CN102931358A - Hemispherical shell organic electroluminescence device and preparation method thereof - Google Patents
Hemispherical shell organic electroluminescence device and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of photoelectric devices, and discloses a hemispherical shell organic electroluminescence device and a preparation method thereof. The hemispherical shell organic electroluminescence device comprises a hemispherical shell base, wherein an anode layer, a p-type doped hole transport layer, an electron blocking layer, a luminescent layer, a hole blocking layer, an n-type doped electron transport layer and a cathode layer are stacked on the internal surface of the hemispherical shell base in sequence. The hemispherical shell organic electroluminescence device is hemispherical, total internal reflection loss caused by the difference between refractive indexes of the luminescent layer and air can be refracted through a curved surface, and the transverse waveguide loss of an organic layer can be captured, so that light transmitting efficiency is greatly improved; and meanwhile, the hemispherical shell organic electroluminescence device does not have angle dependence, and the preparation process is simple.
Description
Technical field
The present invention relates to field of photoelectric devices, relate in particular to a kind of hemisphere shelly organic electroluminescence device and preparation method thereof.
Background technology
1987, the Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in the organic electroluminescent research.They utilize vacuum evaporation technology higher and have an oxine aluminium (Alq of electron-transporting having the aromatic diamine of hole transport ability and fluorescence efficiency first
3) make up and prepared double-deck organic electroluminescence device.Device under the 10V driving voltage, transmitting green light, brightness is up to 1000cd/m
2, efficient reaches 1.5lm/W, and the life-span was above 1000 hours.This landmark work makes people see the practical and business-like rosy prospect of organic electroluminescence devices.Through the development of two more than ten years, owing to taking full advantage of the luminescent material of singlet and triplet state, the internal quantum efficiency of device has reached 100% at present.Because the difference of the inside and outside refractive index of device causes the light that sends at device inside to only have fraction can arrive extraneous air and utilized by us, most of light then is closed in device inside, is finally absorbed by inner material and becomes heat through refraction repeatedly.The light that luminescent layer sends has passed through the process of the optical coupling such as absorption, reflection and refraction of each organic layer, ITO (tin indium oxide) and substrate of glass.When the light that sends from organic layer penetrated device outside, 17% the luminous energy of only having an appointment was seen by the people.Most of photons have lost because of the transversal waveguides of the total reflection at substrate and Air Interface place and organic layer inside.
Existing many researchs improve the coupling efficiency that of organic electroluminescence devices, as: the surface roughness that increases substrate and Air Interface; Etching groove on substrate of glass, these grooves play a part reflective mirror, and light is derived again, can improve 2 times efficient (Opt.Lett.22,396,1997.); Use the close circle lens of refraction index in glass back, by changing the size of lens, change critical angle, again with light-output, light extraction efficiency can be improved 2.2-3 doubly (Opt.Exp.14,6564,2000); Employing improves scattering at substrate surface periodic arrangement silicon microballoon, and lateral wave leaded light vertical sand shooting is gone out (Appl.Phys.Lett.76,1243,2000); Also can adopt the Bragg reflection face of arranged distribution or between substrate of glass and ITO layer, insert the light extraction efficiency (Adv.Mater.13,1149,2001.) that one deck low-refraction material also can increase device; Prepare photonic crystal pattern by the glass substrate at OLED, light takes out efficient and compares with traditional dull and stereotyped OLED and improved 25%, namely brings up to 25% (Appl.Phys.Lett.82,3779,2003.) by original 20%.But these methods generally all can make the preparation process of device more loaded down with trivial details, and make emission spectrum generation angle dependence type, often the raising of the light extraction efficiency of organic electroluminescence device is also insufficient, often can not take into account total reflection and the transversal waveguides loss of organic electroluminescence devices.
Summary of the invention
The object of the present invention is to provide a kind of light extraction efficiency high, do not have dependence of angle, and the simple hemisphere shelly of preparation technology organic electroluminescence device.
