CN104882545A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN104882545A
CN104882545A CN201410071842.6A CN201410071842A CN104882545A CN 104882545 A CN104882545 A CN 104882545A CN 201410071842 A CN201410071842 A CN 201410071842A CN 104882545 A CN104882545 A CN 104882545A
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layer
bis
phenyl
hole injection
electron
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周明杰
钟铁涛
王平
冯小明
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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
    • 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

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  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to an organic electroluminescent device and a preparation method thereof, wherein the organic electroluminescent device has a layered structure and comprises an anode conductive substrate, a first hole injection layer, a first electron injection layer, a second hole injection layer, a hole transport layer, a green light emitting layer, an electron transmission layer, a second electron injection layer and a cathode layer; wherein the anode conductive substrate, the first hole injection layer, the first electron injection layer, the second hole injection layer, the hole transport layer, the green light emitting layer, the electron transmission layer, the second electron injection layer and the cathode layer are successively laminated. The first hole injection layer and the second hole injection layer are made of hole injection material and p-type material which is doped into the hole injection material. The first electron injection layer and the second electron injection layer are made of electron injection material and n-type material which is doped into the electron injection material. According to the organic electroluminescent device, through the added second hole injection layer and the second electron injection layer, working voltage can be reduced and luminous efficiency can be improved effectively.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to field of optoelectronic devices, particularly relate to organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) has the advantage of some uniquenesses: (1) OLED belongs to diffused area source, does not need to obtain large-area white light source by extra light-conducting system as light-emitting diode (LED); (2) due to the diversity of luminous organic material, OLED illumination can the light of design color as required, no matter be Small molecular OLED at present, or polymer organic LED (PLED) has obtained the light of all colours comprising white-light spectrum all; (3) OLED can at multiple substrate as glass, pottery, metal, plastic or other material make, freer when this makes design lighting source; (4) adopt the mode making OLED display to make OLED illumination panel, information can be shown while illumination; (5) OLED also can be used as controlled look in the illumination system, allows user to regulate light atmosphere according to individual demand.Above advantage makes organic electroluminescence become the ideal chose of flat-panel screens fast.
Existing typical organic electroluminescence device comprises substrate and is sequentially formed at anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and the negative electrode on substrate.The principle of luminosity of organic electroluminescence device is: inject electronics by negative electrode, anode injected hole, and the potential difference utilizing extra electric field to produce and impel these electronics and hole to move in organic luminous layer, then combine to reach luminous object.When electronics and hole respectively from negative electrode and positive electrode to move to organic luminous layer again in conjunction with time, electronics and hole must overcome the energy barrier existing for interface between each layer.For anode-side, hole must overcome between anode and hole injection layer, between hole injection layer and hole transmission layer and the energy barrier that between hole transmission layer and organic luminous layer, interface place exists; When larger energy barrier is present in the interface place of above-mentioned each layer, hole should not enter organic luminous layer, and can produce accumulation at the interface place of each layer, so, has risen causing the operating voltage of organic electroluminescence device and service life reduction.
In order to avoid the rising of the operating voltage of organic electroluminescence device, traditional way reduces the organic film thickness between anode and organic luminous layer, but when organic thickness is thinner, the luminous efficiency of organic electroluminescence device can be caused to reduce, cause stability to decline, and easily form the multiple shortcomings such as short circuit.How effectively to reduce the operating voltage of organic electroluminescence device, improving the luminous efficiency of organic electroluminescence device, is that industrial circle needs the problem overcome badly.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, a kind of organic electroluminescence device that effectively can reduce operating voltage and improve luminous efficiency is provided.
For realizing above-mentioned purpose of the present invention, the technical solution adopted in the present invention is:
Organic electroluminescence device of the present invention is layer structure, described organic electroluminescence device comprises: stack gradually anode conducting substrate, first hole injection layer, first electron injecting layer, second hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, second electron injecting layer and cathode layer, described first hole injection layer and the second hole injection layer form by hole-injecting material and the p-type material that is doped in described hole-injecting material, described first electron injecting layer and described second electron injecting layer form by electron injection material and the N-shaped material that is doped in described electron injection material.
Further, in organic electroluminescence device of the present invention:
The material of described anode conducting substrate is tin indium oxide transparent conductive glass, and thickness is 100 ~ 150nm;
Described hole-injecting material in described first hole injection layer and described second hole injection layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane; Described p-type material is MoO 3, WO 3, V 2o 5or ReO 3; The percentage by weight that described p-type material accounts for described hole-injecting material is 25 ~ 35wt%; The thickness of described first hole injection layer and described second hole injection layer is 10 ~ 15nm;
Described electron injection material in described first electron injecting layer and described second electron injecting layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene; Described N-shaped material is Cs 2cO 3, CsF, CsN 3, Li 2cO 3, LiF or Li 2o; The percentage by weight that described N-shaped material accounts for described electron injection material is 25 ~ 35wt%; The thickness of described first electron injecting layer and described second electron injecting layer is 20 ~ 40nm;
The material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane, the thickness of described hole transmission layer is 30 ~ 50nm;
The material of described green light emitting layer is made up of material of main part and the green glow guest materials being doped in material of main part, described material of main part is 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazoles, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane or two (1-naphthyl) anthracene of 9,10-; Green glow guest materials is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridines] and close iridium; The percentage by weight that described green glow guest materials accounts for described material of main part is 2 ~ 10wt%; Described green light emitting layer thickness be 10 ~ 30nm;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene; The thickness of described electron transfer layer is 10 ~ 60nm;
The material of described cathode layer is silver, aluminium or gold, and thickness is 50 ~ 200nm.
