 1.51lm/W, life-span were greater than 100 hours.
The principle of luminosity of OLED is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and the hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton move under electric field action, gives luminescent material with NE BY ENERGY TRANSFER, and excitation electron is from the ground state transition to excitation state, excited energy is through the radiation inactivation, generation photon, release luminous energy.At present, in order to improve luminosity and luminous efficiency, increasing research is to be main with laminated device; This structure normally is together in series several luminescence units as articulamentum with charge generation layer, compares with unit component, and the laminated construction device often has current efficiency and luminosity at double; The original intensity of lamination OLED is bigger; When under identical current density, measuring, be converted into the original intensity of unit component, stacked device has the long life-span; And this laminated device also can be easily becomes white light with the luminescence unit series hybrid of different colours, thereby realizes the emission of white light.
The charge generation layer of laminated device must have electronics power of regeneration and hole power of regeneration, and has reasonable injectability, could effectively electronics and hole be injected into each luminescence unit, thereby realizes the white light emission of device.Research at present many utilizes n type and p type layer to be linked in sequence a plurality of luminescence units as charge generation layer and constitutes; But the easy counterdiffusion mutually of ion in this charge generation layer n type and the p type layer adopts the current efficiency of lamination organic electroluminescence device of this charge generation layer lower.
[summary of the invention]
Based on this, be necessary to provide higher lamination organic electroluminescence device of a kind of current efficiency and preparation method thereof.
A kind of lamination organic electroluminescence device comprises: anode, negative electrode, the charge generation layers that are positioned at two organic electro luminescent layer of said anode and said negative electrode centre and are positioned at two said organic electro luminescent layer centres;
Said charge generation layer comprises the following structure that stacks gradually: n type layer, metal level, boundary layer and p type layer, said n type layer more is close to said anode than said p type layer.
Preferably, the material of said boundary layer is PbO, Sb
2O
5, ZnSe, GaN or SiC.
Preferably, the thickness of said boundary layer is 0.1nm～5nm.
Preferably, the material of said metal level is aluminium, silver or golden.
Preferably, said metal layer thickness is 0.5nm～2nm.
Preferably, the material of said n type layer is Li
2O, Cs
2CO
3, LiF or CsF.
Preferably, the thickness of said n type layer is 2nm～3nm.
Preferably, the material of said p type layer is MoO
3, V
2O
5Or WO
3
Preferably, the thickness of said p type layer is 3nm～10nm.
A kind of preparation method of lamination organic electroluminescence device comprises the steps:
Step 1, anode is provided, and said anode is carried out pre-treatment;
Step 2, the charge generation layers that vapor deposition forms two organic electro luminescent layer and is positioned at two said organic electro luminescent layer centres on a surface of said anode; Said charge generation layer comprises the following structure that stacks gradually: n type layer, metal level, boundary layer and p type layer, and said n type layer more is close to said anode than said p type layer;
Step 3, forming negative electrode away from the organic electro luminescent layer of said anode surface vapor deposition.
This lamination organic electroluminescence device has effectively prevented the mutually counterdiffusion of n type layer with p type layer intermediate ion through between n type layer and p type layer, adding metal level and boundary layer, and metal level directly contacts with n type layer simultaneously, helps the transmission of electronics.This lamination organic electroluminescence device is with respect to traditional lamination organic electroluminescence device that utilizes n type and p type layer as charge generation layer merely, and current efficiency is higher.
[description of drawings]
Fig. 1 is the structural representation of the lamination organic electroluminescence device of an execution mode;
Fig. 2 shows the preparation flow figure of lamination organic electroluminescence device for Fig. 1;
Current efficiency-current density the curve chart of the lamination organic electroluminescence device that Fig. 3 makes for embodiment 1 and Comparative Examples.
[embodiment]
Below in conjunction with accompanying drawing and specific embodiment lamination organic electroluminescence device and preparation method thereof is done further description.