A kind of hemisphere shelly organic electroluminescence device, comprise the substrate of hemisphere shelly, stacked gradually anode layer, p-type doping hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, N-shaped doping electron transfer layer and cathode layer at the inner surface of described hemisphere shelly substrate.
In the above-mentioned hemisphere shelly organic electroluminescence device, the internal diameter of hemisphere shelly substrate is 3～10mm, and the thickness of hemisphere shelly substrate and the radius-thickness ratio between the internal diameter are 0.1～1.0; Regulate thickness according to corresponding internal diameter.
Above-mentioned hemisphere shelly organic electroluminescence device, the material of its functional layer is as follows:
The material of described anode layer is electric conducting material commonly used, as, tin indium oxide, fluorine doped tin oxide, Al-Doped ZnO or mix indium zinc oxide;
The material of described p-type doping hole transmission layer is hole mobile material doping tetrafluoro four cyano 1,4-benzoquinone bismethane, four cyano 1,4-benzoquinone bismethane or molybdenum trioxide;
Described hole mobile material is 4,4 ', 4 " three (3-aminomethyl phenyl aniline) triphenylamine, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4; 4 '-benzidine, 4; 4 ', 4 " three (carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine;
The material of described electronic barrier layer is 1,1-two [4-[N, N '-two (p-tolyl) amino] phenyl] cyclohexane, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine or 4,4 ', 4 " three (carbazole-9-yl) triphenylamine;
The material of described luminescent layer is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine, 1,2,4-triazole derivative or N-aryl benzimidazole doped luminescent materials;
Described luminescent material is 4,4 '-two (9-ethyls-3-carbazole vinyl)-1,10-diphenyl, three (2-phenylpyridine) close iridium, two (2-methyl-diphenyl quinoxaline) (acetylacetone,2,4-pentanedione) and close iridium or three (1-phenyl-isoquinolin) and close iridium;
The material of described hole blocking layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 2,5-two (1-naphthyl)-1,3,4-diazole, 4,7-diphenyl-1,10-phenanthroline or N-aryl benzimidazole;
The material of described N-shaped doping electron transfer layer is electron transport material doping cesium carbonate, cesium azide, cesium fluoride, lithium fluoride or lithium carbonate;
Described electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 2,5-two (1-naphthyl)-1,3,4-diazole, 4,7-diphenyl-1,10-phenanthroline or N-aryl benzimidazole;
The material of described cathode layer is common metal, as, silver, aluminium, platinum, gold or magnesium silver alloy.
Another object of the present invention is to provide the preparation method of above-mentioned hemisphere shelly organic electroluminescence device, comprise the steps:
S1, cleaning, the substrate of dry hemisphere shelly;
S2, employing magnetron sputtering technique are at the inner surface sputter anode layer of described hemisphere shelly substrate;
S3, on described anode layer surface successively evaporation p-type doping hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, N-shaped doping electron transfer layer and cathode layer;
After above-mentioned technique is finished, make described hemisphere shelly organic electroluminescence device.
Hemisphere shelly organic electroluminescence device provided by the invention, owing to being hemispheric, the total internal reflection loss that the difference by luminescent layer and air refraction can be caused penetrates by the curved surface refraction, the transversal waveguides loss of organic layer can also be caught, so light extraction efficiency improves greatly; Simultaneously, this hemisphere shelly organic electroluminescence device does not have dependence of angle, and this dependence is directly determined by semi-spherical shape, and this organic electroluminescence device preparation technology is simple.
Description of drawings
Fig. 1 is the structural representation of hemisphere shelly organic electroluminescence device of the present invention;
Fig. 2 is preparation technology's flow chart of hemisphere shelly organic electroluminescence device of the present invention;
Fig. 3 is embodiment 1,2 and 3 and the brightness of the organic electroluminescence device of Comparative Examples-voltage curve comparison diagram;
Fig. 4 is embodiment 1,2 and 3 and the maximum luminous efficiency figure of the organic electroluminescence device of Comparative Examples.
