CN104078604A - White organic light-emitting diode and manufacturing method thereof - Google Patents

White organic light-emitting diode and manufacturing method thereof Download PDF

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Publication number
CN104078604A
CN104078604A CN201310109511.2A CN201310109511A CN104078604A CN 104078604 A CN104078604 A CN 104078604A CN 201310109511 A CN201310109511 A CN 201310109511A CN 104078604 A CN104078604 A CN 104078604A
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layer
bis
luminescent layer
phenyl
red light
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周明杰
钟铁涛
王平
陈吉星
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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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Priority to CN201310109511.2A priority Critical patent/CN104078604A/en
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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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
    • H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent 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
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

A white organic light-emitting diode comprises an anode layer, a first hole injection layer, a first hole transmission layer, a first light-emitting layer, a first electron transmission layer, a charge generation layer, a second hole injection layer, a second hole transmission layer, a second light-emitting layer, a second electron transmission layer, an electron injection layer and a cathode layer, wherein the anode layer, the first hole injection layer, the first hole transmission layer, the first light-emitting layer, the first electron transmission layer, the charge generation layer, the second hole injection layer, the second hole transmission layer, the second light-emitting layer, the second electron transmission layer, the electron injection layer and the cathode layer are stacked in sequence. The anode layer comprises a glass substrate, a refraction layer and a transparent conducting layer, wherein the glass substrate, the refraction layer and the transparent conducting layer are stacked in sequence. The surface, opposite to the glass substrate, of the refraction layer is provided with a micro-pattern composed of a plurality of protrusions arranged at intervals, and therefore a plurality of gaps are formed between the refraction layer and the glass substrate. The first light-emitting layer comprises a first red light-emitting layer body and a green light-emitting layer body stacked on the first red light-emitting layer body. The second light-emitting layer comprises a second red light-emitting layer body and a blue light-emitting layer body stacked on the second red light-emitting layer body. The white organic light-emitting diode has a higher color rendering index and a lower working current. The invention further relates to a manufacturing method of the white organic light-emitting diode.

Description

White light organic electroluminescent device and preparation method thereof
Technical field
The present invention relates to field of electronic devices, particularly a kind of white light organic electroluminescent device and preparation method thereof.
Background technology
White light organic electroluminescent device (OLED, Organic Light-Emitting Diode) have advantages of that some are unique: (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, the OLED illumination light of design color as required, no matter be little Molecule OLEDs at present, or polymer organic LED (PLED) has all obtained and has comprised the light of white-light spectrum at interior all colours; (3) OLED can make on as glass, pottery, metal, plastic or other material at multiple substrate, freer when this makes to design lighting source; (4) adopt the mode of making OLED demonstration to make OLED illumination panel, can in illumination, show information; (5) OLED also can be used as controlled look in illuminator, allows user to regulate light atmosphere according to individual demand.But there is the problem that color rendering index is lower, operating current is larger in traditional white light organic electroluminescent device.
Summary of the invention
Given this, be necessary to provide white light organic electroluminescent device that a kind of color rendering index is higher and operating current is less and preparation method thereof.
A kind of white light organic electroluminescent device, comprise the anode layer stacking gradually, the first hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole injection layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and cathode layer, described anode layer comprises the glass substrate stacking gradually, dioptric layer and transparency conducting layer, the surface that described dioptric layer is relative with described glass substrate is provided with the micro-pattern being made up of multiple spaced projections, make to form multiple spaces between described dioptric layer and described glass substrate, described the first hole injection layer is laminated on described transparency conducting layer, described the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer of described the first red light luminescent layer, and described the first red light luminescent layer is laminated on described the first hole transmission layer, described the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting of described the second red light luminescent layer, and described the second red light luminescent layer is laminated on described the second hole transmission layer, wherein, described blue light emitting material comprises Blue-light emitting host material and co-doped blue light guest materials and the charge generating material in described Blue-light emitting host material, the mass ratio of described blue light guest materials and described Blue-light emitting host material is 0.05～0.2:1, and the mass ratio of described charge generating material and described Blue-light emitting host material is 0.05～0.1:1, described Blue-light emitting host material is selected from 4,4 '-bis-(9-carbazole) biphenyl, 9,9 '-(1,3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles, 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines, 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine and Isosorbide-5-Nitrae--the one in two (triphenyl silicon) benzene of 5-, described blue light guest materials is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid close iridium, three (2-(4 ', 6 '-bis-fluoro-5 '-cyano group) phenylpyridine-N, C2 ') close iridium, two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium and two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) closes the one in iridium, described charge generating material is selected from the one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide.
In an embodiment, the material of described glass substrate is indium tin oxide glass therein; The material of described dioptric layer is that refractive index is 1.7～1.9 overlay; The width of each projection is 5 microns～20 microns, is highly 5 microns～20 microns, and distance between adjacent two projections is 5 microns～20 microns; The material of described transparency conducting layer is the one in indium tin oxide, aluminium zinc oxide and indium-zinc oxide.
Therein in an embodiment, the material of described the first red light luminescent layer comprises the first ruddiness material of main part and is doped in the first ruddiness guest materials in described the first ruddiness material of main part, and the mass ratio of described the first ruddiness guest materials and described the first ruddiness material of main part is 0.005～0.02:1, the material of described green luminescence layer comprises green glow material of main part and is doped in the green glow guest materials in described green glow material of main part, and the mass ratio of described green glow guest materials and described green glow material of main part is 0.02～0.1:1, the material of described the second red light luminescent layer comprises the second ruddiness material of main part and is doped in the second ruddiness guest materials in described the second ruddiness material of main part, and the mass ratio of described the second ruddiness guest materials and described the second ruddiness material of main part is 0.005～0.02:1, described the first ruddiness material of main part, described green glow material of main part and described the second ruddiness material of main part are selected from respectively 4,4 ', 4 " tri-(carbazole-9-yl) 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 '-bis-(p-tolyl) amino] phenyl] one in two (1-naphthyl) anthracenes of cyclohexane and 9,10-, described the first ruddiness guest materials and described the second ruddiness guest materials are selected from respectively two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) and three (1-phenyl-isoquinolin) and close the one in iridium, described green glow guest materials is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium and three [2-(p-methylphenyl) pyridine] closes the one in iridium (III).
In an embodiment, the thickness of described the first red light luminescent layer is 10 nanometer～30 nanometers therein; The thickness of described green luminescence layer is 10 nanometer～30 nanometers; The thickness of described the second red light luminescent layer is 10 nanometer～30 nanometers; The thickness of described blue light-emitting is 5 nanometer～15 nanometers.
Therein in an embodiment, the material of described the first hole injection layer comprises the first hole mobile material and is doped in the first p-type dopant in described the first hole mobile material, and the mass ratio of described the first p-type dopant and described the first hole mobile material is 0.25～0.35:1; The material of described the second hole injection layer comprises the second hole mobile material and is doped in the second p-type dopant in described the second hole mobile material, and the mass ratio of described the second p-type dopant and described the second hole mobile material is 0.25～0.35:1; Described the first hole mobile material and described the second hole mobile material are selected from respectively N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 4; 4 '-bis-(9-carbazole) biphenyl, N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] one in cyclohexane; Described the first p-type dopant and described the second p-type dopant are selected from respectively the one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide;
The material of the material of described the first hole transmission layer and described the second hole transmission layer is selected from respectively N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 4; 4 '-bis-(9-carbazole) biphenyl, N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] one in cyclohexane;
The material of the material of described the first electron transfer layer and described the second electron transfer layer is selected from respectively 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described charge generation layer is the one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide;
The material of described electron injecting layer comprises electron transport material and is doped in the N-shaped dopant in described electron transport material, and the mass ratio of described N-shaped dopant and described electron transport material is 0.25～0.35:1; Described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; Described N-shaped dopant is the one in cesium carbonate, cesium fluoride, cesium azide, lithium carbonate, lithium fluoride and lithia; And
The material of described cathode layer is the one in silver, aluminium and gold.
In an embodiment, the thickness of described the first hole injection layer is 10 nanometer～15 nanometers therein; The thickness of described the first hole transmission layer is 30 nanometer～50 nanometers; The thickness of described the first electron transfer layer is 10 nanometer～60 nanometers; The thickness of described charge generation layer is 5 nanometer～30 nanometers; The thickness of described the second hole injection layer is 10 nanometer～15 nanometers; The thickness of described the second hole transmission layer is 30 nanometer～50 nanometers; The thickness of described the second electron transfer layer is 10 nanometer～60 nanometers; The thickness of described electron injecting layer is 20 nanometer～40 nanometers; The thickness of described cathode layer is 50 nanometer～200 nanometers.
