CN103633253A - Blue light organic electroluminescent device and preparation method thereof - Google Patents

Blue light organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN103633253A
CN103633253A CN201210312914.2A CN201210312914A CN103633253A CN 103633253 A CN103633253 A CN 103633253A CN 201210312914 A CN201210312914 A CN 201210312914A CN 103633253 A CN103633253 A CN 103633253A
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blue light
glass
tapered protrusion
substrate
layer
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周明杰
王平
钟铁涛
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a blue light organic electroluminescent device with a structure comprising a glass substrate, an anode, a hole injection layer, a hole transmission layer, a blue light-emitting layer, an electron transmission layer, an electron injection layer and a cathode which are laminated in turn. Multiple cone-shaped protrusions are arranged on both surfaces of the glass substrate in arrays. According to the blue light organic electroluminescent device, multiple cone-shaped protrusions are arranged on both surfaces of the glass substrate in arrays. Compared with a conventional blue light organic electroluminescent device adopting a flat glass substrate, the blue light organic electroluminescent device adopting the patterned glass substrate is higher in light emission efficiency. The invention also provides a preparation method of the aforementioned blue light organic electroluminescent device.

Description

A kind of blue light organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to organic electroluminescent field, relate in particular to a kind of blue light organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device, also referred to as Organic Light Emitting Diode (OLED), is a kind of device that electric energy is converted into luminous energy.1987, C.W.Tang and partner thereof are first by hole mobile material N, N '-diphenyl N, N '-bis-(3 tolyl)-4,4-' benzidine as hole transmission layer, there is electron transport ability oxine aluminium as electron transfer layer and luminescent layer, made and there is double-deck small molecular blue light organic electroluminescence device.
Organic electroluminescence device (OLED) has advantages of that some are unique: (1) OLED belongs to diffused area source, does not need by extra light-conducting system, to obtain large-area white light source as light-emitting diode (LED); (2) due to the diversity of luminous organic material, OLED illumination is the 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 white-light spectrum at the light of 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.
Traditional blue light organic electroluminescence device adopts prepares each layer of structure on smooth glass substrate, and smooth glass substrate makes luminous efficiency lower.
Summary of the invention
Based on this, provide blue light organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A blue light organic electroluminescence device, comprises the following structure stacking gradually:
Substrate of glass, anode, hole injection layer, hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode;
Described substrate of glass two sides is equipped with the tapered protrusion of a plurality of array arrangements.
In one embodiment, the height of described tapered protrusion is 5 μ m ~ 10 μ m, and the length of side of bottom surface is 5 μ m ~ 20 μ m, and the spacing of every two adjacent described tapered protrusion is 1 μ m ~ 5 μ m.
In one embodiment, the tapered protrusion that described substrate of glass two sides is provided with arranges for corresponding.
In one embodiment, the thickness of described substrate of glass is 0.7mm ~ 1.1mm.0.7mm～1.1mm
In one embodiment, described anode is provided with the tapered protrusion of a plurality of array arrangements away from a side setting of described substrate of glass.
In one embodiment, the material of described hole injection layer is that mass ratio is poly-3,4-dioxy ethene thiophene and the polyphenyl sulfonate of 2:1 ~ 6:1;
The thickness of described hole injection layer is 20nm ~ 80nm.
In one embodiment, the material of described blue light-emitting is the material of main part of blue light guest materials of having adulterated;
Described material of main part is 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 the Isosorbide-5-Nitraes of 5---at least one in two (triphenyl silicon) benzene;
Described blue light guest materials is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) 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 pyridine) (5-(pyridine-2-yl)-tetrazolium) close at least one in iridium;
Described blue light guest materials account for described blue light-emitting gross mass mass percent 5% ~ 20%.
In one embodiment, the thickness of described blue light-emitting is 5nm ~ 15nm.
A preparation method for blue light organic electroluminescence device, comprises the steps:
Clean substrate of glass is provided;
In the one side of described substrate of glass, form the tapered protrusion of a plurality of array arrangements;
At the another side of described substrate of glass, form the tapered protrusion of a plurality of array arrangements;
One side in described substrate of glass forms anode, hole injection layer, hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode successively.
In one embodiment, the described one side in substrate of glass forms the step of the tapered protrusion of a plurality of array arrangements and is:
Preparation surface is provided with the polymethyl methacrylate model of the tapered protrusion of a plurality of array arrangements;
Described polymethyl methacrylate model is attached to the one side of described substrate of glass, by reactive ion etching, in the one side of described substrate of glass, forms the tapered protrusion of a plurality of array arrangements.
The two sides of the substrate of glass of this blue light organic electroluminescence device is equipped with the tapered protrusion of a plurality of array arrangements, adopt the blue light organic electroluminescence device of the substrate of glass of this patterning, compare with the blue light organic electroluminescence device of the traditional smooth substrate of glass of employing, luminous efficiency is higher.