Embodiment
A kind of hemisphere shelly organic electroluminescence device provided by the invention, as shown in Figure 1, comprise hemisphere shelly substrate 101, stacked gradually anode layer 102, p-type doping hole transmission layer 103, electronic barrier layer 104, luminescent layer 105, hole blocking layer 106, N-shaped doping electron transfer layer 107 and cathode layer 108 at the inner surface of described hemisphere shelly substrate;
In the above-mentioned hemisphere shelly organic electroluminescence device, the internal diameter of hemisphere shelly substrate (such as, glass) is 3～10mm, and the thickness of substrate and the pass between the internal diameter are: radius-thickness ratio
Be 0.1～1.0; Regulate thickness according to corresponding internal diameter.
Above-mentioned hemisphere shelly organic electroluminescence device, the material of its functional layer is as follows:
The material of described anode layer is electric conducting material commonly used, as, tin indium oxide (ITO), fluorine doped tin oxide (FTO), Al-Doped ZnO (AZO) or mix indium zinc oxide (IZO); The preferred ITO of the material of anode layer; The thickness of anode layer is 100～200nm, and thickness is preferably 150nm;
The material of described p-type doping hole transmission layer be hole mobile material (as, 4,4 ', 4 " three (3-aminomethyl phenyl aniline) triphenylamine (m-MTDATA); N; N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4; 4 '-benzidine (TPD); 4,4 ', 4 " three (carbazole-9-yl) triphenylamine (TCTA); N; N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB)) doping tetrafluoro four cyano 1,4-benzoquinone bismethane (F4-TCNQ); four cyano 1,4-benzoquinone bismethane (TCNQ) or molybdenum trioxide (MoO
3); The material of p-type doping hole transmission layer is preferably m-MTDATA:F4-TCNQ, and the thickness of p-type doping hole transmission layer is 20～80nm, and thickness is preferably 40nm;
The material of described electronic barrier layer is 1,1-two [4-[N, N '-two (p-tolyl) amino] phenyl] cyclohexane (TAPC), N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) or 4,4 ', 4 " and three (carbazole-9-yl) triphenylamine (TCTA); The material of electronic barrier layer is preferably TAPC; The thickness of electronic barrier layer is 2～20nm, and thickness is preferably 5nm;
The material of described luminescent layer is 4,4 ', 4 " three (carbazole-9-yl) triphenylamine (TCTA), 1; 2; 4-triazole derivative (such as TAZ) or N-aryl benzimidazole (TPBI) doped luminescent material (as, 4,4 '-two (9-ethyls-3-carbazole vinyl)-1; 10-diphenyl (BCzVBi), three (2-phenylpyridines) close iridium (Ir (ppy)
3), two (2-methyl-diphenyl quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3)); The material of described luminescent layer is preferably TCTA:Ir (ppy)
3Light emitting layer thickness is 30～60nm, is preferably 40nm;
The material of described hole blocking layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-two (1-naphthyl)-1,3,4-diazole (BND), 4,7-diphenyl-1,10-phenanthroline (Bphen) or N-aryl benzimidazole (TPBI); The material of hole blocking layer is preferably Bphen; The hole barrier layer thickness is 2～20nm, and thickness is preferably 10nm;
The material of described N-shaped doping electron transfer layer be electron transport material (as, 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-two (1-naphthyl)-1,3,4-diazole (BND), 4,7-diphenyl-1,10-phenanthroline (Bphen) or N-aryl benzimidazole (TPBI)) doping cesium carbonate (Cs
2CO
3), cesium azide (CsN
3), cesium fluoride (CsF), lithium fluoride (LiF) or lithium carbonate (Li
2CO
3); The material of N-shaped doping electron transfer layer is preferably Bphen:Cs
2CO
3N-shaped doping electric transmission layer thickness is 40～80nm, and thickness is preferably 40nm;
The material of described cathode layer is common metal, as, silver (Ag), aluminium (Al), platinum (Pt), gold (Au) or magnesium silver alloy (Mg:Ag), wherein, the mass ratio of Mg and Ag is 10: 1; It is 10: 1 Mg that the material of cathode layer is preferably mass ratio: the Ag alloy; The thickness of cathode layer is 100～200nm, and thickness is preferably 150nm.