The present invention also proposes a kind of preparation method of organic electroluminescence device, and it comprises the following steps: adopt vacuum deposition method on anode conducting substrate, form the first hole injection layer, the first electron injecting layer, the second hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the second electron injecting layer and cathode layer successively;
Wherein:
Vacuum is steamed when crossing described first hole injection layer and described second hole injection layer, all by material doped for p-type enter in hole-injecting material, thus form described first hole injection layer and described second hole injection layer; Described hole-injecting material is N, N'-diphenyl-N, N'-bis-(1-naphthyls)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane, described p-type material is MoO 3, WO 3, V 2o 5or ReO 3, the percentage by weight that described p-type material accounts for described hole-injecting material is 25 ~ 35wt%; Described in vacuum evaporation when the first hole injection layer and described second hole injection layer, set vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is described first hole injection layer and described second hole injection layer thickness of gained after vacuum evaporation are 10 ~ 15nm;
Vacuum is steamed when crossing described first electron injecting layer and described second electron injecting layer, all by material doped for N-shaped enter in electron injection material, thus form described first electron injecting layer and described second electron injecting layer; Described electron injection material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene; Described N-shaped material is Cs 2cO 3, CsF, CsN 3, Li 2cO 3, LiF or Li 2o; Stating the percentage by weight that N-shaped material accounts for described electron injection material is 25 ~ 35wt%; Described in vacuum evaporation when the first electron injecting layer and described second electron injecting layer, set vacuum degree is 8 × 10 -5pa ~ 3 × 10 -4pa, evaporation rate is described first electron injecting layer and described second electron injecting layer thickness of gained after vacuum evaporation are 20 ~ 40nm;
When vacuum is steamed and crossed described hole transmission layer, adopt N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane give are hole mobile material; Vacuum degree set during vacuum evaporation is 1 × 10 -5pa ~ 3 × 10 -3pa, evaporation rate is the thickness of described hole transmission layer gained after vacuum evaporation is 30 ~ 50nm;
When vacuum is steamed and crossed described green light emitting layer, adopt 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane or two (1-naphthyl) anthracene of 9,10-be as material of main part; Adopt three (2-phenylpyridines) to close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridines] and close iridium as green glow guest materials; Be doped in material of main part by green glow guest materials, thus form described green light emitting layer, wherein, the percentage by weight that green glow guest materials accounts for described material of main part is 2 ~ 10wt%; Vacuum degree set during vacuum evaporation is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is the thickness of described green light emitting layer gained after vacuum evaporation is 10 ~ 30nm;
When vacuum is steamed and is crossed described electron transfer layer, adopt 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phens, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene are as electron transport material; Vacuum degree set during vacuum evaporation is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate the thickness of described electron transfer layer gained after vacuum evaporation is 10 ~ 60nm;
Described in vacuum evaporation during cathode layer, adopt silver, aluminium or gold as raw material, vacuum degree set during vacuum evaporation is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is the thickness of described cathode layer gained after vacuum evaporation is 50 ~ 200nm.
Compared with prior art, a kind of organic electroluminescence device of the present invention and preparation method thereof, has following advantage:
First, organic electroluminescence device of the present invention is provided with the first electrical pumping layer and the second hole injection layer between the first hole injection layer and hole transmission layer, and its order is successively: the first hole injection layer, the first electron injecting layer, the second hole injection layer, hole transmission layer.First electron injecting layer is located between the first hole injection layer and the second hole injection layer, thus a uneven internal field can be formed respectively at the first hole injection layer and the intersection of the first electron injecting layer and the intersection of the second hole injection layer and the first electron injecting layer, this is conducive to the transmittability adjusting hole, thus make cavity energy overcome the energy barrier existing for interface between each layer, connect and reduce the operating voltage of organic electroluminescence device, increase the logarithm of both hole and electron, strengthen the recombination probability of both hole and electron, improve the luminous efficiency of organic electroluminescence device,
Second, first hole injection layer of the present invention and the second hole injection layer are all doped with p-type material, thus improve the HOMO(highest occupied molecular orbital of the first hole injection layer and the second hole injection layer) energy level, reduce the energy barrier between the first hole injection layer and anode and the energy barrier between the second hole injection layer and hole transmission layer, thus make hole more easily arrive green light emitting layer, improve hole injection efficiency, reduce operating voltage, and then improve luminous efficiency and the life-span of organic electroluminescence device;
3rd, second electron injecting layer of the present invention is doped with N-shaped material, thus the minimum occupied molecular orbital of the LUMO(reducing the second electron injecting layer) energy level, reduce the energy barrier between the second electron injecting layer and negative electrode, thus make electronics more easily arrive green light emitting layer, improve electron injection efficiency, reduce operating voltage, and then improve luminous efficiency and the life-span of organic electroluminescence device.
In sum, organic electroluminescence device of the present invention is by arranging the first electrical pumping layer and the second hole injection layer between the first hole injection layer and hole transmission layer, thus improve efficiency of transmission and the injection efficiency in hole, reduce the operating voltage of organic electroluminescence device, and then improve luminous efficiency and the life-span of organic electroluminescence device.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 1 ~ 6.
Embodiment
Below in conjunction with embodiment, elaboration is further given to organic electroluminescence device of the present invention and preparation method thereof.
The invention provides a kind of organic electroluminescence device, described organic electroluminescence device is layer structure, and described organic electroluminescence device comprises successively: the anode conducting substrate stacked gradually, the first hole injection layer, the first electron injecting layer, the second hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, the second electron injecting layer, cathode layer.