The lamination organic electroluminescence device of an execution mode as shown in Figure 1 comprises: anode, negative electrode, the charge generation layers that are positioned at two organic electro luminescent layer of anode and negative electrode centre and are positioned at two said organic electro luminescent layer centres.
In the present embodiment, the number of organic electro luminescent layer is two, and the number of charge generation layer is one; In other embodiment, organic electro luminescent layer also can be three, four or more, and charge generation layer is two, three or more, is provided with a charge generation layer in the middle of per two adjacent organic electro luminescent layer.
The material of anode can be indium tin oxide glass, fluorine-containing tin oxide glass, the zinc oxide of mixing aluminium, magnesium-indium oxide, nickel-tungsten oxide, metal nitride, metal selenide or metal sulfide, and wherein the thickness of the conductive layer of anode is 100nm～150nm.
Zinc sulphide (ZnS) layer that negative electrode can be selected to stack gradually, silver (Ag) layer and aluminium (Al) layer, zinc sulfide layer than aluminium lamination more near anode.Negative electrode also can be zinc sulphide (ZnS) layer, silver (Ag) layer and zinc sulphide (ZnS) layer that stacks gradually.Wherein, the thickness of zinc sulfide layer is 30nm～50nm, and the thickness of silver layer is 10nm～20nm, and the thickness of aluminium lamination is 1nm～2nm.
Through this range upon range of cathode construction, can obtain the transparent negative electrode of better conductivity.
Each organic electro luminescent layer structure can be identical, also can be inequality.Organic electro luminescent layer can comprise the following structure that is arranged in order: hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer.Hole injection layer more is close to anode than electron injecting layer.
Special; Organic electro luminescent layer can only comprise luminescent layer, all the other each layer structures, as: hole injection layer, hole transmission layer, electronic barrier layer, hole blocking layer, electron transfer layer and electron injecting layer; Can add arbitrarily according to demand, also can not add.
In a preferred embodiment, the structure of organic electro luminescent layer is hole transmission layer, luminescent layer and the electron transfer layer that stacks gradually.
The material of hole injection layer can be molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2O
5), thickness is 10nm～15nm.
The material of hole transmission layer can be 1,1-two [4-[N, N '-two (p-tolyl) amino] phenyl] cyclohexane (TAPC), N, N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4,4 '-benzidine (TPD), 4,4 '; 4 " three (carbazole-9-yl) triphenylamine (TCTA), N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine (NPB), 1,3,5-triphenylbenzene (TDAPB) or CuPc (CuPc).
Luminescent layer can be single layer structure, also can be sandwich construction, and every layer of structural thickness is 10nm～20nm.
The material of luminescent layer can be four-tert-butyl group perylene (TBP), 4-(dintrile methyl)-2-butyl-6-(1; 1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9; 10-two-β-naphthylene anthracene (AND), two (2-methyl-oxine)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-isopropyl-6-(1; 1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq
3), two (4,6-difluorophenyl pyridine-N, C
2) the pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-four (1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) and closes iridium (Ir (MDQ)
2(acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq)
2(acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) and three (2-phenylpyridines) close iridium (Ir (ppy)
3) at least a.
The material of electron transfer layer can be 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-two (1-naphthyl)-1,3,4-diazole (BND), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (like TAZ), N-aryl benzimidazole (TPBI) or quinoxaline derivant (TPQ), thickness is 20nm～80nm.
The material of electron injecting layer can be Cs
2CO
3, CsN
3, LiF, CsF, CaF
2, MgF
2Or NaF, thickness is 1nm～2nm.
Charge generation layer comprises the following structure that stacks gradually: n type layer, metal level, boundary layer and p type layer, n type layer more is close to anode than p type layer.
The material of n type layer is Li
2O, Cs
2CO
3, LiF or CsF, thickness is 2nm～3nm.
The material of metal level is aluminium (Al), silver (Ag) or gold (Au), and thickness is 0.5nm～2nm.
The material of boundary layer is PbO, Sb
2O
5, ZnSe, GaN or SiC, thickness is 0.1nm～5nm.