The preparation method of above-mentioned hemisphere shelly organic electroluminescence device as shown in Figure 2, comprises the steps:
S1, with hemisphere substrate (such as, glass), use successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
S2, adopt magnetron sputtering technique, the substrate of described hemisphere shelly is put into the vacuum cavity of magnetron sputtering apparatus, the inner surface sputter anode layer in the substrate of hemisphere shelly makes hemisphere shelly anode substrate; Then will be coated with glass spin coating photoresist, exposure, development, the chloroazotic acid etching of anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
S3, hemisphere shelly anode substrate put into the organic vacuum cavity of evaporated device, successively evaporation p-type doping hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, N-shaped doping electron transfer layer on described anode layer surface; Subsequently, substrate moves in the vacuum metal cavity of evaporated device, at described N-shaped doping electron transfer layer surface evaporation one deck cathode layer;
After above-mentioned technique is finished, make described hemisphere shelly organic electroluminescence device.
Hemisphere shelly organic electroluminescence device provided by the invention, owing to being hemispheric, the total internal reflection loss that the difference by luminescent layer and air refraction can be caused penetrates by the curved surface refraction, the transversal waveguides loss of organic layer can also be caught, so light extraction efficiency improves greatly; Simultaneously, this hemisphere shelly organic electroluminescence device does not have dependence of angle, and this dependence is directly determined by semi-spherical shape, and this organic electroluminescence device preparation technology is simple.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The structure of the hemisphere shelly organic electroluminescence device of the present embodiment is: glass/ITO/m-MTDATA:F4-TCNQ/TAPC/TCTA:Ir (ppy)
3/ Bphen/Bphen:Cs
2CO
3/ Mg:Ag.
The preparation process of the hemisphere shelly organic electroluminescence device of the present embodiment is as follows:
1, is that 5mm, thickness are the hemisphere substrate of glass of 2mm with internal diameter, uses successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
2, the hemisphere substrate of glass is put into the organic vacuum cavity of magnetron sputtering apparatus, the ito anode layer that sputter one deck 150nm is thick; Then will be coated with glass spin coating photoresist, exposure, development, the chloroazotic acid etching of ito anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
3, ITO hemisphere glass is put into the organic vacuum cavity of evaporated device, (material is m-MTDATA:F4-TCNQ to evaporation p-type doping hole transmission layer successively, thickness is 40nm), electronic barrier layer (material is TAPC, and thickness is 5nm), (material is TCTA:Ir (ppy) to luminescent layer
3Thickness is 40nm), hole blocking layer (material is Bphen, and thickness is 10nm), (material is Bphen:Cs to N-shaped doping electron transfer layer
2CO
3Thickness 40nm);
4, substrate is moved into the vacuum metal cavity of evaporated device, (material is that mass ratio is 10: 1 magnesium silver alloy, i.e. Mg:Ag to continue the evaporation cathode layer on N-shaped doping electron transfer layer surface; Thickness 150nm);
After above-mentioned technique is finished, make the organic electroluminescence device of described hemisphere shelly.
The structure of the hemisphere shelly organic electroluminescence device of the present embodiment is: glass/FTO/TPD:TCNQ/TPD/TCTA:Ir (ppy)
3/ PBD/PBD:LiF/Ag.
The preparation process of the hemisphere shelly organic electroluminescence device of the present embodiment is as follows:
1, is that 5mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, uses successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
2, the hemisphere substrate of glass is put into the organic vacuum cavity of magnetron sputtering apparatus, the FTO anode layer that sputter one deck 180nm is thick; Then will be coated with glass spin coating photoresist, exposure, development, the chloroazotic acid etching of FTO anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
3, FTO hemisphere glass is put into the organic vacuum cavity of evaporated device, (material is TPD:TCNQ to evaporation p-type doping hole transmission layer successively, thickness is 20nm), electronic barrier layer (material is TPD, and thickness is 5nm), (material is TCTA:Ir (ppy) to luminescent layer
3, thickness is 30nm), hole blocking layer (material is PBD, and thickness is 2nm), (material is PBD:LiF to N-shaped doping electron transfer layer; Thickness 60nm);
4, substrate is moved into the vacuum metal cavity of evaporated device, (material is Ag to continue the evaporation cathode layer on N-shaped doping electron transfer layer surface; Thickness 100nm);
After above-mentioned technique is finished, make the organic electroluminescence device of described hemisphere shelly.