A preparation method for white light organic electroluminescent device, comprises the steps:
On a surface of dioptric layer, make the micro-pattern being formed by multiple spaced projections, described dioptric layer is there is to surface and the glass substrate pressing of described micro-pattern, then on another surface of described dioptric layer, deposition forms transparency conducting layer, obtain anode layer, wherein, between described dioptric layer and described glass substrate, form multiple spaces;
On described transparency conducting layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively;
On described the first hole transmission layer, form the first luminescent layer, described the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on described the first red light luminescent layer, described the first red light luminescent layer is formed on described the first hole transmission layer, and described the first red light luminescent layer and described green luminescence layer are prepared by vacuum evaporation;
On described green luminescence layer, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer successively;
On described the second hole transmission layer, form the second luminescent layer, described the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on described the second red light luminescent layer, described the second red light luminescent layer is formed on described the second hole transmission layer, and described the second red light luminescent layer and described blue light-emitting are prepared by vacuum evaporation; Wherein, described blue light emitting material comprises Blue-light emitting host material and co-doped blue light guest materials and the charge generating material in described Blue-light emitting host material, the mass ratio of described blue light guest materials and described Blue-light emitting host material is 0.05～0.2:1, and the mass ratio of described charge generating material and described Blue-light emitting host material is 0.05～0.1:1; Described Blue-light emitting host material is selected from 4,4 '-bis-(9-carbazole) biphenyl, 9,9 '-(1,3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles, 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines, 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine and Isosorbide-5-Nitrae--the one in two (triphenyl silicon) benzene of 5-; Described blue light guest materials is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid close iridium, three (2-(4 ', 6 '-bis-fluoro-5 '-cyano group) phenylpyridine-N, C2 ') close iridium, two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium and two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) closes the one in iridium; Described charge generating material is selected from the one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide; And
On described blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and cathode layer successively, obtains white light organic electroluminescent device.
Therein in an embodiment, described dioptric layer is had and also comprises before the surface of described micro-pattern and described glass substrate pressing described glass substrate is cleaned and the step of surface activation process successively; The step of described cleaning is: glass substrate is adopted to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, and then dry.
In an embodiment, before on described transparency conducting layer, vacuum evaporation forms described the first hole injection layer, also comprise described anode layer in 60 DEG C～80 DEG C vacuumizes 15 minutes～30 minutes therein.
In an embodiment, the vacuum degree that vacuum evaporation forms described the first hole injection layer is 8 × 10 therein -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the first hole transmission layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the first red light luminescent layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described green luminescence layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the first electron transfer layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described charge generation layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the second hole injection layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the second hole transmission layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the second red light luminescent layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described blue light-emitting is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the second electron transfer layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described electron injecting layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is and
The vacuum degree that vacuum evaporation forms described cathode layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
Above-mentioned white light organic electroluminescent device comprises the anode layer stacking gradually, the first hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole injection layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and cathode layer, what adopt is PIN laminated construction, and anode layer comprises the glass substrate stacking gradually, dioptric layer and transparency conducting layer, the surface that dioptric layer is relative with glass substrate is provided with micro-pattern of multiple spaced projection compositions, make to form between dioptric layer and glass substrate multiple spaces, thereby make the centre of anode layer containing air, be conducive to strengthen the bright dipping of transparency conducting layer, the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on the first red light luminescent layer, the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on the second red light luminescent layer, thereby on the basis of the first luminescent layer, supplement the strong and spectral component of red blue light, and whole organic electroluminescence device has comprised red-green-blue luminescent layer, have wider spectral region, half-wave peak width, makes organic electroluminescence device have higher color rendering index, in addition, adopt the organic electroluminescence device of this laminated construction, under equal brightness, electric current can reduce by half, and makes it have lower operating current, and the material of blue light-emitting comprises Blue-light emitting host material and co-doped blue light guest materials and the charge generating material in Blue-light emitting host material, the blue light-emitting of this co-doped form, can improve the combined efficiency of electron hole, thereby be conducive to improve the luminous efficiency of organic electroluminescence device, therefore, above-mentioned white light organic electroluminescent device not only has higher color rendering index, reach 80, also there is higher luminous efficiency, luminous efficiency can reach 15.3lm/W, there is less operating current, be that above-mentioned white light organic electroluminescent device has higher color rendering index and less operating current, be conducive to increase the useful life of white light organic electroluminescent device.
Brief description of the drawings
Fig. 1 is the structural representation of the white light organic electroluminescent device of an execution mode;
Fig. 2 is the preparation method's of the white light organic electroluminescent device of an execution mode flow chart.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments white light organic electroluminescent device and preparation method thereof is described in further detail below.
As shown in Figure 1, the white light organic electroluminescent device 100 of one execution mode, comprises the anode layer 110, the first hole injection layer 120, the first hole transmission layer 130, the first luminescent layer 140, the first electron transfer layer 150, charge generation layer 160, the second hole injection layer 170, the second hole transmission layer 180, the second luminescent layer 190, the second electron transfer layer 210, electron injecting layer 220 and the cathode layer 230 that stack gradually.
Anode layer 110 comprises the glass substrate 112, dioptric layer 114 and the transparency conducting layer 116 that stack gradually.The material of glass substrate 112 can be the conventional baseplate material in this area, is preferably indium tin oxide glass (ITO).Preferably, the thickness of glass substrate 112 is 100 nanometers.The material of dioptric layer 114 is that refractive index is 1.7～1.9 overlay, and for example, overlay can be polyurethane plastic (PU), PEN (PEN) or polyimides (PI).The dioptric layer 114 with above-mentioned index of refraction has high refraction index, can strengthen bright dipping.The surface that dioptric layer 114 is relative with glass substrate 112 is provided with micro-patterns 1142 of multiple spaced projection compositions, makes to form between dioptric layer 114 and glass substrate 112 multiple spaces 1144.Dioptric layer 114 has behind the surface and glass substrate 112 laminatings of micro-pattern 1142, and projection connects with glass substrate 112, makes to form space between adjacent two projections, thereby can reach the effect that strengthens bright dipping.Preferably, the width of each projection is 5 microns～20 microns, is highly 5 microns～20 microns, and distance between adjacent two projections is 5 microns～20 microns, goes out preferably light effect thereby have.The material of transparency conducting layer 116 can, for the conventional transparent material with electric conductivity in this area, be preferably the one in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide (IZO).
The first hole injection layer 120 is laminated on transparency conducting layer 116.Wherein, the material of the first hole injection layer 120 comprises the first hole mobile material and is doped in the first p-type dopant in the first hole mobile material, and the mass ratio of the first p-type dopant and the first hole mobile material is 0.25～0.35:1.The first hole mobile material is N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 4; 4 '-bis-(9-carbazole) biphenyl (CBP), N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] one in cyclohexane (TAPC); The first p-type dopant is molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) and rhenium trioxide (ReO 3) in one.
Preferably, the thickness of the first hole injection layer 120 is 10 nanometer～15 nanometers.
The material of the first hole transmission layer 130 is selected from N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 4; 4 '-bis-(9-carbazole) biphenyl (CBP), N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] one in cyclohexane (TAPC).
Preferably, the thickness of the first hole transmission layer 130 is 30 nanometer～50 nanometers.
The first luminescent layer 140 comprises the first red light luminescent layer 142 and green luminescence layer 144, the first red light luminescent layer 142 that are laminated on the first red light luminescent layer 142 are laminated on the first hole transmission layer 130.Wherein, the material of the first red light luminescent layer 142 comprises the first ruddiness material of main part and is doped in the first ruddiness guest materials in the first ruddiness material of main part, and the mass ratio of the first ruddiness guest materials and the first ruddiness material of main part is 0.005～0.02:1.The material of green luminescence layer 144 comprises green glow material of main part and is doped in the green glow guest materials in green glow material of main part, and the mass ratio of green glow guest materials and green glow material of main part is 0.02～0.1:1.The first ruddiness material of main part and green glow material of main part are selected from respectively 4,4 ', 4 '-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9 '-(1,3-phenyl) two-9H-carbazole (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 '-bis-(p-tolyl) amino] phenyl] one in two (1-naphthyl) anthracenes (ADN) of cyclohexane (TAPC) and 9,10-.The first ruddiness guest materials is selected from two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) and closes iridium (Ir (MDQ) 2(acac)), two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi) 2ir (acac)), two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) ((F-BT) 2ir (acac)), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp) 2(acac)) and three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) in one.Green glow guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2(acac)) and three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) in one.
Preferably, the thickness of the first red light luminescent layer 142 is 10 nanometer～30 nanometers; The thickness of green luminescence layer 144 is 10 nanometer～30 nanometers.
The first electron transfer layer 150 is laminated on green luminescence layer 144.The material of the first electron transfer layer 150 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
Preferably, the thickness of the first electron transfer layer 150 is 10 nanometer～60 nanometers.
The material of charge generation layer 160 is molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) and rhenium trioxide (ReO 3) in one.These materials are ambipolar material, use the charge generation layer 160 of these materials also to have bipolarity.
Preferably, the thickness of charge generation layer 160 is 20 nanometer～40 nanometers.
The material of the second hole injection layer 170 comprises the second hole mobile material and is doped in the second p-type dopant in the second hole mobile material, and the mass ratio of the second p-type dopant and the second hole mobile material is 0.25～0.35:1.The second hole mobile material is selected from N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 4; 4 '-bis-(9-carbazole) biphenyl (CBP), N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] one in cyclohexane (TAPC); The second p-type dopant is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) and rhenium trioxide (ReO 3) in one.
Preferably, the thickness of the second hole injection layer 170 is 10 nanometer～15 nanometers.
The material of the second hole transmission layer 180 is selected from N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 4; 4 '-bis-(9-carbazole) biphenyl (CBP), N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] one in cyclohexane (TAPC).
Preferably, the thickness of the second hole transmission layer 180 is 30 nanometer～50 nanometers.