The material of p type layer is MoO
3, V
2O
5Or WO
3, thickness is 3nm～10nm.
In this execution mode; Because the existence of n type layer and p type layer; Can omit electron injecting layer and hole injection layer in the charge generation layer adjacent interfaces, promptly the lamination organic electroluminescence device can be the following structure that stacks gradually: anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, n type layer, metal level, boundary layer, p type layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
This lamination organic electroluminescence device has effectively prevented the mutually counterdiffusion of n type layer with p type layer intermediate ion through between n type layer and p type layer, adding metal level and boundary layer, and metal level directly contacts with n type layer simultaneously, helps the transmission of electronics.This lamination organic electroluminescence device is with respect to traditional lamination organic electroluminescence device that utilizes n type and p type layer as charge generation layer merely, and current efficiency is higher.
The preparation method of above-mentioned lamination organic electroluminescence device as shown in Figure 2 comprises the steps:
S10, anode is provided, and antianode carries out pre-treatment.
General, anode can be selected indium tin oxide glass, fluorine-containing tin oxide glass, the zinc oxide of mixing aluminium, magnesium-indium oxide, nickel-tungsten oxide, metal nitride, metal selenide or metal sulfide.
The operation of pre-treatment comprises: antianode is used liquid detergent, ethanol, acetone and pure water ultrasonic cleaning successively; Each washing is adopted and is cleaned 5min; Stop 5min, and the method for triplicate, dry after washing is accomplished; Anode to drying carries out the oxygen content of surface activation process with increase anode surface conductive layer at last, thereby improves the work function of conductive layer surface.
S20, the charge generation layer that vapor deposition forms two organic electro luminescent layer and is positioned at two organic electro luminescent layer centres on a surface of anode.
Charge generation layer comprises the following structure that stacks gradually: n type layer, metal level, boundary layer and p type layer, n type layer more is close to anode than p type layer.
The material of n type layer is Li
2O, Cs
2CO
3, LiF or CsF, thickness is 2nm～3nm.
The material of metal level is aluminium (Al), silver (Ag) or gold (Au), and thickness is 0.5nm～2nm.
The material of boundary layer is PbO, Sb
2O
5, ZnSe, GaN or SiC, thickness is 0.1nm～5nm.
The material of p type layer is MoO
3, V
2O
5Or WO
3, thickness is 3nm～10nm.
In this execution mode; Because the existence of n type layer and p type layer; Can omit electron injecting layer and hole injection layer in the charge generation layer adjacent interfaces, promptly the lamination organic electroluminescence device can be the following structure that stacks gradually: anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, n type layer, metal level, boundary layer, p type layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
With the said structure is example, the concrete evaporate process of brief account.
Vapor deposition forms hole injection layer on the surface of anode, and thickness is 10nm～15nm, and vacuum degree is 7 * 10
-5Pa～5 * 10
-5Pa, evaporation rate does
Vapor deposition forms hole transmission layer on hole injection layer, thickness 40nm～60nm, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate does
Vapor deposition on hole transmission layer forms luminescent layer, and luminescent layer can be individual layer and sandwich construction, and every layer of structural thickness is 10nm～20nm, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate does
Vapor deposition forms electron transfer layer on luminescent layer, and thickness is 20nm～80nm, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate does
Vapor deposition forms n type layer on electron transfer layer, and thickness is 2nm～3nm, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate does
Vapor deposition forms metal level on n type layer, and thickness is 0.5nm～2n, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate does
Vapor deposition forms boundary layer on metal level, thickness 0.1nm～5nm, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate
Vapor deposition forms p type layer on boundary layer, thickness 3nm～10nm, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate
Vapor deposition forms hole transmission layer on p type layer, evaporation thickness 40nm～60nm, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate does
Vapor deposition on hole transmission layer forms luminescent layer, and luminescent layer can be individual layer and sandwich construction, and every layer of structural thickness is 10nm～20nm, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate does
Vapor deposition forms electron transfer layer on luminescent layer, and thickness is 20nm～80nm, and vacuum degree is 5 * 10
-5Pa～3 * 10
-5Pa, evaporation rate does
Vapor deposition forms electron injecting layer on electron transfer layer, and thickness is 1nm～2nm, and vacuum degree is 7 * 10
-5Pa～5 * 10
-5Pa, evaporation rate does
S30, forming negative electrode away from the organic electro luminescent layer of said anode surface vapor deposition, obtain the lamination organic electroluminescence device.