Accompanying drawing explanation
Fig. 1 is the structural representation of the blue light organic electroluminescence device of an execution mode;
Fig. 2 is that the substrate of glass of blue light organic electroluminescence device is as shown in Figure 1 near the schematic diagram of the one side of anode;
Fig. 3 is that the substrate of glass of blue light organic electroluminescence device is as shown in Figure 1 away from the schematic diagram of the one side of anode;
Fig. 4 is the preparation method's of blue light organic electroluminescence device as shown in Figure 1 flow chart;
Fig. 5 is the luminous efficiency figure of the blue light organic electroluminescence device of embodiment 1 ~ embodiment 7 preparations.
Embodiment
For the ease of understanding the present invention, below with reference to relevant drawings, the present invention is described more fully.In accompanying drawing, provided preferred embodiment of the present invention.But the present invention can realize in many different forms, be not limited to embodiment described herein.On the contrary, providing the object of these embodiment is to make to the understanding of disclosure of the present invention more thoroughly comprehensively.
The blue light organic electroluminescence device of an execution mode as shown in Figure 1, comprises the following structure stacking gradually:
Substrate of glass 10, anode 20, hole injection layer 30, hole transmission layer 40, blue light-emitting 50, electron transfer layer 60, electron injecting layer 70 and negative electrode 80.
The glass that substrate of glass 10 can selective refraction rate is 2.0 ~ 2.6.Thereby make the refractive index ratio anode 20 of substrate of glass 10 want large, light incides optically denser medium by optically thinner medium like this, avoids occurring total reflection, reduces the loss of light.
The thickness of substrate of glass 10 can be 0.7mm ~ 1.1mm.
In conjunction with Fig. 2 and Fig. 3, the one side of substrate of glass 10 is provided with the tapered protrusion 12 of a plurality of array arrangements, and the another side of substrate of glass is provided with the tapered protrusion 14 of a plurality of array arrangements.Tapered protrusion 12 and tapered protrusion 14 are conducive to light and enter substrate of glass 10 from anode 20, and are conducive to light and penetrate from substrate of glass 10.
Tapered protrusion 12 and tapered protrusion 14 can be correspondence setting.
The height of tapered protrusion 12 is 5 μ m ~ 10 μ m, and the length of side of bottom surface is 5 μ m ~ 20 μ m, and the spacing of every two adjacent tapered protrusion 12 is 1 μ m ~ 5 μ m.
The height of tapered protrusion 14 is 5 μ m ~ 10 μ m, and the length of side of bottom surface is 5 μ m ~ 20 μ m, and the spacing of every two adjacent tapered protrusion 14 is 1 μ m ~ 5 μ m.
The material of anode 20 can be ITO, and the thickness of anode 20 can be 100nm ~ 150nm.
Anode 20 also arranges away from a side of substrate of glass 10 tapered protrusion 22 that is provided with a plurality of array arrangements.Tapered protrusion 22 is identical with the shape of tapered protrusion 12, and corresponding setting.
The material of hole injection layer 30 is that mass ratio is poly-3,4-dioxy ethene thiophene (PEDOT) and the polyphenyl sulfonate (PSS) of 2:1 ~ 6:1.
The thickness of hole injection layer 30 is 20nm ~ 80nm.
The material of hole transmission layer 40 can be 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] at least one in cyclohexane (TAPC).
The thickness of hole transmission layer 40 can be 30nm ~ 50nm.
The material of blue light-emitting 50 is the material of main part of blue light guest materials of having adulterated.
Blue light guest materials account for blue light-emitting 50 gross mass mass percent 5% ~ 20%.
Material of main part can be CBP(4,4'-bis-(9-carbazole) biphenyl), mCP(9,9'-(1,3-phenyl) two-9H-carbazole), CzSi(9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-), 26DCzPPY(2, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-), 35DCzPPY(3, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 5-) and UGH2(1, at least one two (triphenyl silicon) benzene of 4--).
Blue light guest materials can be FIrpic(two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium), FIr6(two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium), FCNIr(tri-(2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium), FIrtaz(two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium) and two (4,6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazoliums) of FIrN4(close iridium) at least one.
The thickness of blue light-emitting 50 is 5nm ~ 15nm.
The material of electron transfer layer 60 can be 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, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
The thickness of electron transfer layer 60 can be 10nm ~ 60nm.
The material of electron injecting layer 70 can be the Cs that adulterated 2cO 3, CsF, CsN 3, Li 2cO 3, LiF and Li 2the electron transport material of at least one in O.
Electron transport material can be 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, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
Cs 2cO 3, CsF, CsN 3, Li 2cO 3, LiF and Li 2o account for electron injecting layer 70 gross mass mass percent 25% ~ 35%.
The thickness of electron injecting layer 70 can be 20nm ~ 40nm.
The material of negative electrode 80 can be silver (Ag), aluminium (Al) or gold (Au) etc., and the thickness of negative electrode 80 is 50nm ~ 200nm.