The present invention also provides the preparation method of above-mentioned organic electroluminescence device, the steps include:
A) anode conducting substrate pre-treatment
With ito glass (being also tin indium oxide transparent conductive glass) as anode conducting substrate, successively use liquid detergent, deionized water, acetone and ethanol purge respectively, all clean with supersonic wave cleaning machine, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on the surface of ito glass, improve the work function on the surface of ito glass; The thickness of ito glass is 100 ~ 150nm;
B) preparation of the first hole injection layer
Adopt N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane (TAPC), as hole-injecting material, adopts MoO 3, WO 3, V 2o 5or ReO 3as p-type material, being that the p-type material of 25 ~ 35:100 adulterates mutually with hole-injecting material by weight ratio, is 1 × 10 in vacuum degree -5pa ~ 1 × 10 -3pa and evaporation rate are setting under, on anode conducting substrate, vacuum evaporation forms the first hole injection layer, and the thickness of the first hole injection layer is 10 ~ 15nm;
C) preparation of the first electron injecting layer
4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phens (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) is adopted to close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI) as electron injection material, adopt Cs 2cO 3, CsF, CsN 3, Li 2cO 3, LiF or Li 2o is as N-shaped material, and being that the N-shaped material of 25 ~ 35:100 adulterates mutually with electron injection material by weight ratio, is 8 × 10 in vacuum degree -5pa ~ 3 × 10 -4pa and evaporation rate are setting under, on the first hole injection layer, vacuum evaporation forms the first electron injecting layer, and the thickness of the first electron injecting layer is 20 ~ 40nm;
D) preparation of the second hole injection layer
Adopt N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane (TAPC), as hole-injecting material, adopts MoO 3, WO 3, V 2o 5or ReO 3as p-type material, being that the p-type material of 25 ~ 35:100 adulterates mutually with hole-injecting material by weight ratio, is 1 × 10 in the vacuum degree of vacuum evaporation -5pa ~ 1 × 10 -3pa and evaporation rate are setting under, on the first electron injecting layer, vacuum evaporation forms the second hole injection layer, and the thickness of the second hole injection layer is 10 ~ 15nm;
E) preparation of hole transmission layer
Adopt N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane (TAPC), as hole mobile material, is 1 × 10 in vacuum degree -5pa ~ 1 × 10 -3pa and evaporation rate are setting under, on the second hole injection layer vacuum evaporation formed hole transmission layer, the thickness 30 ~ 50nm of hole transmission layer;
F) preparation of green light emitting layer
Adopt 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazoles (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane (TAPC) or 9,10-two (1-naphthyl) anthracene (ADN) are as material of main part; Three (2-phenylpyridines) are adopted to close iridium (Ir (ppy) 3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2(acac)) or three [2-(p-methylphenyl) pyridines] close iridium (Ir (mppy) 3) as green glow guest materials, the green glow guest materials of weight ratio 2 ~ 10:100 is adulterated mutually with material of main part, be 1 × 10 in vacuum degree -5pa ~ 1 × 10 -3pa and evaporation rate are setting under, on hole transmission layer vacuum evaporation formed green light emitting layer, the thickness of green light emitting layer is 10 ~ 30nm;
G) preparation of electron transfer layer
4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phens (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) is adopted to close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), as electron transport material, is 1 × 10 in vacuum degree -5pa ~ 1 × 10 -3pa and evaporation rate are setting under, on green light emitting layer vacuum evaporation formed electron transfer layer, electric transmission layer thickness is 10 ~ 60nm;
H) preparation of the second electron injecting layer
4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phens (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) is adopted to close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI) as electron injection material, adopt Cs 2cO 3, CsF, CsN 3, Li 2cO 3, LiF or Li 2the N-shaped material of 25 ~ 35:100, as N-shaped material, adulterates with electron injection material by O mutually, is 8 × 10 in vacuum degree -5pa ~ 3 × 10 -4pa and evaporation rate are setting under, vacuum evaporation forms the second electron injecting layer on the electron transport layer, and the thickness of the second electron injecting layer is 20 ~ 40nm;
I) preparation of cathode layer
Adopting silver (Ag), aluminium (Al) or gold (Au) as the material of cathode layer, is 1 × 10 in vacuum degree -5pa ~ 1 × 10 -3pa and evaporation rate are setting under, on the second electron injecting layer vacuum evaporation formed cathode layer, the thickness of cathode layer is 50 ~ 200nm.
With embodiment 1 ~ 6, organic electroluminescence device of the present invention and preparation method thereof is illustrated below, because the structure of the organic electroluminescence device of embodiment 1 ~ 6 is basically identical, therefore is all shown as with Fig. 1 and illustrates:
embodiment 1
As shown in Figure 1, the present embodiment 1 provides a kind of organic electroluminescence device, described organic electroluminescence device is layer structure, and described organic electroluminescence device comprises successively: anode conducting substrate 101, first hole injection layer 102, first electron injecting layer 103, second hole injection layer 104, hole transmission layer 105, green light emitting layer 106, electron transfer layer 107, second electron injecting layer 108 and cathode layer 109.
The expression formula of described organic electroluminescence device is: ito glass/MoO 3: NPB (30:100)/Cs 2cO 3: Bphen (30:100)/MoO 3: NPB (30:100)/NPB/Ir (ppy) 3: TCTA (10:100)/Bphen/Cs 2cO 3: Bphen (30:100)/Ag, wherein, colon ": " represents that the former is entrained in the latter.