The second luminescent layer 190 comprises the second red light luminescent layer 192 and is laminated in the blue light-emitting 194 on the second red light luminescent layer 192, and the second red light luminescent layer 192 is laminated on the second hole transmission layer 180.The material of the second red light luminescent layer 192 comprises the second ruddiness material of main part and is doped in the second ruddiness guest materials in the second ruddiness material of main part, and the mass ratio of the second ruddiness guest materials and the second ruddiness material of main part is 0.005～0.02:1.The second ruddiness material of main part is selected from 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), 9; 9 '-(1; 3-phenyl) two-9H-carbazole (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 '-bis-(p-tolyl) amino] phenyl] one in two (1-naphthyl) anthracenes (ADN) of cyclohexane (TAPC) and 9,10-; The second ruddiness guest materials is selected from two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) and closes iridium (Ir (MDQ) 2(acac)), two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi) 2ir (acac)), two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) ((F-BT) 2ir (acac)), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp) 2(acac)) and three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) in one.The material of blue light-emitting 194 comprises Blue-light emitting host material and co-doped blue light guest materials and the charge generating material in Blue-light emitting host material, and the mass ratio of blue light guest materials and Blue-light emitting host material is 0.05～0.2:1.The mass ratio of charge generating material and Blue-light emitting host material is 0.05～0.1:1; Blue-light emitting host material is selected from 4,4 '-bis-(9-carbazole) biphenyl (CBP), 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP), 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles (CzSi), 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY), 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine (35DCzPPY) and Isosorbide-5-Nitrae--the one in two (triphenyl silicon) benzene (UGH2) of 5-.Blue light guest materials is selected from two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), three (2-(4 ', 6 '-bis-fluoro-5 '-cyano group) phenylpyridine-N, C2 ') close iridium (FCNIr), two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium (FIrtaz) and two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) close the one in iridium (FIrN4), charge generating material is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) and rhenium trioxide (ReO 3) in one.
The material that the material of blue light-emitting 194 adopts above-mentioned blue light guest materials and above-mentioned charge generating material co-doped to form in above-mentioned Blue-light emitting host material, the HOMO of above-mentioned Blue-light emitting host material or LUMO can extreme difference be 0.3eV left and right, and the triplet of above-mentioned Blue-light emitting host material is poor is 0.5eV left and right, above-mentioned charge generating material is bipolar materials, can improve electron-hole recombinations probability, therefore, the material that the material of blue light-emitting 194 adopts above-mentioned blue light guest materials and above-mentioned charge generating material co-doped to form in above-mentioned Blue-light emitting host material, can improve the combined efficiency of electron hole.
In the material of blue light-emitting 194, the mass ratio of blue light guest materials and Blue-light emitting host material is 0.05～0.2:1, can propose high-octane transfer; The mass ratio of charge generating material and Blue-light emitting host material is 0.05～0.1:1, and the charge-doping material of this ratio contributes to improve the compound of electron hole.
Preferably, the thickness of the second red light luminescent layer 192 is 10 nanometer～30 nanometers; The thickness of blue light-emitting 194 is 5 nanometer～15 nanometers.
The second electron transfer layer 210 is laminated on blue light-emitting 194.The material of the second electron transfer layer 210 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
Preferably, the thickness of the second electron transfer layer 210 is 10 nanometer～60 nanometers.
The material of electron injecting layer 220 comprises electron transport material and is doped in the N-shaped dopant in electron transport material, and the mass ratio of N-shaped dopant and electron transport material is 0.25～0.35:1; Electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4, and 7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI); N-shaped dopant is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), cesium azide (CsN 3), lithium carbonate (Li 2cO 3), lithium fluoride (LiF) and lithia (Li 2o) one in.
Preferably, the thickness of electron injecting layer 220 is 20 nanometer～40 nanometers
The material of cathode layer 230 is the one in silver (Ag), aluminium (Al) and gold (Au).
Preferably, the thickness of cathode layer 230 is 50 nanometer～200 nanometers.
Above-mentioned white light organic electroluminescent device 100 comprises the anode layer 110 stacking gradually, the first hole injection layer 120, the first hole transmission layer 130, the first luminescent layer 140, the first electron transfer layer 150, charge generation layer 160, the second hole injection layer 170, the second hole transmission layer 180, the second luminescent layer 190, the second electron transfer layer 210, electron injecting layer 220 and cathode layer 230, what adopt is PIN laminated construction, and anode layer 110 comprises the glass substrate 112 stacking gradually, dioptric layer 114 and transparency conducting layer 116, the surface that dioptric layer 114 is relative with glass substrate 112 is provided with micro-pattern 1142 of multiple spaced projection compositions, make to form between dioptric layer 114 and glass substrate 112 multiple spaces 1144, thereby make the centre of anode layer 110 containing air, be conducive to strengthen the bright dipping of transparency conducting layer 116, the first luminescent layer 140 comprises the first red light luminescent layer 142 and is laminated in the green luminescence layer 144 on the first red light luminescent layer 142, the second luminescent layer comprises the second red light luminescent layer 192 and is laminated in the blue light-emitting 194 on the second red light luminescent layer 192, thereby on the basis of the first luminescent layer 140, supplement the strong and spectral component of red blue light, and whole organic electroluminescence device 100 has comprised red-green-blue luminescent layer, there is wider spectral region, half-wave peak width, makes organic electroluminescence device 100 have higher color rendering index, in addition, adopt the organic electroluminescence device 100 of this laminated construction, under equal brightness, electric current can reduce by half, and makes it have lower operating current, and the material of blue light-emitting 194 comprises Blue-light emitting host material and co-doped blue light guest materials and the charge generating material in Blue-light emitting host material, the blue light-emitting 194 of this co-doped form, can improve the combined efficiency of electron hole, thereby be conducive to improve the luminous efficiency of organic electroluminescence device 100, therefore, above-mentioned white light organic electroluminescent device 100 not only has higher color rendering index, reach 80, also there is higher luminous efficiency, luminous efficiency can reach 15.3lm/W, there is less operating current, be that above-mentioned white light organic electroluminescent device 100 has higher color rendering index and less operating current, be conducive to increase the useful life of white light organic electroluminescent device 100.
As shown in Figure 2, the preparation method of the white light organic electroluminescent device of an execution mode, comprises the steps:
Step S310: make the micro-pattern being formed by multiple spaced projections on a surface of dioptric layer, dioptric layer is there is to surface and the glass substrate pressing of micro-pattern, then on another surface of dioptric layer, deposition forms transparency conducting layer, obtain anode layer, wherein, between dioptric layer and glass substrate, form multiple spaces.
Preferably, dioptric layer is had and also comprise before the surface of micro-pattern and glass substrate pressing glass substrate is cleaned and the step of surface activation process successively; The step of cleaning is: glass substrate is adopted to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, and then dry.In specific embodiment, clean 5 minutes at every turn, stop 5 minutes, repeat respectively 3 times, and then use oven for drying.By the glass substrate after cleaning is carried out to surface activation process, can increase the oxygen content of glass baseplate surface, improve the work function of glass baseplate surface.
Preferably, before vacuum evaporation forms the first hole injection layer on transparency conducting layer, also comprise anode layer in 60 DEG C～80 DEG C vacuumizes 15 minutes～30 minutes, thereby reduce remaining water and gas.
Step S320: vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively on transparency conducting layer.
Preferably, to form the vacuum degree of the first hole injection layer be 8 × 10 in vacuum evaporation -5pa～3 × 10 -4pa, evaporation rate is
Preferably, to form the vacuum degree of the first hole transmission layer be 8 × 10 in vacuum evaporation -5pa～3 × 10 -4pa, evaporation rate is
Step S330: form the first luminescent layer on the first hole transmission layer, the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on the first red light luminescent layer, the first red light luminescent layer is formed on the first hole transmission layer, and the first red light luminescent layer and green luminescence layer are prepared by vacuum evaporation.
Preferably, to form the vacuum degree of the first red light luminescent layer be 8 × 10 in vacuum evaporation -5pa～3 × 10 -4pa, evaporation rate is
Preferably, the vacuum degree of vacuum evaporation formation green luminescence layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
Step S340: vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer successively on green luminescence layer.
Preferably, to form the vacuum degree of the first electron transfer layer be 8 × 10 in vacuum evaporation -5pa～3 × 10 -4pa, evaporation rate is
Preferably, the vacuum degree of vacuum evaporation formation charge generation layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
Preferably, to form the vacuum degree of the second hole injection layer be 8 × 10 in vacuum evaporation -5pa～3 × 10 -4pa, evaporation rate is
Preferably, to form the vacuum degree of the second hole transmission layer be 8 × 10 in vacuum evaporation -5pa～3 × 10 -4pa, evaporation rate is
Step S350: form the second luminescent layer on the second hole transmission layer, the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on the second red light luminescent layer, the second red light luminescent layer is formed on the second hole transmission layer, and the second red light luminescent layer and blue light-emitting are prepared by vacuum evaporation, wherein, the material of blue light-emitting comprises Blue-light emitting host material and co-doped blue light guest materials and the charge generating material in Blue-light emitting host material, and the mass ratio of blue light guest materials and Blue-light emitting host material is 0.05～0.2:1, the mass ratio of charge generating material and Blue-light emitting host material is 0.05～0.1:1, Blue-light emitting host material is selected from 4,4 '-bis-(9-carbazole) biphenyl (CBP), 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP), 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles (CzSi), 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY), 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine (35DCzPPY) and Isosorbide-5-Nitrae--the one in two (triphenyl silicon) benzene (UGH2) of 5-, blue light guest materials is selected from two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), three (2-(4 ', 6 '-bis-fluoro-5 '-cyano group) phenylpyridine-N, C2 ') close iridium (FCNIr), two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium (FIrtaz) and two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) close the one in iridium (FIrN4), charge generating material is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) and rhenium trioxide (ReO 3) in one.