The two sides of the substrate of glass 10 of this blue light organic electroluminescence device is provided with tapered protrusion 12 and the tapered protrusion 14 of a plurality of array arrangements, adopt the blue light organic electroluminescence device of the substrate of glass 10 of this patterning, compare with the blue light organic electroluminescence device of the traditional smooth substrate of glass of employing, luminous efficiency is higher.
The preparation method of above-mentioned blue light organic electroluminescence device as shown in Figure 4, comprises the steps:
S10, provide clean substrate of glass 10.
The glass that substrate of glass 10 can selective refraction rate is 2.0 ~ 2.6.Thereby make the refractive index ratio anode 20 of substrate of glass 10 want large, light incides optically denser medium by optically thinner medium like this, avoids occurring total reflection, reduces the loss of light.
The thickness of substrate of glass 10 can be 0.7mm ~ 1.1mm.
The one side of S20, the substrate of glass 10 that obtains at S10 forms the tapered protrusion 12 of a plurality of array arrangements.
First, preparation surface is provided with the polymethyl methacrylate model of the tapered protrusion of a plurality of array arrangements.
Polymethyl methacrylate (PMMA) model that can prepare as follows the tapered protrusion that is provided with a plurality of array arrangements: get a glass, photoresist is coated on glass surface, photoetching development is made the figure of design.With BOE(HF acid, follow NH 4f mixed solution, wherein, the mass fraction of HF is 45% ~ 55%, HN 4the mass fraction of F is 35% ~ 45%) process this glass surface, erode without the glassy layer under photoresist, then with KOH solution, this glass surface is made to opposite sex corrosion, make this glass surface form the cone tank of a plurality of array arrangements, and fall photoresist with acetone solution.At glass surface after excessive erosion, pass through magnetron sputtering Ti/Cu(or Ni/Co) Seed Layer, electroforming is carried out in electro-coppering (or Ni, Fe).Then at the glass surface that forms the cone tank of a plurality of array arrangements, apply PMMA, after peeling off, obtain being provided with polymethyl methacrylate (PMMA) model of the tapered protrusion of a plurality of array arrangements.
Then polymethyl methacrylate model is attached to the one side of substrate of glass 10, by reactive ion etching, in the one side of substrate of glass 10, forms the tapered protrusion 12 of a plurality of array arrangements.
The concrete steps of reactive ion (RIE) etching are as follows:
The substrate of glass 10 that is pasted with polymethyl methacrylate model is placed in to bracket, is evacuated to 3 * 10 -3pa, then passes into CHF 3start etching, polymethyl methacrylate model and substrate of glass 10 can synchronously be removed by reactive ion, until polymethyl methacrylate model is etched away entirely, thereby in the one side of substrate of glass 10, form the tapered protrusion 12 of a plurality of array arrangements.
The height of controlling tapered protrusion 12 by the size of photoresist is 5 μ m ~ 10 μ m, and the length of side of bottom surface is 5 μ m ~ 20 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion 12 is 1 μ m ~ 5 μ m.
The another side of S30, the substrate of glass 10 that obtains at S20 forms the tapered protrusion 14 of a plurality of array arrangements.
The method of tapered protrusion 14 that forms a plurality of array arrangements is identical with S20.
The height of controlling tapered protrusion 14 by the size of photoresist is 5 μ m ~ 10 μ m, and the length of side of bottom surface is 5 μ m ~ 20 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion 14 is 1 μ m ~ 5 μ m.
Tapered protrusion 12 and tapered protrusion 14 can be correspondence setting.
The sequencing that is understandable that S20 and S30 can be changed.
S40, in the one side of substrate of glass 10, form successively anode 20, hole injection layer 30, hole transmission layer 40, blue light-emitting 50, electron transfer layer 60, electron injecting layer 70 and negative electrode 80.
In present embodiment, be chosen in the structures such as one side formation anode 20 that glass basis 10 is provided with tapered protrusion 12.In other execution mode, the one side that also can be chosen in tapered protrusion 14 forms the structures such as anode 20.
Base vacuum degree 2 * 10 -4pa, the one side that is provided with the tapered protrusion 12 of a plurality of array arrangements by magnetron sputtering in substrate of glass 10 forms anode 20.
The material of anode 20 can be ITO, and the thickness of anode 20 can be 100nm～150nm.
Due to anode 20 by magnetron sputtering deposition in substrate of glass 10, thereby make anode 20 away from a side of substrate of glass 10, also be provided with the tapered protrusion 22 of a plurality of array arrangements.Tapered protrusion 22 is identical with the shape of tapered protrusion 12, and corresponding setting.
On anode 20, spin coating forms hole injection layer 30.
According to mass ratio, be that 2:1 ~ 6:1 will gather 3,4-dioxy ethene thiophene (PEDOT) and polyphenyl sulfonate (PSS) are mixed with mass fraction after mixing be 1% ~ 5% solution, and this solution is spin-coated on anode 20, then at 100 ℃ ~ 200 ℃, heat 15min ~ 60min, obtain hole injection layer 30.