Embodiment 3
The structure of the hemisphere shelly organic electroluminescence device of the present embodiment is: glass/AZO/TCTA:MoO
3/ TCTA/TPBi:Ir (ppy)
3/ TPBi/TPBI:Li
2CO
3/ Al.
The preparation process of the hemisphere shelly organic electroluminescence device of the present embodiment is as follows:
1, is that 5mm, thickness are the hemisphere substrate of glass of 5mm with internal diameter, uses successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
2, the hemisphere substrate of glass is put into the organic vacuum cavity of magnetron sputtering apparatus, the AZO anode layer that sputter one deck 200nm is thick; Then will be coated with glass spin coating photoresist, exposure, development, the chloroazotic acid etching of AZO anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
3, AZO hemisphere glass is put into the organic vacuum cavity of evaporated device, (material is TCTA:MoO to evaporation p-type doping hole transmission layer successively
3, thickness is 60nm), electronic barrier layer (material is TCTA, and thickness is 10nm), (material is TPBi:Ir (ppy) to luminescent layer
3Thickness is 50nm), hole blocking layer (material is TPBi, and thickness is 20nm), (material is TPBI:Li to N-shaped doping electron transfer layer
2CO
3Thickness 80nm);
4, substrate is moved into the vacuum metal cavity of evaporated device, (material is Al to continue the evaporation cathode layer on N-shaped doping electron transfer layer surface; Thickness 200nm);
After above-mentioned technique is finished, make the organic electroluminescence device of described hemisphere shelly.
The structure of the hemisphere shelly organic electroluminescence device of the present embodiment is: glass/IZO/NPB:MoO
3/ TAPC/TCTA:Ir (piq)
3/ Alq
3/ Alq
3: CsN
3/ Pt.
The preparation process of the hemisphere shelly organic electroluminescence device of the present embodiment is as follows:
1, is that 5mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, uses successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
2, the hemisphere substrate of glass is put into the organic vacuum cavity of magnetron sputtering apparatus, the IZO anode layer that sputter one deck 100nm is thick; Then will be coated with glass spin coating photoresist, exposure, development, the chloroazotic acid etching of IZO anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
3, IZO hemisphere glass is put into the organic vacuum cavity of evaporated device, (material is NPB:MoO to evaporation p-type doping hole transmission layer successively
3, thickness is 80nm), electronic barrier layer (material is TAPC, and thickness is 20nm), (material is TCTA:Ir (piq) to luminescent layer
3Thickness is 40nm), (material is Alq to hole blocking layer
3, thickness is 20nm), (material is Alq to N-shaped doping electron transfer layer
3: CsN
3Thickness 100nm);
4, substrate is moved into the vacuum metal cavity of evaporated device, (material is Pt to continue the evaporation cathode layer on N-shaped doping electron transfer layer surface; Thickness 100nm);
After above-mentioned technique is finished, make the organic electroluminescence device of described hemisphere shelly.
Embodiment 5
The structure of the hemisphere shelly organic electroluminescence device of the present embodiment is: glass/ITO/m-MTDATA:F4-TCNQ/TAPC/TCTA:BCzVBi/BND/BND:CsF/Au.