The present embodiment 1 also provides the preparation method of above-mentioned organic electroluminescence device, the steps include:
A) anode conducting substrate 101 pre-treatment
With ito glass (being also tin indium oxide transparent conductive glass) as anode conducting substrate 101, successively use liquid detergent, deionized water, acetone and ethanol purge respectively, all clean with supersonic wave cleaning machine, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on the surface of ito glass, improve the work function on the surface of ito glass; The thickness of ito glass is 150nm;
B) preparation of the first hole injection layer 102
Be the MoO of 30:100 by percentage by weight 3adulterating with NPB phase, is 1 × 10 in vacuum degree -5pa and evaporation rate are setting under, on anode conducting substrate 101, vacuum evaporation forms the thickness of the first hole injection layer 102, first hole injection layer 102 is 12.5nm;
C) preparation of the first electron injecting layer 103
Be the Cs of 30:100 by percentage by weight 2cO 3adulterating with Bphen phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first hole injection layer 102, vacuum evaporation forms the thickness of the first electron injecting layer 103, first electron injecting layer 103 is 30nm;
D) preparation of the second hole injection layer 104
Be the MoO of 30:100 by percentage by weight 3adulterating with NPB phase, is 1 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first electron injecting layer 103, vacuum evaporation forms the thickness of the second hole injection layer 104, second hole injection layer 104 is 12.5nm;
E) preparation of hole transmission layer 105
Adopting NPB as hole mobile material, is 1 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second hole injection layer 104 vacuum evaporation formed hole transmission layer 105, the thickness of hole transmission layer 105 is 40nm;
F) preparation of green light emitting layer 106
Adopt TCTA as material of main part, adopt Ir (ppy) 3as green glow guest materials, be the Ir (ppy) of 10:100 by percentage by weight 3adulterating with TCTA phase, is 1 × 10 in vacuum degree -5pa and evaporation rate are setting under, on hole transmission layer 105 vacuum evaporation formed green light emitting layer 106, the thickness of green light emitting layer 106 is 20nm;
G) preparation of electron transfer layer 107
Adopting Bphen as electron transport material, is 1 × 10 in vacuum degree -5pa and evaporation rate are setting under, on green light emitting layer 106 vacuum evaporation formed electron transfer layer 107, electron transfer layer 107 thickness is 35nm;
H) preparation of the second electron injecting layer 108
Be the Cs of 30:100 by percentage by weight 2cO 3adulterating with Bphen phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on electron transfer layer 107, vacuum evaporation forms the thickness of the second electron injecting layer 108, second electron injecting layer 108 is 30nm;
I) preparation of cathode layer 109
Adopting Ag as the material of cathode layer 109, is 1 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second electron injecting layer 108 vacuum evaporation formed cathode layer, the thickness of cathode layer 109 is 125nm.
Embodiment 2
As shown in Figure 1, the present embodiment 2 provides a kind of organic electroluminescence device, described organic electroluminescence device is layer structure, and described organic electroluminescence device comprises successively: anode conducting substrate 101, first hole injection layer 102, first electron injecting layer 103, second hole injection layer 104, hole transmission layer 105, green light emitting layer 106, electron transfer layer 107, second electron injecting layer 108, cathode layer 109.
The expression formula of described organic electroluminescence device is: ito glass/WO 3: TCTA (25:100)/CsF:BCP (25:100)/WO 3: TCTA (25:100)/TCTA/Ir (ppy) 2(acac): mCP (2:100)/BCP/CsF:BCP (25:100)/Al, wherein, colon ": " represents that the former is entrained in the latter.
The present embodiment 2 also provides the preparation method of above-mentioned organic electroluminescence device, and its step is as follows:
A) anode conducting substrate 101 pre-treatment
With ito glass (being also tin indium oxide transparent conductive glass) as anode conducting substrate 101, successively use liquid detergent, deionized water, acetone and ethanol purge respectively, all clean with supersonic wave cleaning machine, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on the surface of ito glass, improve the work function on the surface of ito glass; The thickness of ito glass is 120nm;
B) preparation of the first hole injection layer 102
Be the WO of 25:100 by percentage by weight 3adulterating with TCTA phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on anode conducting substrate 101, vacuum evaporation forms the thickness of the first hole injection layer 102, first hole injection layer 102 is 10nm;
C) preparation of the first electron injecting layer 103
Being that CsF with the BCF phase of 25:100 is adulterated by percentage by weight, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first hole injection layer 102, vacuum evaporation forms the thickness of the first electron injecting layer 103, first electron injecting layer 103 is 20nm;
D) preparation of the second hole injection layer 104
Be the WO of 25:100 by percentage by weight 3adulterating with TCTA phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first electron injecting layer 103, vacuum evaporation forms the thickness of the second hole injection layer 104, second hole injection layer 104 is 10nm;
E) preparation of hole transmission layer 105
Adopting TCTA as hole mobile material, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second hole injection layer 104 vacuum evaporation formed hole transmission layer 105, the thickness 30nm of hole transmission layer 105;
F) preparation of green light emitting layer 106
Adopt mCP as material of main part, adopt Ir (ppy) 2(acac) as green glow guest materials, be the Ir (ppy) of 2:100 by percentage by weight 2(acac) adulterating with mCP phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on hole transmission layer 105 vacuum evaporation formed green light emitting layer 106, the thickness of green light emitting layer 106 is 10nm;
G) preparation of electron transfer layer 107
Adopting BCP as electron transport material, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on green light emitting layer 106 vacuum evaporation formed electron transfer layer 107, electron transfer layer 107 thickness is 10nm;
H) preparation of the second electron injecting layer 108
Being that CsF with the BCF phase of 25:100 is adulterated by percentage by weight, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on electron transfer layer 107, vacuum evaporation forms the thickness of the second electron injecting layer 108, second electron injecting layer 108 is 20nm;
I) preparation of cathode layer 109
Adopting Al as the material of cathode layer 109, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second electron injecting layer 108 vacuum evaporation formed cathode layer 109, the thickness of cathode layer 109 is 50nm.
Embodiment 3
As shown in Figure 1, the present embodiment 3 provides a kind of organic electroluminescence device, described organic electroluminescence device is layer structure, and described organic electroluminescence device comprises successively: anode conducting substrate 101, first hole injection layer 102, first electron injecting layer 103, second hole injection layer 104, hole transmission layer 105, green light emitting layer 106, electron transfer layer 107, second electron injecting layer 108, cathode layer 109.