Preferably, to form the vacuum degree of the second red light luminescent layer be 8 × 10 in vacuum evaporation -5pa～3 × 10 -4pa, evaporation rate is
Preferably, the vacuum degree that vacuum evaporation forms blue light-emitting is 8 × 10-5Pa～3 × 10-4Pa, and evaporation rate is
Step S360: vacuum evaporation forms the second electron transfer layer, electron injecting layer and cathode layer successively on blue light-emitting, obtains white light organic electroluminescent device.
Preferably, to form the vacuum degree of the second electron transfer layer be 8 × 10 in vacuum evaporation -5pa～3 × 10 -4pa, evaporation rate is
Preferably, the vacuum degree of vacuum evaporation formation electron injecting layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
Preferably, the vacuum degree of vacuum evaporation formation cathode layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The preparation method of above-mentioned white light organic electroluminescent device is simple, and easily operation, and the white light organic electroluminescent device of preparing has higher color rendering index and less operating current, is conducive to industrialization and produces.
Be below specific embodiment part:
Embodiment 1
The structure of the white light organic electroluminescent device of the present embodiment is: ITO/PU/ITO/NPB:MoO 3/ NPB/TCTA:Ir (MDQ) 2(acac)/TCTA:Ir (ppy) 3/ Bphen/MoO 3/ NPB:MoO 3/ NPB/TCTA:Ir (MDQ) 2(acac)/CBP:Firpic:MoO 3/ Bphen/Bphen:Cs 2cO 3/ Ag.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) be that the ito glass substrate of 100 nanometers adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively by thickness, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On a surface of dioptric layer, make the micro-pattern being made up of multiple spaced projections, the width of each projection is 5 microns, is highly 5 microns, and the distance between adjacent two projections is 5 microns; Dioptric layer is there is to surface and the ito glass substrate pressing of micro-pattern, between dioptric layer and glass substrate, form multiple spaces; Then on another surface of dioptric layer, deposition forms indium tin oxide (ITO) transparency conducting layer, obtains anode layer, by anode layer in 80 DEG C of vacuumizes 15 minutes; Wherein, the material of dioptric layer is polyurethane plastic (PU), and anode layer is expressed as: ITO/PU/ITO.
(2) on transparency conducting layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is molybdenum trioxide (MoO 3) doping N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), is expressed as: NPB:MoO 3, wherein, molybdenum trioxide (MoO 3) and N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB) mass ratio is 0.3:1, and the thickness of the first hole injection layer is 12.5 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the first hole transmission layer is N, N '-diphenyl-N, and N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is
(3) on the first hole transmission layer, form the first luminescent layer, the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on the first red light luminescent layer, the first red light luminescent layer is formed on the first hole transmission layer, and the first red light luminescent layer and green luminescence layer are prepared by vacuum evaporation: the material of the first red light luminescent layer is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2) 4,4 of doping (acac) ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:Ir (MDQ) 2(acac), wherein, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2(acac)) with 4,4 ', 4 " mass ratio of tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.01:1, and the thickness of the first red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of green luminescence layer is that three (2-phenylpyridines) close iridium (Ir (ppy) 3) doping 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:Ir (ppy) 3, wherein, three (2-phenylpyridines) close iridium (Ir (ppy) 3) with 4,4 ', 4 " mass ratio of tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.06:1, and the thickness of green luminescence layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the first luminescent layer is expressed as: TCTA:Ir (MDQ) 2(acac)/TCTA:Ir (ppy) 3.
(4) on green luminescence layer, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer successively: the material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), thickness is 35 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of charge generation layer is molybdenum trioxide (MoO 3), thickness is 17.5 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the second hole injection layer is molybdenum trioxide (MoO 3) doping N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), is expressed as: NPB:MoO 3, wherein, molybdenum trioxide (MoO 3) and N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the mass ratio of 4 '-diamines (NPB) is 0.3:1, and the thickness of the second hole injection layer is 12.5 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the second hole transmission layer is N, N '-diphenyl-N, and N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is
(5) on the second hole transmission layer, form the second luminescent layer, the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on the second red light luminescent layer, the second red light luminescent layer is formed on the second hole transmission layer, and the second red light luminescent layer and blue light-emitting are prepared by vacuum evaporation: the material of the second red light luminescent layer is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2) 4,4 of doping (acac) ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:Ir (MDQ) 2(acac), wherein, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2(acac)) with 4,4 ', 4 " mass ratio of tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.01:1, and the thickness of the second red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of blue light-emitting is that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls close iridium (FIrpic) and molybdenum trioxide (MoO 3) 4,4 '-bis-(9-carbazole) biphenyl (CBP) of co-doped, be expressed as: CBP:Firpic:MoO 3, wherein, the mass ratio that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic) and 4,4 '-bis-(9-carbazole) biphenyl (CBP) is 0.125:1, molybdenum trioxide (MoO 3) with the mass ratio of 4,4 '-bis-(9-carbazole) biphenyl (CBP) be 0.075:1, the thickness of blue light-emitting is 10 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the second luminescent layer is expressed as: TCTA:Ir (MDQ) 2(acac)/CBP:Firpic:MoO 3.
(6) on blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and cathode layer successively, obtain white light organic electroluminescent device: the material of the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), thickness is 35 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of electron injecting layer is cesium carbonate (Cs 2cO 3) doping 4,7-diphenyl-1,10-phenanthroline (Bphen), is expressed as: Bphen:Cs 2cO 3, wherein, cesium carbonate (Cs 2cO 3) with 4,7-diphenyl-1,10-phenanthroline (Bphen) mass ratio is 0.3:1, and the thickness of electron injecting layer is 30 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of cathode layer is silver (Ag), and thickness is 125 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the structure that obtains the present embodiment is ITO/PU/ITO/NPB:MoO 3/ NPB/TCTA:Ir (MDQ) 2(acac)/TCTA:Ir (ppy) 3/ Bphen/MoO 3/ NPB:MoO 3/ NPB/TCTA:Ir (MDQ) 2(acac)/CBP:Firpic:MoO 3/ Bphen/Bphen:Cs 2cO 3the white light organic electroluminescent device of/Ag.Wherein, brace "/" represents layer structure, NPB:MoO 3and TCTA:Ir (MDQ) 2etc. (acac) colon ": " in represents that doping mixes, lower with.White light organic electroluminescent device prepared by the present embodiment is at 1000cd/m 2under luminous efficiency and color rendering index in table 1.
Embodiment 2
The structure of the white light organic electroluminescent device of the present embodiment is: ITO/PU/AZO/TCTA:WO 3/ TCTA/mCP:PQIr/mCP:Ir (ppy) 2(acac)/BCP/V 2o 5/ TCTA:WO 3/ TCTA/mCP:PQIr/mCP:FIr6:V 2o 5/ BCP/BCP:CsF/Al.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) be that the ito glass substrate of 100 nanometers adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively by thickness, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On a surface of dioptric layer, make the micro-pattern being made up of multiple spaced projections, the width of each projection is 10 microns, is highly 10 microns, and the distance between adjacent two projections is 10 microns; Dioptric layer is there is to surface and the ito glass substrate pressing of micro-pattern, between dioptric layer and glass substrate, form multiple spaces; Then on another surface of dioptric layer, deposition forms aluminium zinc oxide (AZO) transparency conducting layer, obtains anode layer, by anode layer in 80 DEG C of vacuumizes 15 minutes; Wherein, the material of dioptric layer is polyurethane plastic (PU), and anode layer is expressed as: ITO/PU/AZO.
(2) on transparency conducting layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is tungstic acid (WO 3) doping 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:WO 3, wherein, tungstic acid (WO 3) with 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) mass ratio is 0.25:1, and the thickness of the first hole injection layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the first hole transmission layer is 4,4 ', 4 '-tri-(carbazole-9-yl) triphenylamine (TCTA), thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is
(3) on the first hole transmission layer, form the first luminescent layer, the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on the first red light luminescent layer, the first red light luminescent layer is formed on the first hole transmission layer, and the first red light luminescent layer and green luminescence layer are prepared by vacuum evaporation: the material of the first red light luminescent layer be two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close that iridium (III) (PQIr) adulterates 9, 9 '-(1, 3-phenyl) two-9H-carbazole (mCP), be expressed as: mCP:PQIr, wherein, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr) with 9, 9 '-(1, 3-phenyl) mass ratio of two-9H-carbazole (mCP) is 0.005:1, the thickness of the first red light luminescent layer is 10 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of green luminescence layer is acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2(acac)) 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP) of doping, is expressed as: mCP:Ir (ppy) 2(acac), wherein, acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2(acac) be) 0.02:1 with the mass ratio of 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP), the thickness of green luminescence layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the first luminescent layer is expressed as: mCP:PQIr/mCP:Ir (ppy) 2(acac).