The THICKNESS CONTROL of hole injection layer 30 is 20nm ~ 80nm.
Then evaporation forms hole transmission layer 40, blue light-emitting 50, electron transfer layer 60, electron injecting layer 70 and negative electrode 80.
The material of hole transmission layer 40 can be 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] at least one in cyclohexane (TAPC).
Evaporation conditions is: vacuum degree 8 * 10 -5pa ~ 3 * 10 -4pa, evaporation rate
Figure BDA00002073390000071
The thickness of hole transmission layer 40 can be 30nm ~ 50nm.
The material of blue light-emitting 50 is the material of main part of blue light guest materials of having adulterated.
Evaporation conditions is: vacuum degree 8 * 10 -5pa ~ 3 * 10 -4pa, evaporation rate
Figure BDA00002073390000081
Blue light guest materials account for blue light-emitting 50 gross mass mass percent 5% ~ 20%.
Material of main part can be CBP(4,4'-bis-(9-carbazole) biphenyl), mCP(9,9'-(1,3-phenyl) two-9H-carbazole), CzSi(9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-), 26DCzPPY(2, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-), 35DCzPPY(3, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 5-) and UGH2(1, at least one two (triphenyl silicon) benzene of 4--).
Blue light guest materials can be FIrpic(two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium), FIr6(two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium), FCNIr(tri-(2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium), FIrtaz(two (4,6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium) and two (4,6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazoliums) of FIrN4(close iridium) at least one.
The thickness of blue light-emitting 50 is 5nm ~ 15nm.
The material of electron transfer layer 60 can be 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, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
Evaporation conditions is: vacuum degree 8 * 10 -5pa ~ 3 * 10 -4pa, evaporation rate
Figure BDA00002073390000082
The thickness of electron transfer layer 60 can be 10nm ~ 60nm.
The material of electron injecting layer 70 can be the Cs that adulterated 2cO 3, CsF, CsN 3, Li 2cO 3, LiF and Li 2the electron transport material of at least one in O.
Evaporation conditions is: vacuum degree 8 * 10 -5pa ~ 3 * 10 -4pa, evaporation rate
Figure BDA00002073390000083
Electron transport material can be 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, at least one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
Cs 2cO 3, CsF, CsN 3, Li 2cO 3, LiF and Li 2o account for electron injecting layer 70 gross mass mass percent 25% ~ 35%.
The thickness of electron injecting layer 70 can be 20nm ~ 40nm.
The material of negative electrode 80 can be silver (Ag), aluminium (Al) or gold (Au) etc.
Evaporation conditions is: vacuum degree 8 * 10 -5pa ~ 3 * 10 -4pa, evaporation rate
The thickness of negative electrode 80 is 50nm ~ 200nm.
It is below specific embodiment.In embodiment, photoresist adopts DTFR-EL100, and Shenzhen De Tong photoelectric material Co., Ltd produces.
Embodiment 1
1, providing thickness is the clean substrate of glass of 0.7mm.
2, in the one side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
First, preparation surface is provided with the polymethyl methacrylate model of the tapered protrusion of a plurality of array arrangements.
Concrete steps are: get a glass, photoresist is coated on glass surface, photoetching development is made the figure of design.With BOE(HF acid, with NH4F mixed solution, wherein, the mass fraction of HF is 50%, HN 4the mass fraction of F is 40%) process this glass surface, erode without the glassy layer under photoresist, then with KOH solution, this glass surface is made to opposite sex corrosion, make this glass surface form the cone tank of a plurality of array arrangements, and fall photoresist with acetone solution.At glass surface after excessive erosion, by magnetron sputtering Ti/Cu Seed Layer, electroforming is carried out in electro-coppering.Then at the glass surface that forms the cone tank of a plurality of array arrangements, apply PMMA, after peeling off, obtain being provided with polymethyl methacrylate (PMMA) model of the tapered protrusion of a plurality of array arrangements.
Then polymethyl methacrylate model is attached to the one side of substrate of glass, by reactive ion etching, in the one side of substrate of glass, forms the tapered protrusion of a plurality of array arrangements.
The concrete steps of reactive ion etching are as follows:
The substrate of glass that is pasted with polymethyl methacrylate model is placed in to bracket, is evacuated to 3 * 10 -3pa, then passes into CHF 3start etching, polymethyl methacrylate model and substrate of glass can synchronously be removed by reactive ion, until polymethyl methacrylate model is etched away entirely, thereby in the one side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
The height of controlling tapered protrusion by the size of photoresist is 7 μ m, and the length of side of bottom surface is 10 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 3 μ m.
3, at the another side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Specific practice is identical with the step in 2.
The height of controlling tapered protrusion by the size of photoresist is 7 μ m, and the length of side of bottom surface is 10 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 3 μ m.
4, a magnetron sputtering in substrate of glass forms anode.