The expression formula of described organic electroluminescence device is: ito glass/V 2o 5: CBP (35:100)/CsN 3: BAlq (35:100)/V 2o 5: CBP (35:100)/CBP/Ir (mppy) 3: CBP (10:100)/BAlq/CsN 3: BAlq (35:100)/Au, wherein, colon ": " represents that the former is entrained in the latter.
The present embodiment 3 also provides the preparation method of above-mentioned organic electroluminescence device, and its step is as follows:
A) anode conducting substrate 101 pre-treatment
With ito glass (being also tin indium oxide transparent conductive glass) as anode conducting substrate 101, successively use liquid detergent, deionized water, acetone and ethanol purge respectively, all clean with supersonic wave cleaning machine, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on the surface of ito glass, improve the work function on the surface of ito glass; The thickness of ito glass is 100nm;
B) preparation of the first hole injection layer 102
Be the V of 35:100 by percentage by weight 2o 5adulterating with CBP phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on anode conducting substrate 101, vacuum evaporation forms the thickness of the first hole injection layer 102, first hole injection layer 102 is 15nm;
C) preparation of the first electron injecting layer 103
Be the CsN of 35:100 by percentage by weight 3adulterating with BAlq phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first hole injection layer 102, vacuum evaporation forms the thickness of the first electron injecting layer 103, first electron injecting layer 103 is 40nm;
D) preparation of the second hole injection layer 104
Be the V of 35:100 by percentage by weight 2o 5adulterating with CBP phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first electron injecting layer 103, vacuum evaporation forms the thickness of the second hole injection layer 104, second hole injection layer 104 is 15nm;
E) preparation of hole transmission layer 105
Adopting CBP as hole mobile material, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second hole injection layer 104 vacuum evaporation formed hole transmission layer 105, the thickness 50nm of hole transmission layer 105;
F) preparation of green light emitting layer 106
Adopt CBP as material of main part, adopt Ir (mppy) 3as green glow guest materials, be the Ir (mppy) of 10:100 by percentage by weight 3adulterating with CBP phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on hole transmission layer 105 vacuum evaporation formed green light emitting layer 106, the thickness of green light emitting layer 106 is 30nm;
G) preparation of electron transfer layer 107
Adopting BAlq as electron transport material, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on green light emitting layer 106 vacuum evaporation formed electron transfer layer 107, electron transfer layer 107 thickness is 60nm;
H) preparation of the second electron injecting layer 108
Be the CsN of 35:100 by percentage by weight 3adulterating with BAlq phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on electron transfer layer 107, vacuum evaporation forms the thickness of the second electron injecting layer 108, second electron injecting layer 108 is 40nm;
I) preparation of cathode layer 109
Adopting Au as the material of cathode layer 109, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second electron injecting layer 108 vacuum evaporation formed cathode layer 109, the thickness of cathode layer 109 is 200nm.
Embodiment 4
As shown in Figure 1, the present embodiment 4 provides a kind of organic electroluminescence device, described organic electroluminescence device is layer structure, and described organic electroluminescence device comprises successively: anode conducting substrate 101, first hole injection layer 102, first electron injecting layer 103, second hole injection layer 104, hole transmission layer 105, green light emitting layer 106, electron transfer layer 107, second electron injecting layer 108, cathode layer 109.
The expression formula of described organic electroluminescence device is: ito glass/ReO 3: TPD (30:100)/Li 2cO 3: Alq 3(30:100)/ReO 3: TPD (30:100)/TPD/Ir (ppy) 3: TPD (10:100)/Alq 3/ Li 2cO 3: Alq 3(30:100)/Ag, wherein, colon ": " represents that the former is entrained in the latter.
The present embodiment 4 also provides the preparation method of above-mentioned organic electroluminescence device, and its step is as follows:
A) anode conducting substrate 101 pre-treatment
With ito glass (being also tin indium oxide transparent conductive glass) as anode conducting substrate 101, successively use liquid detergent, deionized water, acetone and ethanol purge respectively, all clean with supersonic wave cleaning machine, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on the surface of ito glass, improve the work function on the surface of ito glass; The thickness of ito glass is 100nm;
B) preparation of the first hole injection layer 102
Be the ReO of 30:100 by percentage by weight 3adulterating with TPD phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on anode conducting substrate 101, vacuum evaporation forms the thickness of the first hole injection layer 102, first hole injection layer 102 is 13nm;
C) preparation of the first electron injecting layer 103
Be the Li of 30:100 by percentage by weight 2cO 3and Alq 3adulterating mutually, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first hole injection layer 102, vacuum evaporation forms the thickness of the first electron injecting layer 103, first electron injecting layer 103 is 30nm;
D) preparation of the second hole injection layer 104
Be the ReO of 30:100 by percentage by weight 3adulterating with TPD phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first electron injecting layer 103, vacuum evaporation forms the thickness of the second hole injection layer 104, second hole injection layer 104 is 13nm;
E) preparation of hole transmission layer 105
Adopting TPD as hole mobile material, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second hole injection layer 104 vacuum evaporation formed hole transmission layer 105, the thickness 40nm of hole transmission layer 105;
F) preparation of green light emitting layer 106
Adopt TPD as material of main part, adopt Ir (ppy) 3as green glow guest materials, be the Ir (ppy) of 5:100 by percentage by weight 3adulterating with TPD phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on hole transmission layer 105 vacuum evaporation formed green light emitting layer 106, the thickness of green light emitting layer 106 is 20nm;
G) preparation of electron transfer layer 107
Adopt Alq 3as electron transport material, be 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on green light emitting layer 106 vacuum evaporation formed electron transfer layer 107, electron transfer layer 107 thickness is 30nm;
H) preparation of the second electron injecting layer 108
Be the Li of 30:100 by percentage by weight 2cO 3and Alq 3adulterating mutually, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on electron transfer layer 107, vacuum evaporation forms the thickness of the second electron injecting layer 108, second electron injecting layer 108 is 30nm;
I) preparation of cathode layer 109
Adopting Ag as the material of cathode layer 109, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second electron injecting layer 108 vacuum evaporation formed cathode layer 109, the thickness of cathode layer 109 is 100nm.