(4) on green luminescence layer, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer successively: the material of the first electron transfer layer is 4,7-diphenyl-1,10-Phen (BCP), thickness is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of charge generation layer is vanadic oxide (V 2o 5), thickness is 5 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the second hole injection layer is tungstic acid (WO 3) doping 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), is expressed as: TCTA:WO 3, wherein, tungstic acid (WO 3) with 4,4 ', 4 " mass ratio of tri-(carbazole-9-yl) triphenylamine (TCTA) is 0.25:1, and the thickness of the second hole injection layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the second hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is
(5) on the second hole transmission layer, form the second luminescent layer, the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on the second red light luminescent layer, the second red light luminescent layer is formed on the second hole transmission layer, and the second red light luminescent layer and blue light-emitting are prepared by vacuum evaporation: the material of the second red light luminescent layer be two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close that iridium (III) (PQIr) adulterates 9, 9 '-(1, 3-phenyl) two-9H-carbazole (mCP), be expressed as: mCP:PQIr, wherein, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr) with 9, 9 '-(1, 3-phenyl) mass ratio of two-9H-carbazole (mCP) is 0.005:1, the thickness of the second red light luminescent layer is 10 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of blue light-emitting is that two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6) and vanadic oxide (V 2o 5) 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP) of co-doped, be expressed as: mCP:FIr6:V 2o 5, wherein, the mass ratio that two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6) and 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP) is 0.05:1, vanadic oxide (V 2o 5) with the mass ratio of 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP) be 0.05:1, the thickness of the second blue light-emitting is 5 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the second luminescent layer is expressed as: mCP:PQIr/mCP:FIr6:V 2o 5.
(6) on blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and cathode layer successively, obtain white light organic electroluminescent device: the material of the second electron transfer layer is 4,7-diphenyl-1,10-Phen (BCP), thickness is 10 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of electron injecting layer is 4 of cesium fluoride (CsF) doping, 7-diphenyl-1,10-Phen (BCP), be expressed as: BCP:CsF, wherein, cesium fluoride (CsF) and 4,7-diphenyl-1,10-Phen (BCP) mass ratio is 0.25:1, and the thickness of electron injecting layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of cathode layer is aluminium (Al), and thickness is 50 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the structure that obtains the present embodiment is ITO/PU/AZO/TCTA:WO 3/ TCTA/mCP:PQIr/mCP:Ir (ppy) 2(acac)/BCP/V 2o 5/ TCTA:WO 3/ TCTA/mCP:PQIr/mCP:FIr6:V 2o 5the white light organic electroluminescent device of/BCP/BCP:CsF/Al.White light organic electroluminescent device prepared by the present embodiment is at 1000cd/m 2under luminous efficiency and color rendering index in table 1.
Embodiment 3
The structure of the white light organic electroluminescent device of the present embodiment is: ITO/PU/IZO/CBP:V 2o 5/ CBP/CBP:(fbi) 2ir (acac)/CBP:Ir (mppy) 3/ BAlq/WO 3/ CBP:V 2o 5/ CBP/CBP:(fbi) 2ir (acac)/CzSi:FCNIr:WO 3/ BAlq/BAlq:CsN 3/ Au.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) be that the ito glass substrate of 100 nanometers adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively by thickness, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On a surface of dioptric layer, make the micro-pattern being made up of multiple spaced projections, the width of each projection is 15 microns, is highly 15 microns, and the distance between adjacent two projections is 15 microns; Dioptric layer is there is to surface and the ito glass substrate pressing of micro-pattern, between dioptric layer and glass substrate, form multiple spaces; Then on another surface of dioptric layer, deposition forms indium-zinc oxide (IZO) transparency conducting layer, obtains anode layer, by anode layer in 60 DEG C of vacuumizes 30 minutes; Wherein, the material of dioptric layer is polyurethane plastic (PU), and anode layer is expressed as: ITO/PU/IZO.
(2) on transparency conducting layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is vanadic oxide (V 2o 5) doping 4,4 '-bis-(9-carbazole) biphenyl (CBP), be expressed as: CBP:V 2o 5, wherein, vanadic oxide (V 2o 5) with 4,4 '-bis-(9-carbazole) biphenyl (CBP) mass ratioes be 0.35:1, the thickness of the first hole injection layer is 15 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the first hole transmission layer is 4,4 '-bis-(9-carbazole) biphenyl (CBP), and thickness is 50 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is
(3) on the first hole transmission layer, form the first luminescent layer, the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on the first red light luminescent layer, the first red light luminescent layer is formed on the first hole transmission layer, and the first red light luminescent layer and green luminescence layer are prepared by vacuum evaporation: the material of the first red light luminescent layer is that two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi) 2ir (acac)) doping 4,4 '-bis-(9-carbazole) biphenyl (CBP), be expressed as: CBP:(fbi) 2ir (acac), wherein, two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi) 2ir (acac)) with the mass ratio of 4,4 '-bis-(9-carbazole) biphenyl (CBP) be 0.02:1, the thickness of the first red light luminescent layer is 30 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of green luminescence layer is that three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) doping 4,4 '-bis-(9-carbazole) biphenyl (CBP), be expressed as: CBP:Ir (mppy) 3, wherein, three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) with the mass ratio of 4,4 '-bis-(9-carbazole) biphenyl (CBP) be 0.1:1, the thickness of green luminescence layer is 30 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the first luminescent layer is expressed as: CBP:(fbi) 2ir (acac)/CBP:Ir (mppy) 3.
(4) on green luminescence layer, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer successively: the material of the first electron transfer layer is that 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), thickness is 60 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of charge generation layer is tungstic acid (WO 3), thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the second hole injection layer is vanadic oxide (V 2o 5) doping 4,4 '-bis-(9-carbazole) biphenyl (CBP), be expressed as: CBP:V 2o 5, wherein, vanadic oxide (V 2o 5) with the mass ratio of 4,4 '-bis-(9-carbazole) biphenyl (CBP) be 0.35:1, the thickness of the second hole injection layer is 15 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the second hole transmission layer is 4,4 '-bis-(9-carbazole) biphenyl (CBP), and thickness is 50 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is
(5) on the second hole transmission layer, form the second luminescent layer, the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on the second red light luminescent layer, the second red light luminescent layer is formed on the second hole transmission layer, and the second red light luminescent layer and blue light-emitting are prepared by vacuum evaporation: the material of the second red light luminescent layer is that two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi) 2ir (acac)) doping 4,4 '-bis-(9-carbazole) biphenyl (CBP), be expressed as: CBP:(fbi) 2ir (acac), wherein, two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi) 2ir (acac)) with the mass ratio of 4,4 '-bis-(9-carbazole) biphenyl (CBP) be 0.02:1, the thickness of the second red light luminescent layer is 30 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of blue light-emitting is three (2-(4 ', 6 '-bis-fluoro-5 '-cyano group) phenylpyridine-N, C2 ') close iridium (FCNIr) and tungstic acid (WO 3) 9-(4-2-methyl-2-phenylpropane base)-3 of co-doped, two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-, are expressed as: CzSi:FCNIr:WO 3, wherein, three (2-(4 ', 6 '-bis-fluoro-5 '-cyano group) phenylpyridine-N, C2 ') close iridium (FCNIr) and 9-(4-2-methyl-2-phenylpropane base)-3, the mass ratio of two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-is 0.2:1, tungstic acid (WO 3) and 9-(4-2-methyl-2-phenylpropane base)-3, the mass ratio of two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-is 0.1:1, and the thickness of blue light-emitting is 15 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the second luminescent layer is expressed as: CBP:(fbi) 2ir (acac)/CzSi:FCNIr:WO 3.
(6) on blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and cathode layer successively, obtain white light organic electroluminescent device: the material of the second electron transfer layer is that 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), thickness is 60 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of electron injecting layer is cesium azide (CsN 3) doping 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), be expressed as: BAlq:CsN 3, wherein, cesium azide (CsN 3) to close aluminium (BAlq) mass ratio be 0.35:1 with 4-biphenyl phenolic group-bis-(2-methyl-oxine), the thickness of electron injecting layer is 40 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of cathode layer is gold (Au), and thickness is 200 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the structure that obtains the present embodiment is ITO/PU/IZO/CBP:V 2o 5/ CBP/CBP:(fbi) 2ir (acac)/CBP:Ir (mppy) 3/ BAlq/WO 3/ CBP:V 2o 5/ CBP/CBP:(fbi) 2ir (acac)/CzSi:FCNIr:WO 3/ BAlq/BAlq:CsN 3the white light organic electroluminescent device of/Au.White light organic electroluminescent device prepared by the present embodiment is at 1000cd/m 2under luminous efficiency and color rendering index in table 1.