Base vacuum degree is 2 * 10 -4pa, the material of anode is ITO, thickness is 150nm.
5, after to be 4:1 mix PEDOT and PSS according to mass ratio, be mixed with mass fraction and be 3% solution, and this solution is spin-coated on anode, then at 150 ℃, heat 40min, control thickness is 60nm, obtains hole injection layer.
6, on hole injection layer, evaporation forms hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode successively.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000101
evaporation rate, on hole injection layer, form hole transmission layer, the material of hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), the thickness of the hole transmission layer of formation is 40nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000102
evaporation rate, on hole transmission layer, form blue light-emitting, the material of blue light-emitting is the FIrpic(two (4 that adulterated, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium) CBP(4,4'-bis-(9-carbazole) biphenyl), FIrpic account for blue light-emitting gross mass mass percent 12.5%, the thickness of the blue light-emitting of formation is 10nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000103
evaporation rate, on blue light-emitting, form electron transfer layer, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), the thickness of the electron transfer layer of formation is 35nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with evaporation rate, on electron transfer layer, form electron injecting layer, the material of electron injecting layer is the Cs that adulterated 2cO 34,7-diphenyl-1,10-phenanthroline (Bphen), Cs 2cO 3account for electron injecting layer gross mass mass percent 30%, the thickness 30nm of the electron injecting layer of formation.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000105
evaporation rate, on electron injecting layer, form negative electrode, the material of negative electrode is Ag, the thickness of the negative electrode of formation is 125nm.
Embodiment 2
1, providing thickness is the clean substrate of glass of 0.8mm.
2, in the one side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.Difference is, when preparation surface is provided with the polymethyl methacrylate model of tapered protrusion of a plurality of array arrangements, with BOE(HF acid with NH 4f mixed solution, wherein, the mass fraction of HF is 45%, HN 4the mass fraction of F is 45%) processing glass surface.
The height of controlling tapered protrusion by the size of photoresist is 5 μ m, and the length of side of bottom surface is 5 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 5 μ m.
3, at the another side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.Difference is, when preparation surface is provided with the polymethyl methacrylate model of tapered protrusion of a plurality of array arrangements, with BOE(HF acid with NH 4f mixed solution, wherein, the mass fraction of HF is 45%, HN 4the mass fraction of F is 45%) processing glass surface.
The height of controlling tapered protrusion by the size of photoresist is 5 μ m, and the length of side of bottom surface is 5 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 5 μ m.
4, a magnetron sputtering in substrate of glass forms anode.
Base vacuum degree is 2 * 10 -4pa, the material of anode is ITO, thickness is 120nm.
5, after to be 2:1 mix PEDOT and PSS according to mass ratio, be mixed with mass fraction and be 1% solution, and this solution is spin-coated on anode, then at 100 ℃, heat 15min, control thickness is 20nm, obtains hole injection layer.
6, on hole injection layer, evaporation forms hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode successively.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000111
evaporation rate, on hole injection layer, form hole transmission layer, the material of hole transmission layer is 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), the thickness of the hole transmission layer of formation is 30nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000112
evaporation rate, on hole transmission layer, form blue light-emitting, the material of blue light-emitting is the FIr6(two (4 that adulterated, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium) mCP(9,9'-(1,3-phenyl) two-9H-carbazole), FIr6 account for blue light-emitting gross mass mass percent 5%, the thickness of the blue light-emitting of formation is 5nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000113
evaporation rate, on blue light-emitting, form electron transfer layer, the material of electron transfer layer is 4,7-diphenyl-1,10-Phen (BCP), the thickness of the electron transfer layer of formation is 10nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000121
evaporation rate, on electron transfer layer, form electron injecting layer, the material of electron injecting layer is 4 of the CsF that adulterated, 7-diphenyl-1,10-Phen (BCP), CsF account for electron injecting layer gross mass mass percent 25%, the thickness 20nm of the electron injecting layer of formation.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000122
evaporation rate, on electron injecting layer, form negative electrode, the material of negative electrode is Al, the thickness of the negative electrode of formation is 50nm.
Embodiment 3
1, providing thickness is the clean substrate of glass of 0.9mm.
2, in the one side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.Difference is, when preparation surface is provided with the polymethyl methacrylate model of tapered protrusion of a plurality of array arrangements, with BOE(HF acid with NH 4f mixed solution, wherein, the mass fraction of HF is 55%, HN 4the mass fraction of F is 35%) processing glass surface.
The height of controlling tapered protrusion by the size of photoresist is 10 μ m, and the length of side of bottom surface is 20 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 1 μ m.
3, at the another side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.Difference is, when preparation surface is provided with the polymethyl methacrylate model of tapered protrusion of a plurality of array arrangements, with BOE(HF acid with NH 4f mixed solution, wherein, the mass fraction of HF is 55%, HN 4the mass fraction of F is 35%) processing glass surface.