The preparation process of the hemisphere shelly organic electroluminescence device of the present embodiment is as follows:
1, is that 8mm, thickness are the hemisphere substrate of glass of 5mm with internal diameter, uses successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
2, the hemisphere substrate of glass is put into the organic vacuum cavity of magnetron sputtering apparatus, the ito anode layer that sputter one deck 150nm is thick; Then will be coated with glass spin coating photoresist, exposure, development, the chloroazotic acid etching of ito anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
3, ITO hemisphere glass is put into the organic vacuum cavity of evaporated device, (material is m-MTDATA:F4-TCNQ to evaporation p-type doping hole transmission layer successively, thickness is 40nm), electronic barrier layer (material is TAPC, and thickness is 5nm), (material is TCTA:BCzVBi to luminescent layer; Thickness is 60nm), hole blocking layer (material is BND, and thickness is 12nm), (material is BND:CsF to N-shaped doping electron transfer layer; Thickness 40nm);
4, substrate is moved into the vacuum metal cavity of evaporated device, (material is Au to continue the evaporation cathode layer on N-shaped doping electron transfer layer surface; Thickness 120nm);
After above-mentioned technique is finished, make the organic electroluminescence device of described hemisphere shelly.
The structure of the hemisphere shelly organic electroluminescence device of the present embodiment is: glass/ITO/m-MTDATA:F4-TCNQ/TAPC/TPBi:Ir (MDQ)
2(acac)/Bphen/Bphen:Cs
2CO
3/ Mg:Ag.
The preparation process of the hemisphere shelly organic electroluminescence device of the present embodiment is as follows:
1, is that 3mm, thickness are the hemisphere substrate of glass of 1mm with internal diameter, uses successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
2, the hemisphere substrate of glass is put into the organic vacuum cavity of magnetron sputtering apparatus, the ito anode layer that sputter one deck 150nm is thick; Then will be coated with glass spin coating photoresist, exposure, development, the chloroazotic acid etching of ito anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
3, ITO hemisphere glass is put into the organic vacuum cavity of evaporated device, (material is m-MTDATA:F4-TCNQ to evaporation p-type doping hole transmission layer successively, thickness is 40nm), electronic barrier layer (material is TAPC, and thickness is 5nm), (material is TPBi:Ir (MDQ) to luminescent layer
2(acac); Thickness is 40nm), hole blocking layer (material is Bphen, and thickness is 10nm), (material is Bphen:Cs to N-shaped doping electron transfer layer
2CO
3Thickness 40nm);
4, substrate is moved into the vacuum metal cavity of evaporated device, (material is that mass ratio is 10: 1 magnesium silver alloy, i.e. Mg:Ag to continue the evaporation cathode layer on N-shaped doping electron transfer layer surface; Thickness 150nm);
After above-mentioned technique is finished, make the organic electroluminescence device of described hemisphere shelly.
Embodiment 7
The structure of the hemisphere shelly organic electroluminescence device of the present embodiment is: glass/ITO/m-MTDATA:F4-TCNQ/TAPC/TCTA:Ir (ppy)
3/ Bphen/Bphen:Cs
2CO
3/ Au.
The preparation process of the hemisphere shelly organic electroluminescence device of the present embodiment is as follows:
1, is that 8mm, thickness are the hemisphere substrate of glass of 4mm with internal diameter, uses successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
2, the hemisphere substrate of glass is put into the organic vacuum cavity of magnetron sputtering apparatus, the ito anode layer that sputter one deck 150nm is thick; Then will be coated with glass spin coating photoresist, exposure, development, the chloroazotic acid etching of ito anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
3, ITO hemisphere glass is put into the organic vacuum cavity of evaporated device, (material is m-MTDATA:F4-TCNQ to evaporation p-type doping hole transmission layer successively, thickness is 40nm), electronic barrier layer (material is TAPC, and thickness is 5nm), (material is TCTA:Ir (ppy) to luminescent layer
3Thickness is 40nm), hole blocking layer (material is Bphen, and thickness is 10nm), (material is Bphen:Cs to N-shaped doping electron transfer layer
2CO
3Thickness 40nm);
4, substrate is moved into the vacuum metal cavity of evaporated device, (material is that mass ratio is 10: 1 magnesium silver alloy, i.e. Mg:Ag to continue the evaporation cathode layer on N-shaped doping electron transfer layer surface; Thickness 150nm);
After above-mentioned technique is finished, make the organic electroluminescence device of described hemisphere shelly.