Embodiment 4
The structure of the white light organic electroluminescent device of the present embodiment is: ITO/PEN/ITO/TPD:ReO 3/ TPD/TPD:(F-BT) 2ir (acac)/TPD:Ir (ppy) 3/ Alq 3/ ReO 3/ TPD:ReO 3/ TPD/TPD:(F-BT) 2ir (acac)/26DCzPPY:FIrtaz:ReO 3/ Alq 3/ Alq 3: Li 2cO 3/ Ag.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) be that the ito glass substrate of 100 nanometers adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively by thickness, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On a surface of dioptric layer, make the micro-pattern being made up of multiple spaced projections, the width of each projection is 20 microns, is highly 20 microns, and the distance between adjacent two projections is 20 microns; Dioptric layer is there is to surface and the ito glass substrate pressing of micro-pattern, between dioptric layer and glass substrate, form multiple spaces; Then on another surface of dioptric layer, deposition forms indium tin oxide (ITO) transparency conducting layer, obtains anode layer, by anode layer in 70 DEG C of vacuumizes 20 minutes; Wherein, the material of dioptric layer is PEN (PEN), and anode layer is expressed as: ITO/PEN/ITO.
(2) on transparency conducting layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is rhenium trioxide (ReO 3) doping N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), is expressed as: TPD:ReO 3, wherein, rhenium trioxide (ReO 3) and N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) mass ratio is 0.3:1, and the thickness of the first hole injection layer is 13 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the first hole transmission layer is N, N '-bis-(3-aminomethyl phenyl)-N, and N '-diphenyl-4,4 '-benzidine (TPD), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is
(3) on the first hole transmission layer, form the first luminescent layer, the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on the first red light luminescent layer, the first red light luminescent layer is formed on the first hole transmission layer, and the first red light luminescent layer and green luminescence layer are prepared by vacuum evaporation: the material of the first red light luminescent layer be two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) ((F-BT) 2ir (acac)) N of doping, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), is expressed as: TPD:(F-BT) 2ir (acac), wherein, two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) closes iridium (III) ((F-BT) 2ir (acac)) and N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, the mass ratio of 4 '-benzidine (TPD) is 0.01:1, and the thickness of the first red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of green luminescence layer is that three (2-phenylpyridines) close iridium (Ir (ppy) 3) doping N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), is expressed as: TPD:Ir (ppy) 3, wherein, three (2-phenylpyridines) close iridium (Ir (ppy) 3) and N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, the mass ratio of 4 '-benzidine (TPD) is 0.05:1, and the thickness of green luminescence layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the first luminescent layer is expressed as: TPD:(F-BT) 2ir (acac)/TPD:Ir (ppy) 3.
(4) on green luminescence layer, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer successively: the material of the first electron transfer layer is oxine aluminium (Alq 3), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of charge generation layer is rhenium trioxide (ReO 3), thickness is 20 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the second hole injection layer is rhenium trioxide (ReO 3) doping N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), is expressed as: TPD:ReO 3, wherein, rhenium trioxide (ReO 3) and N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, the mass ratio of 4 '-benzidine (TPD) is 0.3:1, and the thickness of the second hole injection layer is 12 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of the second hole transmission layer is N, N '-bis-(3-aminomethyl phenyl)-N, and N '-diphenyl-4,4 '-benzidine (TPD), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is
(5) on the second hole transmission layer, form the second luminescent layer, the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on the second red light luminescent layer, the second red light luminescent layer is formed on the second hole transmission layer, and the second red light luminescent layer and blue light-emitting are prepared by vacuum evaporation: the material of the second red light luminescent layer be two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close the N of iridium (III) ((F-BT) 2Ir (acac)) doping, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine (TPD), be expressed as: TPD:(F-BT) 2ir (acac), wherein, two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) closes iridium (III) ((F-BT) 2ir (acac)) and N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, the mass ratio of 4 '-benzidine (TPD) is 0.01:1, and the thickness of the second red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of blue light-emitting is that two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazoles) are closed iridium (FIrtaz) and rhenium trioxide (ReO 3) co-doped 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-, are expressed as: 26DCzPPY:FIrtaz:ReO 3wherein, two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium (FIrtaz) and 2, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-is 0.12:1, rhenium trioxide (ReO 3) with 2, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-is 0.07:1, the thickness of blue light-emitting is 10 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the second luminescent layer is expressed as: TPD:(F-BT) 2ir (acac)/26DCzPPY:FIrtaz:ReO 3.
(6) on blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and cathode layer successively, obtains white light organic electroluminescent device: the material of the second electron transfer layer is oxine aluminium (Alq 3), thickness is 30 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of electron injecting layer is lithium carbonate (Li 2cO 3) doping oxine aluminium (Alq 3), be expressed as: Alq 3: Li 2cO 3, wherein, lithium carbonate (Li 2cO 3) and oxine aluminium (Alq 3) mass ratio be 0.3:1, the thickness of electron injecting layer is 30 nanometers, the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the material of cathode layer is silver (Ag), and thickness is 100 nanometers, and the vacuum degree of vacuum evaporation is 5 × 10 -5pa, evaporation rate is the structure that obtains the present embodiment is ITO/PEN/ITO/TPD:ReO 3/ TPD/TPD:(F-BT) 2ir (acac)/TPD:Ir (ppy) 3/ Alq 3/ ReO 3/ TPD:ReO 3/ TPD/TPD:(F-BT) 2ir (acac)/26DCzPPY:FIrtaz:ReO 3/ Alq 3/ Alq 3: Li 2cO 3the white light organic electroluminescent device of/Ag.White light organic electroluminescent device prepared by the present embodiment is at 1000cd/m 2under luminous efficiency and color rendering index in table 1.
Embodiment 5
The structure of the white light organic electroluminescent device of the present embodiment is: ITO/PI/ITO/TAPC:MoO 3/ TAPC/TAPC:Ir (btp) 2(acac)/TAPC:Ir (ppy) 2(acac)/TAZ/MoO 3/ TAPC:MoO 3/ TAPC/TAPC:Ir (btp) 2(acac)/35DCzPPY:FIrN4:MoO 3/ TAZ/TAZ:LiF/Al.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) be that the ito glass substrate of 100 nanometers adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively by thickness, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On a surface of dioptric layer, make the micro-pattern being made up of multiple spaced projections, the width of each projection is 11 microns, is highly 11 microns, and the distance between adjacent two projections is 11 microns; Dioptric layer is there is to surface and the ito glass substrate pressing of micro-pattern, between dioptric layer and glass substrate, form multiple spaces; Then on another surface of dioptric layer, deposition forms indium tin oxide (ITO) transparency conducting layer, obtains anode layer, by anode layer in 80 DEG C of vacuumizes 15 minutes; Wherein, the material of dioptric layer is polyimides (PI), and anode layer is expressed as: ITO/PI/ITO.
(2) on transparency conducting layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is molybdenum trioxide (MoO 3) doping 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:MoO 3, wherein, molybdenum trioxide (MoO 3) with 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.25:1, and the thickness of the first hole injection layer is 10 nanometers, and the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the material of the first hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is
(3) on the first hole transmission layer, form the first luminescent layer, the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on the first red light luminescent layer, the first red light luminescent layer is formed on the first hole transmission layer, and the first red light luminescent layer and green luminescence layer are prepared by vacuum evaporation: the material of the first red light luminescent layer is that two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp) 2(acac)) 41 of doping, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:Ir (btp) 2(acac), wherein, two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp) 2(acac)) with 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.01:1, and the thickness of the first red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the material of green luminescence layer is (Ir (ppy) 2(acac)) 1 of doping, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:Ir (ppy) 2(acac), wherein, (Ir (ppy) 2(acac)) with 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.07:1, and the thickness of green luminescence layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the first luminescent layer is expressed as: TAPC:Ir (btp) 2(acac)/TAPC:Ir (ppy) 2(acac).
(4) on green luminescence layer, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer successively: the material of the first electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), thickness is 40 nanometers, and the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the material of charge generation layer is molybdenum trioxide (MoO 3), thickness is 20 nanometers, the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the material of the second hole injection layer is molybdenum trioxide (MoO 3) doping 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:MoO 3, wherein, molybdenum trioxide (MoO 3) with 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.28:1, and the thickness of the second hole injection layer is 13 nanometers, and the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the material of the second hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is
(5) on the second hole transmission layer, form the second luminescent layer, the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on the second red light luminescent layer, the second red light luminescent layer is formed on the second hole transmission layer, and the second red light luminescent layer and blue light-emitting are prepared by vacuum evaporation: the material of the second red light luminescent layer is that two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp) 2(acac)) 1 of doping, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), be expressed as: TAPC:Ir (btp) 2(acac), wherein, two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp) 2(acac)) with 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] mass ratio of cyclohexane (TAPC) is 0.01:1, and the thickness of the second red light luminescent layer is 20 nanometers, and the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the material of blue light-emitting is that two (4,6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazoliums) close iridium (FIrN4) and molybdenum trioxide (MoO 3) co-doped 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines (35DCzPPY) of 5-, are expressed as: 35DCzPPY:FIrN4:MoO 3wherein, two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) closes iridium (FIrN4) and 3, two (3-(9H-carbazole-9-yl) phenyl) pyridine (35DCzPPY) mass ratioes of 5-are 0.12:1, molybdenum trioxide (MoO 3) with 3, the mass ratio of two (3-(9H-carbazole-9-yl) phenyl) pyridines (35DCzPPY) of 5-is 0.07:1, the thickness of blue light-emitting is 10 nanometers, the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the second luminescent layer is expressed as: TAPC:Ir (btp) 2(acac)/35DCzPPY:FIrN4:MoO 3.