The height of controlling tapered protrusion by the size of photoresist is 10 μ m, and the length of side of bottom surface is 20 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 1 μ m.
4, a magnetron sputtering in substrate of glass forms anode.
Base vacuum degree is 2 * 10 -4pa, the material of anode is ITO, thickness is 100nm.
5, after to be 6:1 mix PEDOT and PSS according to mass ratio, be mixed with mass fraction and be 5% solution, and this solution is spin-coated on anode, then at 100 ℃, heat 60min, control thickness is 80nm, obtains hole injection layer.
6, on hole injection layer, evaporation forms hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode successively.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000131
evaporation rate, on hole injection layer, form hole transmission layer, the material of hole transmission layer is 4,4'-bis-(9-carbazole) biphenyl (CBP), the thickness of the hole transmission layer of formation is 50nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000132
evaporation rate, on hole transmission layer, form blue light-emitting, the material of blue light-emitting is the FCNIr(tri-(2-(4' that adulterated, the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium) CzSi(9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-), FCNIr account for blue light-emitting gross mass mass percent 20%, the thickness of the blue light-emitting of formation is 15nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000133
evaporation rate, on blue light-emitting, form electron transfer layer, the material of electron transfer layer is that 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), the thickness of the electron transfer layer of formation is 60nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with evaporation rate, on electron transfer layer, form electron injecting layer, the material of electron injecting layer is the CsN that adulterated 34-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), CsN 3account for electron injecting layer gross mass mass percent 35%, the thickness 40nm of the electron injecting layer of formation.
In vacuum degree 5 * 10 -5under the condition of Pa, with evaporation rate, on electron injecting layer, form negative electrode, the material of negative electrode is Au, the thickness of the negative electrode of formation is 200nm.
Embodiment 4
1, providing thickness is the clean substrate of glass of 1mm.
2, in the one side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.
The height of controlling tapered protrusion by the size of photoresist is 8 μ m, and the length of side of bottom surface is 11 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 3 μ m.
3, at the another side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.
The height of controlling tapered protrusion by the size of photoresist is 8 μ m, and the length of side of bottom surface is 11 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 3 μ m.
4, a magnetron sputtering in substrate of glass forms anode.
Base vacuum degree is 2 * 10 -4pa, the material of anode is ITO, thickness is 100nm.
5, after to be 3:1 mix PEDOT and PSS according to mass ratio, be mixed with mass fraction and be 3% solution, and this solution is spin-coated on anode, then at 200 ℃, heat 20min, control thickness is 40nm, obtains hole injection layer.
6, on hole injection layer, evaporation forms hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode successively.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000141
evaporation rate, on hole injection layer, form hole transmission layer, the material of hole transmission layer is N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), the thickness of the hole transmission layer of formation is 40nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000142
evaporation rate, on hole transmission layer, form blue light-emitting, the material of blue light-emitting is the FIrtaz(two (4 that adulterated, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazole) close iridium) 26DCzPPY(2, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-), FIrtaz account for blue light-emitting gross mass mass percent 12%, the thickness of the blue light-emitting of formation is 10nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000143
evaporation rate, on blue light-emitting, form electron transfer layer, the material of electron transfer layer is oxine aluminium (Alq 3), the thickness of the electron transfer layer of formation is 30nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000144
evaporation rate, on electron transfer layer, form electron injecting layer, the material of electron injecting layer is the Li that adulterated 2cO 3oxine aluminium (Alq 3), Li 2cO 3account for electron injecting layer gross mass mass percent 30%, the thickness 30nm of the electron injecting layer of formation.In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000145
evaporation rate, on electron injecting layer, form negative electrode, the material of negative electrode is Ag, the thickness of the negative electrode of formation is 100nm.
Embodiment 5:
1, providing thickness is the clean substrate of glass of 1.1mm.
2, in the one side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.
The height of controlling tapered protrusion by the size of photoresist is 6 μ m, and the length of side of bottom surface is 8 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 4 μ m.
3, at the another side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.
The height of controlling tapered protrusion by the size of photoresist is 6 μ m, and the length of side of bottom surface is 8 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 4 μ m.
4, a magnetron sputtering in substrate of glass forms anode.
Base vacuum degree is 2 * 10 -4pa, the material of anode is ITO, thickness is 100nm.
5, after to be 5:1 mix PEDOT and PSS according to mass ratio, be mixed with mass fraction and be 4% solution, and this solution is spin-coated on anode, then at 120 ℃, heat 30min, control thickness is 50nm, obtains hole injection layer.
