CN104979491A - Organic light emission diode and preparation method therefor - Google Patents
Organic light emission diode and preparation method therefor Download PDFInfo
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- CN104979491A CN104979491A CN201410134556.XA CN201410134556A CN104979491A CN 104979491 A CN104979491 A CN 104979491A CN 201410134556 A CN201410134556 A CN 201410134556A CN 104979491 A CN104979491 A CN 104979491A
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Abstract
An organic light emission diode comprises a flexible substrate, a light matching layer, an anode layer, a light emitting unit and a cathode layer which are sequentially laminated. The material of the light matching layer is a mixture of inorganic nanometer particles and a light-cured binder with the mass ratio of 10-30:100. The refractive index of the light-cured binder is larger than 1.6 and is epoxy resin or polyacrylate, and the refractive index of the inorganic nanometer particles is larger than 2.4 at 550nm. According to the organic light emission diode, after the light-cured binder of the light matching layer is added with the inorganic nanometer particles of a higher refractive index, the refractive index of the light matching layer reaches 1.7-1.8. By arranging the light matching layer between the anode layer and the flexible substrate, the difference between refractive indexes of two layers of adjacent structures is reduced, so that the critical angle of total reflection is increased, the light output is increased, and the light extraction efficiency is improved. In addition, the invention provides a preparation method for the organic light emission diode.
Description
Technical field
The present invention relates to electroluminescent technology field, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (Organic Light Emission Diode, OLED) there is the characteristics such as brightness is high, material selection range is wide, driving voltage is low, all solidstate active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, a kind of Display Technique and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of current lot of domestic and foreign researcher.
Flexible OLED luminescent device has the advantage of flexibility and portability.But also there are some problems in traditional OLED light-emitting device, such as, OLED adopts tin indium oxide (Indium Tin Oxides usually, ITO) film is as anode, but ITO needs to adopt rare metal indium, costly, and it needs to adopt higher sputter temperature just can prepare film of high conductivity price usually, for flexible device, this is disadvantageous.At present, in order to replace ito thin film, many software engineering researchers invent anode of medium/medium/metal form (DMD structure), such as, WO
3/ Ag/WO
3structure.This kind of anode can adopt evaporation technology to prepare film forming, is therefore applicable to prepare flexible electrode.
In flexible OLED luminescent device, when light transmits from anode layer to flexible base, board direction, due to refractive index difference, total reflection phenomenon can be produced.And the size of the cirtical angle of total reflection and refractive index difference are inversely proportional to.Due in traditional flexible OLED luminescent device, the WO of anode
3refractive index generally 1.95, and the refractive index of the flexible PET film of substrate is generally about 1.6.Therefore, the refractive index between anode and substrate is comparatively large, and the cirtical angle of total reflection is less.When light is from anode to board transport, easily produce total reflection at the interface of anode and substrate, light output is less, thus makes light extraction efficiency lower.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of light extraction efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the flexible base, board, light matching layer, anode layer, luminescence unit and the cathode layer that stack gradually, described luminescence unit comprises the hole transmission layer, luminescent layer, the electron transfer layer that are sequentially laminated on described anode layer, the material of described smooth matching layer is mass ratio is the inorganic nanoparticles of 10 ~ 30:100 and the mixture of light-curing adhesive, the refractive index of described light-curing adhesive is greater than 1.6, described light-curing adhesive is epoxy resin or polyacrylate, and described inorganic nanoparticles is greater than 2.4 in the refractive index at 550nm place.
Wherein in an embodiment, the thickness of described smooth matching layer is 20 μm ~ 100 μm.
Wherein in an embodiment, described inorganic nanoparticles is vulcanized lead particle, zns particle or titanium dioxide granule.
Wherein in an embodiment, the particle diameter of described inorganic nanoparticles is 5nm ~ 25nm.