(6) on blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and cathode layer successively, obtain white light organic electroluminescent device: the material of the second electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), thickness is 50 nanometers, and the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the material of electron injecting layer is 3-(biphenyl-4-yl)-5-(4-the tert-butyl-phenyl)-4-phenyl-4H-1 of lithium fluoride (LiF) doping, 2,4-triazole (TAZ), be expressed as: TAZ:LiF, wherein, lithium fluoride (LiF) and 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2, the mass ratio of 4-triazole (TAZ) is 0.3:1, and the thickness of electron injecting layer is 30 nanometers, and the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the material of cathode layer is aluminium (Al), and thickness is 100 nanometers, and the vacuum degree of vacuum evaporation is 8 × 10 -5pa, evaporation rate is the structure that obtains the present embodiment is ITO/PI/ITO/TAPC:MoO 3/ TAPC/TAPC:Ir (btp) 2(acac)/TAPC:Ir (ppy) 2(acac)/TAZ/MoO 3/ TAPC:MoO 3/ TAPC/TAPC:Ir (btp) 2(acac)/35DCzPPY:FIrN4:MoO 3the white light organic electroluminescent device of/TAZ/TAZ:LiF/Al.White light organic electroluminescent device prepared by the present embodiment is at 1000cd/m 2under luminous efficiency and color rendering index in table 1.
Embodiment 6
The structure of the white light organic electroluminescent device of the present embodiment is: ITO/PU/NPB:WO 3/ NPB/ADN:Ir (piq) 3/ ADN:Ir (mppy) 3/ UGH2:Firpic/TPBI/V 2o 5/ NPB:WO 3/ NPB/ADN:Ir (piq) 3/ ADN:Ir (mppy) 3/ UGH2:Firpic/TPBI/TPBI:Li 2o/Al.
Being prepared as follows of the white light organic electroluminescent device of this embodiment:
(1) be that the ito glass substrate of 100 nanometers adopts liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively by thickness, each cleaning 5 minutes, stops 5 minutes, repeats respectively 3 times, then use oven for drying, the glass substrate after drying is carried out to surface activation process; On a surface of dioptric layer, make the micro-pattern being made up of multiple spaced projections, the width of each projection is 18 microns, is highly 18 microns, and the distance between adjacent two projections is 18 microns; Dioptric layer is there is to surface and the ito glass substrate pressing of micro-pattern, between dioptric layer and glass substrate, form multiple spaces; Then on another surface of dioptric layer, deposition forms indium tin oxide (ITO) transparency conducting layer, obtains anode layer, by anode layer in 80 DEG C of vacuumizes 15 minutes; Wherein, the material of dioptric layer is polyurethane plastic (PU), and anode layer is expressed as: ITO/PU/ITO.
(2) on transparency conducting layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively: the material of the first hole injection layer is tungstic acid (WO 3) doping N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), is expressed as: NPB:WO 3, wherein, tungstic acid (WO 3) and N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB) mass ratio is 0.3:1, and the thickness of the first hole injection layer is 12 nanometers, and the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the material of the first hole transmission layer is N, N '-diphenyl-N, and N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is
(3) on the first hole transmission layer, form the first luminescent layer, the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on the first red light luminescent layer, the first red light luminescent layer is formed on the first hole transmission layer, and the first red light luminescent layer and green luminescence layer are prepared by vacuum evaporation: the material of the first red light luminescent layer is that three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) doping 9, two (1-naphthyl) anthracenes (ADN) of 10-, are expressed as: ADN:Ir (piq) 3, wherein, three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) with 9, the mass ratio of two (1-naphthyl) anthracenes (ADN) of 10-is 0.01:1, the thickness of the first red light luminescent layer is 20 nanometers, the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the material of green luminescence layer is that three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) doping 9, two (1-naphthyl) anthracenes (ADN) of 10-, are expressed as: ADN:Ir (mppy) 3, wherein, three [2-(p-methylphenyl) pyridines] close iridium (III) (Ir (mppy) 3) with 9, the mass ratio of two (1-naphthyl) anthracenes (ADN) of 10-is 0.06:1, the thickness of green luminescence layer is 20 nanometers, the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the first luminescent layer is expressed as: ADN:Ir (piq) 3/ ADN:Ir (mppy) 3.
(4) on green luminescence layer, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer successively: the material of the first electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), thickness is 40 nanometers, and the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the material of charge generation layer is vanadic oxide (V 2o 5), thickness is 20 nanometers, the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the material of the second hole injection layer is tungstic acid (WO 3) doping N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), is expressed as: NPB:WO 3, wherein, tungstic acid (WO 3) and N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the mass ratio of 4 '-diamines (NPB) is 0.3:1, and the thickness of the second hole injection layer is 12 nanometers, and the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the material of the second hole transmission layer is N, N '-diphenyl-N, and N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), thickness is 40 nanometers, the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is
(5) on the second hole transmission layer, form the second luminescent layer, the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on the second red light luminescent layer, the second red light luminescent layer is formed on the second hole transmission layer, and the second red light luminescent layer and blue light-emitting are prepared by vacuum evaporation: the material of the second red light luminescent layer is that three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) doping 9, two (1-naphthyl) anthracenes (ADN) of 10-, are expressed as: ADN:Ir (piq) 3, wherein, three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) with 9, the mass ratio of two (1-naphthyl) anthracenes (ADN) of 10-is 0.01:1, the thickness of the second red light luminescent layer is 20 nanometers, the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the material of blue light-emitting is that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls close iridium (FIrpic) and vanadic oxide (V 2o 5) co-doped Isosorbide-5-Nitrae--two (triphenyl silicon) benzene (UGH2), are expressed as: UGH2:Firpic:V 2o 5, wherein, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic) and Isosorbide-5-Nitrae--and the mass ratio of two (triphenyl silicon) benzene (UGH2) is 0.12:1, vanadic oxide (V 2o 5) and Isosorbide-5-Nitrae--the mass ratio of two (triphenyl silicon) benzene (UGH2) is 0.07:1, and the thickness of blue light-emitting is 10 nanometers, and the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the second luminescent layer is expressed as: ADN:Ir (piq) 3/ UGH2:Firpic:V 2o 5.
(6) on blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and cathode layer successively, obtain white light organic electroluminescent device: the material of the second electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), thickness is 30 nanometers, and the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the material of electron injecting layer is lithia (Li 2o) 1,3 of doping, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), is expressed as: TPBI:Li 2o, wherein, lithia (Li 2o) with 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) mass ratio is 0.3:1, and the thickness of electron injecting layer is 30 nanometers, and the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the material of cathode layer is aluminium (Al), and thickness is 100 nanometers, and the vacuum degree of vacuum evaporation is 3 × 10 -4pa, evaporation rate is the structure that obtains the present embodiment is ITO/PU/ITO/NPB:WO 3/ NPB/ADN:Ir (piq) 3/ ADN:Ir (mppy) 3/ TPBI/V 2o 5/ NPB:WO 3/ NPB/ADN:Ir (piq) 3/ UGH2:Firpic:V 2o 5/ TPBI/TPBI:Li 2the white light organic electroluminescent device of O/Al.White light organic electroluminescent device prepared by the present embodiment is at 1000cd/m 2under luminous efficiency and color rendering index in table 1.
What table 1 represented is white light organic electroluminescent device prepared by embodiment 1～embodiment 6 is at 1000cd/m 2under luminous efficiency and the data of color rendering index.
Table 1
? Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Luminous efficiency (lm/W) 14.2 15.3 13.7 10.3 11.2 9.5
Color rendering index (CRI) 80 78 79 77.5 76 75
From table 1, can learn, white light organic electroluminescent device prepared by embodiment 1～embodiment 6 is at 1000cd/m 2under luminous efficiency be at least 9.5lm/W, and white light organic electroluminescent device prepared by embodiment 6 is at 1000cd/m 2under luminous efficiency maximum can reach 15.3lm/W, and this kind of traditional white light organic electroluminescent device is at 1000cd/m 2under luminous efficiency maximum can reach 7lm/W, illustrate that white light organic electroluminescent device prepared by embodiment 1～embodiment 6 has less operating current; And the color rendering index of white light organic electroluminescent device prepared by embodiment 1～embodiment 6 is minimum is 75, and white light organic electroluminescent device prepared by embodiment 1 reach as high as 80, and the color rendering index maximum of traditional white light organic electroluminescent device only has 70, illustrate that the color rendering index of white light organic electroluminescent device prepared by embodiment 1～embodiment 6 has higher color rendering index.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, 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 claims.

Claims (10)

1. a white light organic electroluminescent device, it is characterized in that, comprise the anode layer stacking gradually, the first hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole injection layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and cathode layer, described anode layer comprises the glass substrate stacking gradually, dioptric layer and transparency conducting layer, the surface that described dioptric layer is relative with described glass substrate is provided with the micro-pattern being made up of multiple spaced projections, make to form multiple spaces between described dioptric layer and described glass substrate, described the first hole injection layer is laminated on described transparency conducting layer, described the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer of described the first red light luminescent layer, and described the first red light luminescent layer is laminated on described the first hole transmission layer, described the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting of described the second red light luminescent layer, and described the second red light luminescent layer is laminated on described the second hole transmission layer, wherein, described blue light emitting material comprises Blue-light emitting host material and co-doped blue light guest materials and the charge generating material in described Blue-light emitting host material, the mass ratio of described blue light guest materials and described Blue-light emitting host material is 0.05～0.2:1, and the mass ratio of described charge generating material and described Blue-light emitting host material is 0.05～0.1:1, described Blue-light emitting host material is selected from 4,4 '-bis-(9-carbazole) biphenyl, 9,9 '-(1,3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles, 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines, 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine and Isosorbide-5-Nitrae--the one in two (triphenyl silicon) benzene of 5-, described blue light guest materials is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid close iridium, three (2-(4 ', 6 '-bis-fluoro-5 '-cyano group) phenylpyridine-N, C2 ') close iridium, two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium and two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) closes the one in iridium, described charge generating material is selected from the one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide.