Vapor deposition zinc sulfide layer, silver layer and aluminium lamination form negative electrode successively, and the thickness of zinc sulfide layer is 30nm～50nm, and the thickness of silver layer is 10nm～20nm, and the thickness of aluminium lamination is 1nm～2nm, vacuum degree 7 * 10
-5Pa～5 * 10
-5Pa, evaporation rate
Thereby obtain said lamination organic electroluminescence device.
In other execution mode, it is all consistent with aforesaid operations also can to select successively vapor deposition zinc sulfide layer, silver layer and zinc sulfide layer to form parameters such as negative electrode vapor deposition condition and time thickness.
2402) and chroma-luminance meter (Minolta, model: CS-100A) below be the specific embodiment part, used instrument is: high accuracy number source table (U.S. Keithley company, model:.
Embodiment 1
Select indium tin oxide glass as anode, the conductive layer thickness that wherein is made up of indium tin oxide is 100nm.Select liquid detergent, ethanol, acetone and pure water antianode to carry out ultrasonic cleaning successively with supersonic wave cleaning machine, each washing is adopted and was cleaned 5 minutes, stops 5 minutes, repeats 3 times method respectively, and washing is dried with IR bake after accomplishing.Anode to cleaning after drying carries out surface activation process, to increase the oxygen content of conductive layer, improves the work function of anode surface.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole injection layer on anode, material is MoO
3, thickness is 10nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on hole injection layer, material is NPB, thickness is 50nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is closed iridium (Ir (ppy) for three (the 2-phenylpyridines) that mixed
3) 2,2 ', 2 " (1,3, the 5-triphenyl) three-[1-phenyl-1-benzimidazole] (TPBi), the mass ratio of doping is 4%, thickness is 15nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, forming the electron transfer layer material in the luminescent layer surface evaporation is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, evaporating n type layer successively on electron transfer layer: material is Li
2O, thickness are 2nm, metal level: material is Al, and thickness is 1nm, boundary layer: material is PbO, and thickness is 3nm and p type layer: material is MoO
3, thickness is 5nm, obtains comprising the charge generation layer of said structure.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on p type layer, material is 50nm for NPB thickness.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is the Ir (ppy) that TPBi mixes
3, the mass ratio of doping is 4%, thickness is 15nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer, material is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Under the condition of m, vapor deposition forms electron injecting layer on electron transfer layer, and material is LiF, and thickness is 1nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms zinc sulfide layer on electron injecting layer, thickness is 40nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms silver layer on zinc sulfide layer, thickness is 10nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms aluminium lamination on silver layer, thickness is 2nm.Obtaining structure is the transparent negative electrode of ZnS/Ag/Al (the ZnS side is an exiting surface).
Embodiment 2
Select indium tin oxide glass as anode, the conductive layer thickness that wherein is made up of indium tin oxide is 150nm.Select liquid detergent, ethanol, acetone and pure water antianode to carry out ultrasonic cleaning successively with supersonic wave cleaning machine, each washing is adopted and was cleaned 5 minutes, stops 5 minutes, repeats 3 times method respectively, and washing is dried with IR bake after accomplishing.Anode to cleaning after drying carries out surface activation process, to increase the oxygen content of conductive layer, improves the work function of anode surface.
Vacuum degree is 4 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on anode, material is TPD, thickness is 40nm.