Wherein in an embodiment, described anode layer comprises the first medium layer, metal level and the second dielectric layer that stack gradually, and described first medium layer directly contacts with described smooth matching layer;
The material of described first medium layer is tungstic acid, molybdenum trioxide or zinc sulphide, and the thickness of described first medium layer is 40nm ~ 80nm;
The material of described metal level is silver, magnesium, aluminium or gold, and the thickness of described metal level is 15nm ~ 30nm;
The material of described second dielectric layer is tungstic acid, molybdenum trioxide or zinc sulphide, and the thickness of described second dielectric layer is 40nm ~ 80nm.
A preparation method for organic electroluminescence device, comprises the steps:
Flexible base, board is provided;
Screen printing technique is adopted to be printed on described flexible base, board by the mixture of light-curing adhesive and inorganic nanoparticles, then described mixture photocuring is formed light matching layer, the mass ratio of inorganic nanoparticles and described light-curing adhesive described in described mixture is 10 ~ 30:100, the refractive index of described light-curing adhesive is greater than 1.6, described light-curing adhesive is epoxy resin or polyacrylate, and described inorganic nanoparticles is greater than 2.4 in the refractive index at 550nm place;
Vacuum thermal resistance vapour deposition method is adopted to form anode layer on described smooth matching layer;
Adopt vacuum vapour deposition to form luminescence unit on described anode layer, described luminescence unit comprises the hole transmission layer, luminescent layer, the electron transfer layer that are sequentially laminated on described anode layer; And
Vacuum vapour deposition is adopted to form cathode layer on described luminescence unit.
Wherein in an embodiment, the mixture of light-curing adhesive and inorganic nanoparticles is printed in the step on described flexible base, board by described employing screen printing technique, and the silk screen of employing is 600 order ~ 1000 object silk screens.
Wherein in an embodiment; the mixture of described light-curing adhesive and inorganic nanoparticles is prepared as follows; by described light-curing adhesive and the mixing of described inorganic nanoparticles; ultrasonic disperse 1 hour ~ 5 hours, obtains the mixture of described light-curing adhesive and inorganic nanoparticles after mixing.
Wherein in an embodiment, adopt vacuum thermal resistance vapour deposition method to be formed in the step of anode layer on described smooth matching layer, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is 0.1nm/s ~ 1nm/s;
Adopt vacuum vapour deposition to be formed in the step of cathode layer on described luminescence unit, vacuum degree is 1 × 10
-5p
a~ 1 × 10
-3pa, evaporation rate is 0.01nm/s ~ 1nm/s.
Wherein in an embodiment, described employing vacuum thermal resistance vapour deposition method forms being operating as of anode layer on described smooth matching layer, vacuum thermal resistance vapour deposition method is adopted to form first medium layer on described smooth matching layer, the material of described first medium layer is tungstic acid, molybdenum trioxide or zinc sulphide, the thickness of described first medium layer is 40nm ~ 80nm, vacuum thermal resistance vapour deposition method is adopted to form metal level on described first medium layer, the material of described metal level is silver, magnesium, aluminium or gold, the thickness of described metal level is 15nm ~ 30nm, vacuum thermal resistance vapour deposition method is adopted to form second dielectric layer on described metal level, the material of described second dielectric layer is tungstic acid, molybdenum trioxide or zinc sulphide, the thickness of described second dielectric layer is 40nm ~ 80nm, described first medium layer, described metal level forms described anode layer together with described second dielectric layer.
Above-mentioned organic electroluminescence device, light matching layer adopts the inorganic nanoparticles of high index of refraction and the mixture of light-curing adhesive.The refractive index of inorganic nanoparticles at 550nm place is higher than 2.4.The refractive index of light-curing adhesive is greater than 1.6.After adding the inorganic nanoparticles of high index of refraction in light-curing adhesive, the refractive index of light matching layer can reach 1.7 ~ 1.8.By arranging light matching layer between flexible base, board and anode layer, the refractive index difference between adjacent two layers structure can be reduced, thus increase the cirtical angle of total reflection, increase light output, improve light extraction efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the flow chart of the preparation method of the organic electroluminescence device of an execution mode;
Fig. 3 is the luminance-current density characteristic curve figure of organic electroluminescence device prepared by embodiment 1 and comparative example 1.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode, comprise the flexible base, board 110, light matching layer 120, anode layer 130, luminescence unit 140 and the cathode layer 150 that stack gradually.