6, on hole injection layer, evaporation forms hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode successively.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000151
evaporation rate, on hole injection layer, form hole transmission layer, the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), the thickness of the hole transmission layer of formation is 40nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000152
evaporation rate, on hole transmission layer, form blue light-emitting, the material of blue light-emitting is the FIrN4(two (4 that adulterated, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes iridium) 35DCzPPY(3, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 5-), FIrN4 account for blue light-emitting gross mass mass percent 12%, the thickness of the blue light-emitting of formation is 10nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000153
evaporation rate, on blue light-emitting, form electron transfer layer, the material of electron transfer layer is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), the thickness of the electron transfer layer of formation is 50nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000154
evaporation rate, on electron transfer layer, form electron injecting layer, the material of electron injecting layer is 3-(biphenyl-4-yl)-5-(4-the tert-butyl-phenyl)-4-phenyl-4H-1 of LiF of having adulterated, 2,4-triazole (TAZ), LiF account for electron injecting layer gross mass mass percent 30%, the thickness 30nm of the electron injecting layer of formation.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000161
evaporation rate, on electron injecting layer, form negative electrode, the material of negative electrode is Al, the thickness of the negative electrode of formation is 100nm.
Embodiment 6
1, providing thickness is the clean substrate of glass of 1mm.
2, in the one side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.
The height of controlling tapered protrusion by the size of photoresist is 9 μ m, and the length of side of bottom surface is 7 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 4 μ m.
3, at the another side of substrate of glass, form the tapered protrusion of a plurality of array arrangements.
Concrete operations are with embodiment 1.
The height of controlling tapered protrusion by the size of photoresist is 9 μ m, and the length of side of bottom surface is 7 μ m.By controlling photoetching development, the spacing that makes every two adjacent tapered protrusion is 4 μ m.
4, a magnetron sputtering in substrate of glass forms anode.
Base vacuum degree is 2 * 10 -4pa, the material of anode is ITO, thickness is 100nm.
5, after to be 4:1 mix PEDOT and PSS according to mass ratio, be mixed with mass fraction and be 4% solution, and this solution is spin-coated on anode, then at 160 ℃, heat 40min, control thickness is 60nm, obtains hole injection layer.
6, on hole injection layer, evaporation forms hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode successively.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000162
evaporation rate, on hole injection layer, form hole transmission layer, the material of hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), the thickness of the hole transmission layer of formation is 40nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000163
evaporation rate, on hole transmission layer, form blue light-emitting, the material of blue light-emitting is the FIrpic(two (4 that adulterated, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium) UGH2(1, two (triphenyl silicon) benzene of 4--), FIrpic account for blue light-emitting gross mass mass percent 12%, the thickness of the blue light-emitting of formation is 10nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000164
evaporation rate, on blue light-emitting, form electron transfer layer, the material of electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), the thickness of the electron transfer layer of formation is 30nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000171
evaporation rate, on electron transfer layer, form electron injecting layer, the material of electron injecting layer is the Li that adulterated 21,3 of O, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), Li 2o account for electron injecting layer gross mass mass percent 30%, the thickness 30nm of the electron injecting layer of formation.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000172
evaporation rate, on electron injecting layer, form negative electrode, the material of negative electrode is Al, the thickness of the negative electrode of formation is 100nm.
Embodiment 7(comparative example)
It is the ito glass of 150nm that ITO thickness is provided, thickness is that the glassy layer of 0.9mm is as glass substrate, ITO layer is as anode, and it is handled as follows: liquid detergent cleaning → washed with de-ionized water → acetone cleaning → ethanol cleans, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, stops 5 minutes, repeat respectively the method for 3 times, and then use oven for drying.Ito glass after drying is carried out to surface activation process, to increase the oxygen content on ITO surface, improve the work function on ITO surface.
After to be 3:1 mix PEDOT and PSS according to mass ratio, be mixed with mass fraction and be 3% solution, and this solution is spin-coated on anode, then at 150 ℃, heat 40min, control thickness is 70nm, obtains hole injection layer.
On hole injection layer, evaporation forms hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode successively.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000173
evaporation rate, on hole injection layer, form hole transmission layer, the material of hole transmission layer is 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), the thickness of the hole transmission layer of formation is 40nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000174
evaporation rate, on hole transmission layer, form blue light-emitting, the material of blue light-emitting is the FIr6(two (4 that adulterated, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium) CBP(4,4'-bis-(9-carbazole) biphenyl), FIr6 account for blue light-emitting gross mass mass percent 13%, the thickness of the blue light-emitting of formation is 10nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000175
evaporation rate, on blue light-emitting, form electron transfer layer, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), the thickness of the electron transfer layer of formation is 40nm.
In vacuum degree 5 * 10 -5under the condition of Pa, with evaporation rate, on electron transfer layer, form electron injecting layer, the material of electron injecting layer is 1,3, the 5-tri-that adulterated (1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), Cs 2cO 3account for electron injecting layer gross mass mass percent 30%, the thickness 40nm of the electron injecting layer of formation.
In vacuum degree 5 * 10 -5under the condition of Pa, with
Figure BDA00002073390000182
evaporation rate, on electron injecting layer, form negative electrode, the material of negative electrode is Al, the thickness of the negative electrode of formation is 80nm.