Embodiment 5
As shown in Figure 1, the present embodiment 5 provides a kind of organic electroluminescence device, described organic electroluminescence device is layer structure, and described organic electroluminescence device comprises successively: anode conducting substrate 101, first hole injection layer 102, first electron injecting layer 103, second hole injection layer 104, hole transmission layer 105, green light emitting layer 106, electron transfer layer 107, second electron injecting layer 108, cathode layer 109.
The expression formula of described organic electroluminescence device is: ito glass/MoO 3: TAPC (25:100)/LiF:TAZ (30:100)/MoO 3: TAPC (25:100)/TAPC/Ir (ppy) 2(acac): TAPC (3:100)/TAZ/LiF:TAZ (30:100)/Al, wherein, colon ": " represents that the former is entrained in the latter.
The present embodiment 5 also provides the preparation method of above-mentioned organic electroluminescence device, and its step is as follows:
A) anode conducting substrate 101 pre-treatment
With ito glass (being also tin indium oxide transparent conductive glass) as anode conducting substrate 101, successively use liquid detergent, deionized water, acetone and ethanol purge respectively, all clean with supersonic wave cleaning machine, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on the surface of ito glass, improve the work function on the surface of ito glass; The thickness of ito glass is 100nm;
B) preparation of the first hole injection layer 102
Be the MoO of 25:100 by percentage by weight 3adulterating with TAPC phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on anode conducting substrate 101, vacuum evaporation forms the thickness of the first hole injection layer 102, first hole injection layer 102 is 10nm;
C) preparation of the first electron injecting layer 103
Being that LiF with the TAZ phase of 30:100 is adulterated by percentage by weight, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first hole injection layer 102, vacuum evaporation forms the thickness of the first electron injecting layer 103, first electron injecting layer 103 is 30nm;
D) preparation of the second hole injection layer 104
Be the MoO of 25:100 by percentage by weight 3adulterating with TAPC phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first electron injecting layer 103, vacuum evaporation forms the thickness of the second hole injection layer 104, second hole injection layer 104 is 10nm;
E) preparation of hole transmission layer 105
Adopting TAPC as hole mobile material, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second hole injection layer 104 vacuum evaporation formed hole transmission layer 105, the thickness 40nm of hole transmission layer 105;
F) preparation of green light emitting layer 106
Adopt TAPC as material of main part, adopt Ir (ppy) 2(acac) as green glow guest materials, be the Ir (ppy) of 3:100 by percentage by weight 2(acac) adulterating with TAPC phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on hole transmission layer 105 vacuum evaporation formed green light emitting layer 106, the thickness of green light emitting layer 106 is 20nm;
G) preparation of electron transfer layer 107
Adopting TAZ as electron transport material, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on green light emitting layer 106 vacuum evaporation formed electron transfer layer 107, electron transfer layer 107 thickness is 50nm;
H) preparation of the second electron injecting layer 108
Being that LiF with the TAZ phase of 30:100 is adulterated by percentage by weight, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on electron transfer layer 107, vacuum evaporation forms the thickness of the second electron injecting layer 108, second electron injecting layer 108 is 30nm;
I) preparation of cathode layer 109
Adopting Al as the material of cathode layer 109, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the second electron injecting layer 108 vacuum evaporation formed cathode layer 109, the thickness of cathode layer 109 is 100nm.
Embodiment 6
As shown in Figure 1, the present embodiment 6 provides a kind of organic electroluminescence device, described organic electroluminescence device is layer structure, and described organic electroluminescence device comprises successively: anode conducting substrate 101, first hole injection layer 102, first electron injecting layer 103, second hole injection layer 104, hole transmission layer 105, green light emitting layer 106, electron transfer layer 107, second electron injecting layer 108, cathode layer 109.
The expression formula of described organic electroluminescence device is: ito glass/WO 3: NPB (30:100)/Li 2o:TPBI (30:100)/WO 3: NPB (30:100)/NPB/Ir (mppy) 3: ADN (4:100)/TPBI/Li 2o:TPBI (30:100)/Al, wherein, colon ": " represents that the former is entrained in the latter.