2. white light organic electroluminescent device according to claim 1, is characterized in that, the material of described glass substrate is indium tin oxide glass; The material of described dioptric layer is that refractive index is 1.7～1.9 overlay; The width of each projection is 5 microns～20 microns, is highly 5 microns～20 microns, and distance between adjacent two projections is 5 microns～20 microns; The material of described transparency conducting layer is the one in indium tin oxide, aluminium zinc oxide and indium-zinc oxide.
3. white light organic electroluminescent device according to claim 1, it is characterized in that, the material of described the first red light luminescent layer comprises the first ruddiness material of main part and is doped in the first ruddiness guest materials in described the first ruddiness material of main part, and the mass ratio of described the first ruddiness guest materials and described the first ruddiness material of main part is 0.005～0.02:1, the material of described green luminescence layer comprises green glow material of main part and is doped in the green glow guest materials in described green glow material of main part, and the mass ratio of described green glow guest materials and described green glow material of main part is 0.02～0.1:1, the material of described the second red light luminescent layer comprises the second ruddiness material of main part and is doped in the second ruddiness guest materials in described the second ruddiness material of main part, and the mass ratio of described the second ruddiness guest materials and described the second ruddiness material of main part is 0.005～0.02:1, described the first ruddiness material of main part, described green glow material of main part and described the second ruddiness material of main part are selected from respectively 4,4 ', 4 " tri-(carbazole-9-yl) 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 '-bis-(p-tolyl) amino] phenyl] one in two (1-naphthyl) anthracenes of cyclohexane and 9,10-, described the first ruddiness guest materials and described the second ruddiness guest materials are selected from respectively two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) and three (1-phenyl-isoquinolin) and close the one in iridium, described green glow guest materials is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium and three [2-(p-methylphenyl) pyridine] closes the one in iridium (III).
4. white light organic electroluminescent device according to claim 1, is characterized in that, the thickness of described the first red light luminescent layer is 10 nanometer～30 nanometers; The thickness of described green luminescence layer is 10 nanometer～30 nanometers; The thickness of described the second red light luminescent layer is 10 nanometer～30 nanometers; The thickness of described blue light-emitting is 5 nanometer～15 nanometers.
5. white light organic electroluminescent device according to claim 1, it is characterized in that, the material of described the first hole injection layer comprises the first hole mobile material and is doped in the first p-type dopant in described the first hole mobile material, and the mass ratio of described the first p-type dopant and described the first hole mobile material is 0.25～0.35:1; The material of described the second hole injection layer comprises the second hole mobile material and is doped in the second p-type dopant in described the second hole mobile material, and the mass ratio of described the second p-type dopant and described the second hole mobile material is 0.25～0.35:1; Described the first hole mobile material and described the second hole mobile material are selected from respectively N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 4; 4 '-bis-(9-carbazole) biphenyl, N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] one in cyclohexane; Described the first p-type dopant and described the second p-type dopant are selected from respectively the one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide;
The material of the material of described the first hole transmission layer and described the second hole transmission layer is selected from respectively N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine, 4; 4 '-bis-(9-carbazole) biphenyl, N; N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine and 1; 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] one in cyclohexane;
The material of the material of described the first electron transfer layer and described the second electron transfer layer is selected from respectively 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described charge generation layer is the one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide;
The material of described electron injecting layer comprises electron transport material and is doped in the N-shaped dopant in described electron transport material, and the mass ratio of described N-shaped dopant and described electron transport material is 0.25～0.35:1; Described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole and 1, one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; Described N-shaped dopant is the one in cesium carbonate, cesium fluoride, cesium azide, lithium carbonate, lithium fluoride and lithia; And
The material of described cathode layer is the one in silver, aluminium and gold.
6. white light organic electroluminescent device according to claim 1, is characterized in that, the thickness of described the first hole injection layer is 10 nanometer～15 nanometers; The thickness of described the first hole transmission layer is 30 nanometer～50 nanometers; The thickness of described the first electron transfer layer is 10 nanometer～60 nanometers; The thickness of described charge generation layer is 5 nanometer～30 nanometers; The thickness of described the second hole injection layer is 10 nanometer～15 nanometers; The thickness of described the second hole transmission layer is 30 nanometer～50 nanometers; The thickness of described the second electron transfer layer is 10 nanometer～60 nanometers; The thickness of described electron injecting layer is 20 nanometer～40 nanometers; The thickness of described cathode layer is 50 nanometer～200 nanometers.
7. a preparation method for white light organic electroluminescent device, is characterized in that, comprises the steps:
On a surface of dioptric layer, make the micro-pattern being formed by multiple spaced projections, described dioptric layer is there is to surface and the glass substrate pressing of described micro-pattern, then on another surface of described dioptric layer, deposition forms transparency conducting layer, obtain anode layer, wherein, between described dioptric layer and described glass substrate, form multiple spaces;
On described transparency conducting layer, vacuum evaporation forms the first hole injection layer and the first hole transmission layer successively;
On described the first hole transmission layer, form the first luminescent layer, described the first luminescent layer comprises the first red light luminescent layer and is laminated in the green luminescence layer on described the first red light luminescent layer, described the first red light luminescent layer is formed on described the first hole transmission layer, and described the first red light luminescent layer and described green luminescence layer are prepared by vacuum evaporation;
On described green luminescence layer, vacuum evaporation forms the first electron transfer layer, charge generation layer, the second hole injection layer and the second hole transmission layer successively;
On described the second hole transmission layer, form the second luminescent layer, described the second luminescent layer comprises the second red light luminescent layer and is laminated in the blue light-emitting on described the second red light luminescent layer, described the second red light luminescent layer is formed on described the second hole transmission layer, and described the second red light luminescent layer and described blue light-emitting are prepared by vacuum evaporation; Wherein, described blue light emitting material comprises Blue-light emitting host material and co-doped blue light guest materials and the charge generating material in described Blue-light emitting host material, the mass ratio of described blue light guest materials and described Blue-light emitting host material is 0.05～0.2:1, and the mass ratio of described charge generating material and described Blue-light emitting host material is 0.05～0.1:1; Described Blue-light emitting host material is selected from 4,4 '-bis-(9-carbazole) biphenyl, 9,9 '-(1,3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles, 2 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridines, 3 of 6-, two (3-(9H-carbazole-9-yl) phenyl) pyridine and Isosorbide-5-Nitrae--the one in two (triphenyl silicon) benzene of 5-; Described blue light guest materials is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid close iridium, three (2-(4 ', 6 '-bis-fluoro-5 '-cyano group) phenylpyridine-N, C2 ') close iridium, two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium and two (4,6-difluorophenyl pyridines) (5-(pyridine-2-yl)-tetrazolium) closes the one in iridium; Described charge generating material is selected from the one in molybdenum trioxide, tungstic acid, vanadic oxide and rhenium trioxide; And
On described blue light-emitting, vacuum evaporation forms the second electron transfer layer, electron injecting layer and cathode layer successively, obtains white light organic electroluminescent device.
8. the preparation method of white light organic electroluminescent device according to claim 7, it is characterized in that described dioptric layer is had and also comprises before the surface of described micro-pattern and described glass substrate pressing described glass substrate is cleaned and the step of surface activation process successively; The step of described cleaning is: glass substrate is adopted to liquid detergent, deionized water, acetone and ethanol ultrasonic cleaning successively, and then dry.
9. the preparation method of white light organic electroluminescent device according to claim 7, it is characterized in that, before on described transparency conducting layer, vacuum evaporation forms described the first hole injection layer, also comprise described anode layer in 60 DEG C～80 DEG C vacuumizes 15 minutes～30 minutes.
10. the preparation method of white light organic electroluminescent device according to claim 7, is characterized in that, the vacuum degree that vacuum evaporation forms described the first hole injection layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the first hole transmission layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the first red light luminescent layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described green luminescence layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the first electron transfer layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described charge generation layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the second hole injection layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the second hole transmission layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the second red light luminescent layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described blue light-emitting is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described the second electron transfer layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
The vacuum degree that vacuum evaporation forms described electron injecting layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is and
The vacuum degree that vacuum evaporation forms described cathode layer is 8 × 10 -5pa～3 × 10 -4pa, evaporation rate is
CN201310109511.2A 2013-03-29 2013-03-29 White organic light-emitting diode and manufacturing method thereof Pending CN104078604A (en)

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CN110707226A (en) * 2019-10-16 2020-01-17 苏州大学 Organic light-emitting device, preparation method thereof and light-emitting device
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Application publication date: 20141001