The luminous efficiency figure of the blue light organic electroluminescence device of embodiment 1 ~ embodiment 7 preparations as shown in Figure 5, interpreting blueprints can obtain following table:
Brightness (cd/m 2) 100.0 300.0 500.0 700.0 900.0 1100.0 1300.0 1500.0 1700.0
Embodiment 1(lm/W) 23.6 23.0 22.1 21.1 20.1 18.6 17.2 15.2 12.8
Embodiment 2(lm/W) 22.4 21.8 20.9 19.9 18.6 17.3 15.8 14.0 12.1
Embodiment 3(lm/W) 21.5 20.8 19.6 18.6 17.3 16.4 15.0 13.2 11.5
Embodiment 4(lm/W) 20.4 19.7 18.6 17.6 15.9 14.7 13.4 11.5 9.6
Embodiment 5(lm/W) 19.4 18.3 17.0 15.8 13.6 12.5 11.0 8.9 8.0
Embodiment 6(lm/W) 17.9 16.8 15.3 13.8 11.8 10.6 9.0 7.8 6.3
Embodiment 7(lm/W) 12.5 11.1 10.0 8.3 6.8 4.6 3.4 1.8 1.0
As can be seen from the above table, in embodiment 1 ~ embodiment 6, the two sides of the substrate of glass of preparation is equipped with the tapered protrusion of a plurality of array arrangements, the substrate of glass of this patterning has improved the luminous efficiency of blue light organic electroluminescence device, the blue light organic electroluminescence device of comparing the smooth substrate of glass of employing of embodiment 7 preparations, luminous efficiency has improved more than 0.6 times.
The above embodiment has only expressed one or more execution modes 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 blue light organic electroluminescence device, is characterized in that, comprises the following structure stacking gradually:
Substrate of glass, anode, hole injection layer, hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode;
Described substrate of glass two sides is equipped with the tapered protrusion of a plurality of array arrangements.
2. blue light organic electroluminescence device according to claim 1, is characterized in that, the height of described tapered protrusion is 5 μ m ~ 10 μ m, and the length of side of bottom surface is 5 μ m ~ 20 μ m, and the spacing of every two adjacent described tapered protrusion is 1 μ m ~ 5 μ m.
3. blue light organic electroluminescence device according to claim 1, is characterized in that, the tapered protrusion that described substrate of glass two sides is provided with arranges for corresponding.
4. blue light organic electroluminescence device according to claim 1, is characterized in that, the thickness of described substrate of glass is 0.7mm ~ 1.1mm.
5. blue light organic electroluminescence device according to claim 1, is characterized in that, described anode is provided with the tapered protrusion of a plurality of array arrangements away from a side setting of described substrate of glass.
6. blue light organic electroluminescence device according to claim 1, is characterized in that, the material of described hole injection layer is that mass ratio is poly-3,4-dioxy ethene thiophene and the polyphenyl sulfonate of 2:1 ~ 6:1;
The thickness of described hole injection layer is 20nm ~ 80nm.
7. blue light organic electroluminescence device according to claim 1, is characterized in that, the material of described blue light-emitting is the material of main part of blue light guest materials of having adulterated;
Described material of main part is 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 the Isosorbide-5-Nitraes of 5---at least one in two (triphenyl silicon) benzene;
Described blue light guest materials is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) 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 pyridine) (5-(pyridine-2-yl)-tetrazolium) close at least one in iridium;
Described blue light guest materials account for described blue light-emitting gross mass mass percent 5% ~ 20%.
8. blue light organic electroluminescence device according to claim 1, is characterized in that, the thickness of described blue light-emitting is 5nm ~ 15nm.
9. a preparation method for blue light organic electroluminescence device, is characterized in that, comprises the steps:
Clean substrate of glass is provided;
In the one side of described substrate of glass, form the tapered protrusion of a plurality of array arrangements;
At the another side of described substrate of glass, form the tapered protrusion of a plurality of array arrangements;
One side in described substrate of glass forms anode, hole injection layer, hole transmission layer, blue light-emitting, electron transfer layer, electron injecting layer and negative electrode successively.
10. the preparation method of blue light organic electroluminescence device according to claim 9, is characterized in that, the step that the described one side in substrate of glass forms the tapered protrusion of a plurality of array arrangements is:
Preparation surface is provided with the polymethyl methacrylate model of the tapered protrusion of a plurality of array arrangements;
Described polymethyl methacrylate model is attached to the one side of described substrate of glass, by reactive ion etching, in the one side of described substrate of glass, forms the tapered protrusion of a plurality of array arrangements.
CN201210312914.2A 2012-08-29 2012-08-29 Blue light organic electroluminescent device and preparation method thereof Pending CN103633253A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110809829A (en) * 2017-07-03 2020-02-18 默克专利有限公司 Organic electroluminescent device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110809829A (en) * 2017-07-03 2020-02-18 默克专利有限公司 Organic electroluminescent device
CN110809829B (en) * 2017-07-03 2023-07-14 默克专利有限公司 Organic electroluminescent device

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