The structure of the hemisphere shelly organic electroluminescence device of the present embodiment is: glass/ITO/m-MTDATA:F4-TCNQ/TAPC/TCTA:Ir (ppy)
3/ Bphen/Bphen:Cs
2CO
3/ Au.
The preparation process of the hemisphere shelly organic electroluminescence device of the present embodiment is as follows:
1, is that 6mm, thickness are the hemisphere substrate of glass of 3mm with internal diameter, uses successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
2, the hemisphere substrate of glass is put into the organic vacuum cavity of magnetron sputtering apparatus, the ito anode layer that sputter one deck 150nm is thick; Then will be coated with glass spin coating photoresist, exposure, development, the chloroazotic acid etching of ito anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
3, ITO hemisphere glass is put into the organic vacuum cavity of evaporated device, (material is m-MTDATA:F4-TCNQ to evaporation p-type doping hole transmission layer successively, thickness is 40nm), electronic barrier layer (material is TAPC, and thickness is 5nm), (material is TCTA:Ir (ppy) to luminescent layer
3Thickness is 40nm), hole blocking layer (material is Bphen, and thickness is 10nm), (material is Bphen:Cs to N-shaped doping electron transfer layer
2CO
3Thickness 40nm);
4, substrate is moved into the vacuum metal cavity of evaporated device, (material is that mass ratio is 10: 1 magnesium silver alloy, i.e. Mg:Ag to continue the evaporation cathode layer on N-shaped doping electron transfer layer surface; Thickness 150nm);
After above-mentioned technique is finished, make the organic electroluminescence device of described hemisphere shelly.
Comparative Examples
The structure of the organic electroluminescence device of this Comparative Examples is: glass/ITO/m-MTDATA:F4-TCNQ/TAPC/TCTA:Ir (ppy)
3/ Bphen/Bphen:Cs
2CO
3/ Mg:Ag.
The preparation process of the organic electroluminescence device of this Comparative Examples is as follows:
1, the flat glass substrate that 1mm is thick as a comparison
Use successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up post-drying;
2, the flat glass substrate is put into the organic vacuum cavity of magnetron sputtering apparatus, the ito anode layer that sputter one deck 150nm is thick; Then will be coated with flat glass substrate spin coating photoresist, exposure, development, the chloroazotic acid etching of ito anode layer, be etched into needed pattern and size, then the electro-conductive glass that etching is good cleans, use successively each 15min of each ultrasonic cleaning such as pure water, acetone, ethanol, clean up and rear it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W, improves the surperficial work content of electro-conductive glass with this;
3, ito glass is put into the organic vacuum cavity of evaporated device, (material is m-MTDATA:F4-TCNQ to evaporation p-type doping hole transmission layer successively, thickness is 40nm), electronic barrier layer (material is TAPC, and thickness is 5nm), (material is TCTA:Ir (ppy) to luminescent layer
3Thickness is 40nm), hole blocking layer (material is Bphen, and thickness is 10nm), (material is Bphen:Cs to N-shaped doping electron transfer layer
2CO
3Thickness 40nm);
4, substrate is moved into the vacuum metal cavity of evaporated device, (material is that mass ratio is 10: 1 magnesium silver alloy, i.e. Mg:Ag to continue the evaporation cathode layer on N-shaped doping electron transfer layer surface; Thickness 150nm);
After above-mentioned technique is finished, make the organic electroluminescence device of described hemisphere shelly.
Fig. 3 is embodiment 1,2 and 3 and the brightness of the hemisphere shelly organic electroluminescence device of Comparative Examples-voltage curve comparison diagram.
Fig. 4 is embodiment 1,2 and 3 and the maximum luminous efficiency figure of the hemisphere shelly organic electroluminescence device of Comparative Examples.
The used preparation of the present invention and tester are: high vacuum thermal resistance evaporation coating system (scientific instrument development center, Shenyang Co., Ltd, pressure＜10
-4Pa), current-voltage tester (U.S. Keithly company, 2602), the electroluminescent spectrum tester (U.S. photo research company model:, model: PR650) and screen intensity meter (Beijing Normal University, model: ST-86LA).