The present embodiment 6 also provides the preparation method of above-mentioned organic electroluminescence device, and its step is as follows:
A) anode conducting substrate 101 pre-treatment
With ito glass (being also tin indium oxide transparent conductive glass) as anode conducting substrate 101, successively use liquid detergent, deionized water, acetone and ethanol purge respectively, all clean with supersonic wave cleaning machine, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on the surface of ito glass, improve the work function on the surface of ito glass; The thickness of ito glass is 100nm;
B) preparation of the first hole injection layer 102
Be the WO of 30:100 by percentage by weight 3adulterating with NPB phase, is 1 × 10 in vacuum degree -3pa and evaporation rate are setting under, on anode conducting substrate 101, vacuum evaporation forms the thickness of the first hole injection layer 102, first hole injection layer 102 is 12nm;
C) preparation of the first electron injecting layer 103
Be the Li of 30:100 by percentage by weight 2o with TPBI phase is adulterated, and is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the first hole injection layer 102, vacuum evaporation forms the thickness of the first electron injecting layer 103, first electron injecting layer 103 is 30nm;
D) preparation of the second hole injection layer 104
Be the WO of 30:100 by percentage by weight 3adulterating with NPB phase, is 1 × 10 in vacuum degree -3pa and evaporation rate are setting under, on the first electron injecting layer 103, vacuum evaporation forms the thickness of the second hole injection layer 104, second hole injection layer 104 is 12nm;
E) preparation of hole transmission layer 105
Adopting NPB as hole mobile material, is 1 × 10 in vacuum degree -3pa and evaporation rate are setting under, on the second hole injection layer 104 vacuum evaporation formed hole transmission layer 105, the thickness 40nm of hole transmission layer 105;
F) preparation of green light emitting layer 106
Adopt ADN as material of main part, adopt Ir (mppy) 3as green glow guest materials, be the Ir (mppy) of 4:100 by percentage by weight 3adulterating with ADN phase, is 1 × 10 in vacuum degree -3pa and evaporation rate are setting under, on hole transmission layer 105 vacuum evaporation formed green light emitting layer 106, the thickness of green light emitting layer 106 is 20nm;
G) preparation of electron transfer layer 107
Adopting TPBI as electron transport material, is 1 × 10 in vacuum degree -3pa and evaporation rate are setting under, on green light emitting layer 106 vacuum evaporation formed electron transfer layer 107, electron transfer layer 107 thickness is 30nm;
H) preparation of the second electron injecting layer 108
Be the Li of 30:100 by percentage by weight 2o with TPBI phase is adulterated, and is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on electron transfer layer 107, vacuum evaporation forms the thickness of the second electron injecting layer 108, second electron injecting layer 108 is 30nm;
I) preparation of cathode layer 109
Adopting Al as the material of cathode layer 109, is 1 × 10 in vacuum degree -3pa and evaporation rate are setting under, on the second electron injecting layer 108 vacuum evaporation formed cathode layer 109, the thickness of cathode layer 109 is 100nm.
It should be noted that: in the organic electroluminescence device of embodiment 1 ~ 6, first hole injection layer 102 is consistent with the component of the second hole injection layer 104, first electron injecting layer 103 component consistent with the second electron injecting layer 108 is consistent, but in other embodiments, the component of the first hole injection layer 102 and the second hole injection layer 104 also can be inconsistent, in like manner, the component that the first electron injecting layer 103 is consistent with the second electron injecting layer 108 also can be inconsistent.
Comparative example
This comparative example provides a kind of organic electroluminescence device, described organic electroluminescence device is layer structure, and described organic electroluminescence device comprises successively: anode conducting substrate, hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer, cathode layer.
The expression formula of described organic electroluminescence device is: ito glass/V 2o 5: CBP (30:100)/TCTA/Ir (ppy) 3: TCTA (8:100)/Bphen/Li 2o:TPBI (30:100)/Al, wherein, colon ": " represents that the former is entrained in the latter.
This comparative example also provides the preparation method of above-mentioned organic electroluminescence device, and its step is as follows:
A) anode conducting substrate pre-treatment
With ito glass (being also tin indium oxide transparent conductive glass) as anode conducting substrate, successively use liquid detergent, deionized water, acetone and ethanol purge respectively, all clean with supersonic wave cleaning machine, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on the surface of ito glass, improve the work function on the surface of ito glass; The thickness of ito glass is 100nm;
B) preparation of hole injection layer
Be the V of 30:100 by percentage by weight 2o 5adulterating with CBP phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on anode conducting substrate vacuum evaporation formed hole injection layer, the thickness of hole injection layer is 12nm;
E) preparation of hole transmission layer
Adopting TCTA as hole mobile material, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on hole injection layer vacuum evaporation formed hole transmission layer, the thickness 40nm of hole transmission layer;
F) preparation of green light emitting layer
Adopt TCTA as material of main part, adopt Ir (ppy) 3as green glow guest materials, be the Ir (ppy) of 8:100 by percentage by weight 3adulterating with TCTA phase, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on hole transmission layer vacuum evaporation formed green light emitting layer, the thickness of green light emitting layer is 20nm;
G) preparation of electron transfer layer
Adopting Bphen as electron transport material, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on green light emitting layer vacuum evaporation formed electron transfer layer, electric transmission layer thickness is 40nm;
H) preparation of electron injecting layer
Be the Li of 30:100 by percentage by weight 2during O with TPBI phase is adulterated, be 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on the electron transport layer vacuum evaporation formed electron injecting layer, the thickness of electron injecting layer is 30nm;
I) preparation of cathode layer
Adopting Al as the material of cathode layer, is 5 × 10 in vacuum degree -5pa and evaporation rate are setting under, on electron injecting layer vacuum evaporation formed cathode layer, the thickness of cathode layer is 138nm.
Carried out Performance Detection to the organic electroluminescence prepared in each embodiment and comparative example below, test result is as shown in table 1.
Table 1
From table 1, data can be seen, the light efficiency of the organic electroluminescence in various embodiments of the present invention is at more than 18lm/W, and the light efficiency of comparative example is only 13.0m/W.Organic electroluminescence of the present invention effectively improves luminous efficiency and reduces operating voltage.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection range required by claims.

Claims (10)

1. an organic electroluminescence device, described organic electroluminescence device is layer structure, it is characterized in that, described organic electroluminescence device comprises: the anode conducting substrate stacked gradually, first hole injection layer, first electron injecting layer, second hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, second electron injecting layer and cathode layer, described first hole injection layer and described second hole injection layer form by hole-injecting material and the p-type material that is doped in described hole-injecting material, described first electron injecting layer and described second electron injecting layer form by electron injection material and the N-shaped material that is doped in described electron injection material.
2. organic electroluminescence device according to claim 1, is characterized in that, the percentage by weight that described p-type material accounts for described hole-injecting material is 25 ~ 35wt%; The percentage by weight that described N-shaped material accounts for described electron injection material is 25 ~ 35wt%.
3. organic electroluminescence device according to claim 1, is characterized in that,
Described p-type material is MoO 3, WO 3, V 2o 5or ReO 3;
Described hole-injecting material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane;
Described N-shaped material is Cs 2cO 3, CsF, CsN 3, Li 2cO 3, LiF or Li 2o;
Described electron injection material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described first hole injection layer and described second hole injection layer is 10 ~ 15nm; The thickness of described first electron injecting layer and described second electron injecting layer is 20 ~ 40nm.