Vacuum degree is 4 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is closed iridium (Ir (ppy) for three (the 2-phenylpyridines) that mixed
3) 2,2 ', 2 " (1,3, the 5-triphenyl) three-[1-phenyl-1-benzimidazole] (TPBi), the mass ratio of doping is 4%, thickness is 15nm.Vacuum degree is 4 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer, material is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 4 * 10
-5Pa, evaporation rate does
Condition under, evaporating n type layer successively on electron transfer layer: material is Cs
2CO
3, thickness is 2.5nm, metal level: material is Au, thickness is 0.5nm, boundary layer: material is Sb
2O
5, thickness is 0.1nm and p type layer: material is WO
3, thickness is 3nm, obtains comprising the charge generation layer of said structure.
Vacuum degree is 4 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on p type layer, material is 50nm for NPB thickness.
Vacuum degree is 4 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is the Ir (ppy) that TPBi mixes
3, the mass ratio of doping is 4%, thickness is 15nm.
Vacuum degree is 4 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer, material is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 4 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms zinc sulfide layer on electron transfer layer, thickness is 30nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms silver layer on zinc sulfide layer, thickness is 20nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms zinc sulfide layer on silver layer, thickness is 50nm.Obtaining structure is the transparent negative electrode of ZnS/Ag/ZnS.
Embodiment 3
Select indium tin oxide glass as anode, the conductive layer thickness that wherein is made up of indium tin oxide is 100nm.Select liquid detergent, ethanol, acetone and pure water antianode to carry out ultrasonic cleaning successively with supersonic wave cleaning machine, each washing is adopted and was cleaned 5 minutes, stops 5 minutes, repeats 3 times method respectively, and washing is dried with IR bake after accomplishing.Anode to cleaning after drying carries out surface activation process, to increase the oxygen content of conductive layer, improves the work function of anode surface.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole injection layer on anode, material is MoO
3, thickness is 15nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on hole injection layer, material is NPB, thickness is 40nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is closed iridium (Ir (ppy) for three (the 2-phenylpyridines) that mixed
3) 2,2 ', 2 " (1,3, the 5-triphenyl) three-[1-phenyl-1-benzimidazole] (TPBi), the mass ratio of doping is 4%, thickness is 10nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, evaporation forms electron transfer layer on luminescent layer, material is that oxine aluminium (Alq3) is done electron transport material, thickness is 80nm.
Vacuum degree is 4 * 10
-5Pa, evaporation rate does
Condition under, evaporating n type layer successively on electron transfer layer: material is LiF, and thickness is 3nm, metal level: material is Al, and thickness is 2nm, boundary layer: material is ZnSe, and thickness is 4nm and p type layer: material is WO
3, thickness is 10nm, obtains comprising the charge generation layer of said structure.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on p type layer, material is 50nm for NPB thickness.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is the Ir (ppy) that TPBi mixes
3, the mass ratio of doping is 4%, thickness is 15nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer, material is oxine aluminium (Alq3), thickness is 20nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Under the condition of m, vapor deposition forms electron injecting layer on electron transfer layer, and material is LiF, and thickness is 2nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms zinc sulfide layer on electron injecting layer, thickness is 40nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms silver layer on zinc sulfide layer, thickness is 15nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms zinc sulfide layer on silver layer, thickness is 45nm.Obtaining structure is the transparent negative electrode of ZnS/Ag/ZnS.