As can be seen from Figure 3, because having greatly, the light of the organic electroluminescence device (being plate device) of Comparative Examples derives from the side wave of substrate, therefore brightness is not high; The brightness of embodiment 1,2 or 3 hemisphere shelly organic electroluminescence device is then apparently higher than plate device, and their electroluminescence brightness increases with the increase of ball wall thickness.
Can read a book from Fig. 4, the organic electroluminescence device luminous efficiency changes along with the variation of radius-thickness ratio, basically increases with radius-thickness ratio; When light source body has radius-thickness ratio more than the certain value
The time, can obtain high interior external quantum efficiency ratio; Interior external quantum efficiency can be very approaching, compares with slab construction, and the external quantum efficiency maximum has improved nearly 4 times.
Should be understood that, above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. hemisphere shelly organic electroluminescence device, it is characterized in that, comprise the substrate of hemisphere shelly, stacked gradually anode layer, p-type doping hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, N-shaped doping electron transfer layer and cathode layer at the inner surface of described hemisphere shelly substrate.
2. hemisphere shelly organic electroluminescence device according to claim 1 is characterized in that, the internal diameter of described hemisphere shelly substrate is 3～10mm, and the thickness of described hemisphere shelly substrate and the radius-thickness ratio between the internal diameter are 0.1～1.0.
3. hemisphere shelly organic electroluminescence device according to claim 1 is characterized in that, the material of described p-type doping hole transmission layer is hole mobile material doping tetrafluoro four cyano 1,4-benzoquinone bismethane, four cyano 1,4-benzoquinone bismethane or molybdenum trioxide.
4. hemisphere shelly organic electroluminescence device according to claim 2 is characterized in that, described hole mobile material is 4,4 ', 4 " three (3-aminomethyl phenyl aniline) triphenylamine, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4; 4 '-benzidine, 4; 4 ', 4 " three (carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine.
5. hemisphere shelly organic electroluminescence device according to claim 1, it is characterized in that, the material of described electronic barrier layer is 1,1-two [4-[N, N '-two (p-tolyl) amino] phenyl] cyclohexane, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine or 4,4 ', 4 " three (carbazole-9-yl) triphenylamines.
6. hemisphere shelly organic electroluminescence device according to claim 1 is characterized in that, the material of described luminescent layer is 4,4 ' and, 4 " three (carbazole-9-yl) triphenylamine, 1,2,4-triazole derivative or N-aryl benzimidazole doped luminescent materials.
7. hemisphere shelly organic electroluminescence device according to claim 5, it is characterized in that, described luminescent material is 4,4 '-two (9-ethyls-3-carbazole vinyl)-1,10-diphenyl, three (2-phenylpyridine) close iridium, two (2-methyl-diphenyl quinoxaline) (acetylacetone,2,4-pentanedione) and close iridium or three (1-phenyl-isoquinolin) and close iridium.
8. hemisphere shelly organic electroluminescence device according to claim 1, it is characterized in that, the material of described hole blocking layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 2,5-two (1-naphthyl)-1,3,4-diazole, 4,7-diphenyl-1,10-phenanthroline or N-aryl benzimidazole.
9. hemisphere shelly organic electroluminescence device according to claim 1 is characterized in that, the material of described N-shaped doping electron transfer layer is electron transport material doping cesium carbonate, cesium azide, cesium fluoride, lithium fluoride or lithium carbonate; Described electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 2,5-two (1-naphthyl)-1,3,4-diazole, 4,7-diphenyl-1,10-phenanthroline or N-aryl benzimidazole.
10. the preparation method of a hemisphere shelly organic electroluminescence device is characterized in that, comprises the steps:
S1, cleaning, the substrate of dry hemisphere shelly;
S2, employing magnetron sputtering technique are at the inner surface sputter anode layer of described hemisphere shelly substrate;
S3, on described anode layer surface successively evaporation p-type doping hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, N-shaped doping electron transfer layer and cathode layer;
After above-mentioned technique is finished, make described hemisphere shelly organic electroluminescence device.
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