5. organic electroluminescence device according to claim 1, is characterized in that,
The material of described anode conducting substrate is tin indium oxide transparent conductive glass, and thickness is 100 ~ 150nm;
The material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane, the thickness of described hole transmission layer is 30 ~ 50nm;
The material of described green light emitting layer is made up of material of main part and the green glow guest materials being doped in material of main part, described material of main part is 4, 4', 4''-tri-(carbazole-9-base) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazoles, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane or 9, two (1-naphthyl) anthracene of 10-, described green glow guest materials is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridines] close iridium, the percentage by weight that described green glow guest materials accounts for described material of main part is 2 ~ 10wt%, the thickness of described green light emitting layer is 10 ~ 30nm,
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, and 2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, the thickness of described electron transfer layer is 10 ~ 60nm;
The material of described cathode layer is silver, aluminium or gold, and thickness is 50 ~ 200nm.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Adopt vacuum deposition method on anode conducting substrate, form the first hole injection layer, the first electron injecting layer, the second hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, the second electron injecting layer and cathode layer successively, thus obtained described organic electroluminescence device;
Wherein: vacuum is steamed when crossing described first hole injection layer and described second hole injection layer, all by material doped for p-type enter in hole-injecting material, thus form described first hole injection layer and described second hole injection layer; Described hole-injecting material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane; Described p-type material is MoO 3, WO 3, V 2o 5or ReO 3; The percentage by weight that described p-type material accounts for described hole-injecting material is 25 ~ 35wt%;
When vacuum is steamed and is crossed described first electron injecting layer and described second electron injecting layer, all by material doped for N-shaped enter in electron injection material, thus form described first electron injecting layer and described second electron injecting layer, described electron injection material is 4, 7-diphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-Phen, 4-biphenyl phenolic group-two (2-methyl-oxine) closes aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole or 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, described N-shaped material is Cs 2cO 3, CsF, CsN 3, Li 2cO 3, LiF or Li 2o, the percentage by weight that described N-shaped material accounts for described electron injection material is 25 ~ 35wt%.
7. preparation method according to claim 6, it is characterized in that, described first hole injection layer and described second hole injection layer thickness of gained after vacuum evaporation are 10 ~ 15nm, and the thickness of described first electron injecting layer and described second electron injecting layer gained after vacuum evaporation is 20 ~ 40nm.
8. preparation method according to claim 6, is characterized in that, described in vacuum evaporation when the first hole injection layer and described second hole injection layer, set vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is described in vacuum evaporation when the first electron injecting layer and described second electron injecting layer, set vacuum degree is 8 × 10 -5pa ~ 3 × 10 -4pa, evaporation rate is
9. preparation method according to claim 6, is characterized in that,
When vacuum is steamed and crossed described hole transmission layer, adopt N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane give are hole mobile material;
When vacuum is steamed and is crossed described green light emitting layer, adopt 4, 4', 4''-tri-(carbazole-9-base) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazoles, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane or 9, two (1-naphthyl) anthracene of 10-is as material of main part, three (2-phenylpyridines) are adopted to close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridines] close iridium as green glow guest materials, described green glow guest materials is doped in described material of main part, thus form described green light emitting layer, wherein, the percentage by weight that described green glow guest materials accounts for described material of main part is 2 ~ 10wt%,
When vacuum is steamed and is crossed described electron transfer layer, adopt 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phens, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene are as electron transport material;
When vacuum is steamed and crossed described cathode layer, adopt silver, aluminium or gold as raw material.
10. preparation method according to claim 6, is characterized in that,
Described in vacuum evaporation during hole transmission layer, set vacuum degree is 1 × 10 -5pa ~ 3 × 10 -3pa, evaporation rate is the thickness of described hole transmission layer gained after vacuum evaporation is 30 ~ 50nm;
Described in vacuum evaporation during green light emitting layer, set vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is the thickness of described green light emitting layer gained after vacuum evaporation is 10 ~ 30nm;
Described in vacuum evaporation during electron transfer layer, set vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate the thickness of described electron transfer layer gained after vacuum evaporation is 10 ~ 60nm;
Described in vacuum evaporation during cathode layer, set vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is the thickness of described cathode layer gained after vacuum evaporation is 50 ~ 200nm.
CN201410071842.6A 2014-02-28 2014-02-28 Organic electroluminescent device and preparation method thereof Pending CN104882545A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025091A (en) * 2016-07-19 2016-10-12 Tcl集团股份有限公司 Top-emission type OLED device, display panel and manufacturing method
CN109873087A (en) * 2017-12-01 2019-06-11 上海和辉光电有限公司 A kind of dot structure and display panel
CN110447118A (en) * 2017-12-11 2019-11-12 株式会社Lg化学 Organic luminescent device and its manufacturing method
WO2022061939A1 (en) * 2020-09-28 2022-03-31 京东方科技集团股份有限公司 Organic electroluminescent device and display device

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025091A (en) * 2016-07-19 2016-10-12 Tcl集团股份有限公司 Top-emission type OLED device, display panel and manufacturing method
CN109873087A (en) * 2017-12-01 2019-06-11 上海和辉光电有限公司 A kind of dot structure and display panel
CN110447118A (en) * 2017-12-11 2019-11-12 株式会社Lg化学 Organic luminescent device and its manufacturing method
CN110447118B (en) * 2017-12-11 2022-03-01 株式会社Lg化学 Organic light emitting device and method of manufacturing the same
WO2022061939A1 (en) * 2020-09-28 2022-03-31 京东方科技集团股份有限公司 Organic electroluminescent device and display device

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