Embodiment 4
Select indium tin oxide glass as anode, the conductive layer thickness that wherein is made up of indium tin oxide is 100nm.Select liquid detergent, ethanol, acetone and pure water antianode to carry out ultrasonic cleaning successively with supersonic wave cleaning machine, each washing is adopted and was cleaned 5 minutes, stops 5 minutes, repeats 3 times method respectively, and washing is dried with IR bake after accomplishing.Anode to cleaning after drying carries out surface activation process, to increase the oxygen content of conductive layer, improves the work function of anode surface.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole injection layer on anode, material is MoO
3, thickness is 10nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on hole injection layer, material is NPB, thickness is 50nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is closed iridium (Ir (ppy) for three (the 2-phenylpyridines) that mixed
3) 2,2 ', 2 " (1,3, the 5-triphenyl) three-[1-phenyl-1-benzimidazole] (TPBi), the mass ratio of doping is 4%, thickness is 15nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer, material is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, evaporating n type layer successively on electron transfer layer: material is Cs
2CO
3, thickness is 3nm, metal level: material is Ag, and thickness is 2nm, boundary layer: material is GaN, and thickness is 5nm and p type layer: material is WO
3, thickness is 8nm, obtains comprising the charge generation layer of said structure.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on p type layer, material is 50nm for NPB thickness.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is the Ir (ppy) that TPBi mixes
3, the mass ratio of doping is 4%, thickness is 15nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer, material is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Under the condition of m, vapor deposition forms electron injecting layer on electron injecting layer, and material is LiF, and thickness is 1nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms zinc sulfide layer on electron injecting layer, thickness is 50nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms silver layer on zinc sulfide layer, thickness is 18nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms zinc sulfide layer on silver layer, thickness is 30nm.Obtaining structure is the transparent negative electrode of ZnS/Ag/ZnS.
Select indium tin oxide glass as anode, the conductive layer thickness that wherein is made up of indium tin oxide is 100nm.Select liquid detergent, ethanol, acetone and pure water antianode to carry out ultrasonic cleaning successively with supersonic wave cleaning machine, each washing is adopted and was cleaned 5 minutes, stops 5 minutes, repeats 3 times method respectively, and washing is dried with IR bake after accomplishing.Anode to cleaning after drying carries out surface activation process, to increase the oxygen content of conductive layer, improves the work function of anode surface.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole injection layer on anode, material is MoO
3, thickness is 10nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on hole injection layer, material is NPB, thickness is 50nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is closed iridium (Ir (ppy) for three (the 2-phenylpyridines) that mixed
3) 2,2 ', 2 " (1,3, the 5-triphenyl) three-[1-phenyl-1-benzimidazole] (TPBi), the mass ratio of doping is 4%, thickness is 15nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer surface, material is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, evaporating n type layer successively on electron transfer layer: material is CsF, and thickness is 2.2nm, metal level: material is Ag, and thickness is 1.2nm, boundary layer: material is SiC, and thickness is 4nm and p type layer: material is V
2O
5, thickness is 4nm, obtains comprising the charge generation layer of said structure.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on p type layer, material is 50nm for NPB thickness.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is the Ir (ppy) that TPBi mixes
3, the mass ratio of doping is 4%, thickness is 15nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer, material is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron injecting layer on electron transfer layer, material is LiF, thickness is 1nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms zinc sulfide layer on electron injecting layer, thickness is 40nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms silver layer on zinc sulfide layer, thickness is 10nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms aluminium lamination on silver layer, thickness is 1nm.Obtaining structure is the transparent negative electrode of ZnS/Ag/Al (the ZnS side is an exiting surface).
Comparative Examples
Select indium tin oxide glass as anode, the conductive layer thickness that wherein is made up of indium tin oxide is 100nm.Select liquid detergent, ethanol, acetone and pure water antianode to carry out ultrasonic cleaning successively with supersonic wave cleaning machine, each washing is adopted and was cleaned 5 minutes, stops 5 minutes, repeats 3 times method respectively, and washing is dried with IR bake after accomplishing.Anode to cleaning after drying carries out surface activation process, to increase the oxygen content of conductive layer, improves the work function of anode surface.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole injection layer on anode, material is MoO
3, thickness is 10nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on hole injection layer, material is NPB, thickness is 50nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is closed iridium (Ir (ppy) for three (the 2-phenylpyridines) that mixed
3) 2,2 ', 2 " (1,3, the 5-triphenyl) three-[1-phenyl-1-benzimidazole] (TPBi), the mass ratio of doping is 4%, thickness is 15nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer, material is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, evaporating n type layer successively on electron transfer layer: material is Li
2O, thickness are 2nm and p type layer: material is MoO
3, thickness is 5nm, obtains comprising the charge generation layer of said structure.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms hole transmission layer on p type layer, material is 50nm for NPB thickness.
Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms luminescent layer on hole transmission layer, material is the Ir (ppy) that TPBi mixes
3, the mass ratio of doping is 4%, thickness is 15nm.Vacuum degree is 3 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron transfer layer on luminescent layer, material is oxine aluminium (Alq3), thickness is 40nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms electron injecting layer on electron transfer layer, material is LiF, thickness is 1nm.
Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms zinc sulfide layer on electron injecting layer, thickness is 40nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms silver layer on zinc sulfide layer, thickness is 10nm.Vacuum degree is 5 * 10
-5Pa, evaporation rate does
Condition under, vapor deposition forms aluminium lamination on silver layer, thickness is 2nm.Obtaining structure is the transparent negative electrode of ZnS/Ag/Al (the ZnS side is an exiting surface).
Current density-energy efficiency the figure of the end emission of the lamination organic electroluminescence device that embodiment 1 as shown in Figure 3 and Comparative Examples make.
The anode exiting surface of curve 1 corresponding embodiment 1, the anode exiting surface of curve 2 corresponding Comparative Examples.The negative electrode exiting surface of curve 3 corresponding embodiment 1, the negative electrode exiting surface of curve 4 corresponding Comparative Examples.
By reading data as shown in the table among the figure:
Meter reading can draw, under identical current density, and the energy efficiency of the anode exiting surface that the energy efficiency of the anode exiting surface of the lamination organic electroluminescence device that embodiment 1 makes makes apparently higher than Comparative Examples.The energy efficiency of the negative electrode exiting surface that the energy efficiency of the negative electrode exiting surface of the lamination organic electroluminescence device that embodiment 1 makes makes apparently higher than Comparative Examples.
Above embodiment has only expressed several kinds of execution modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with accompanying claims.
Claims (10)
1. a lamination organic electroluminescence device is characterized in that, comprising: anode, negative electrode, the charge generation layers that are positioned at two organic electro luminescent layer of said anode and said negative electrode centre and are positioned at two said organic electro luminescent layer centres;
Said charge generation layer comprises the following structure that stacks gradually: n type layer, metal level, boundary layer and p type layer, said n type layer more is close to said anode than said p type layer.
2. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the material of said boundary layer is PbO, Sb
2O
5, ZnSe, GaN or SiC.
3. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the thickness of said boundary layer is 0.1nm～5nm.
4. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the material of said metal level is aluminium, silver or golden.
5. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, said metal layer thickness is 0.5nm～2nm.
6. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the material of said n type layer is Li
2O, Cs
2CO
3, LiF or CsF.
7. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the thickness of said n type layer is 2nm～3nm.
8. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the material of said p type layer is MoO
3, V
2O
5Or WO
3
9. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the thickness of said p type layer is 3nm～10nm.
10. the preparation method of a lamination organic electroluminescence device is characterized in that, comprises the steps:
Step 1, anode is provided, and said anode is carried out pre-treatment;
Step 2, the charge generation layers that vapor deposition forms two organic electro luminescent layer and is positioned at two said organic electro luminescent layer centres on a surface of said anode; Said charge generation layer comprises the following structure that stacks gradually: n type layer, metal level, boundary layer and p type layer, and said n type layer more is close to said anode than said p type layer;
Step 3, forming negative electrode away from the organic electro luminescent layer of said anode surface vapor deposition.
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| CN104253233A (en) * | 2013-06-26 | 2014-12-31 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN104253228A (en) * | 2013-06-26 | 2014-12-31 | 海洋王照明科技股份有限公司 | Organic light emitting diode and preparation method thereof |
| CN107611271A (en) * | 2017-08-10 | 2018-01-19 | 上海天马有机发光显示技术有限公司 | Organic light emitting diode, display panel and display device |
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Application publication date: 20121226 |