Flexible base, board 110 can be polymeric transparent film.Such as, flexible base, board 110 can be PETG (polyethylene terephthalate, PET) film, polyethersulfone resin (Poly (ethersulfones), PES) film, Merlon (Polycarbonate, PC) film or polyimides (Polyimide, PI) film etc.The thickness of flexible base, board 110 can be 0.1mm ~ 0.5mm.
The material of light matching layer 120 is mass ratio is the inorganic nanoparticles of 10 ~ 30:100 and the mixture of light-curing adhesive.
The refractive index of light-curing adhesive is greater than 1.6, and light-curing adhesive can be epoxy resin or polyacrylate.
Inorganic nanoparticles is greater than 2.4 in the refractive index at 550nm place.Inorganic nanoparticles can be vulcanized lead (PbS) particle, zinc sulphide (ZnS) particle or titanium dioxide (TiO
2) particle etc.The particle diameter of inorganic nanoparticles can be 5nm ~ 25nm.
The thickness of light matching layer 120 can be 20 μm ~ 100 μm.
Anode layer 130 comprises the first medium layer 132, metal level 134 and the second dielectric layer 136 that stack gradually.First medium layer 132 directly contacts with light matching layer 120.For convenience of description, hereinafter, anode layer 130 first medium layer 132/ metal level 134/ second dielectric layer 136 represents.
The material of first medium layer 132 can be tungstic acid (WO
3), molybdenum trioxide (MoO
3) or zinc sulphide (ZnS).Certainly, the material of first medium layer 132 also can have hole injection efficiency for other, and the material that light transmission is good.The thickness of first medium layer 132 can be 40nm ~ 80nm.
The material of metal level 134 can be silver (Ag), magnesium (Mg), aluminium (Al) or gold (Au).Certainly, the material of metal level 134 also can be other metal materials.The thickness of metal level 134 can be 15nm ~ 30nm.
The material of second dielectric layer 136 can be WO
3, MoO
3or ZnS.Certainly, the material of second dielectric layer 136 also can have hole injection efficiency for other, and the material that light transmission is good.The thickness of second dielectric layer 136 can be 40nm ~ 80nm.
In the present embodiment, the structure of anode layer 130 can be WO
3layer/Ag layer/WO
3layer.The structure of anode layer 130 can also be MoO
3layer/Al layer/MoO
3layer.
Luminescence unit 140 comprises the hole transmission layer 142 be sequentially laminated on anode layer 130, luminescent layer 144 and electron transfer layer 146.
The material of hole transmission layer 142 can be N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD) or N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD).
The thickness of hole transmission layer 142 can be 20nm ~ 60nm.
The material of luminescent layer 144 is the mixture of luminescent material and material of main part.The mass ratio of luminescent material and material of main part can be 5:100 ~ 30:100.
Luminescent material can be fluorescent material or phosphor material.Fluorescent material is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), dimethylquinacridone (DMQA), 5, 6, 11, 12-tetraphenyl naphthonaphthalene (Rubrene), 2, 3, 6, 7-tetrahydrochysene-1, 1, 7, 7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9, 9A, 1GH] cumarin (C545T), 4, 4'-bis-(2, 2-diphenylethyllene)-1, 1'-biphenyl (DPVBi), 4, 4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) and 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl (BCzVBi).Phosphor material is selected from two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (FIrpic), two (4,6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid conjunction iridium (FIr6), two (4,6-bis-fluoro-5-cyano-phenyl pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium (FIrN4), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq)
2(acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) and three (2-phenylpyridines) close iridium (Ir (ppy)
3) at least one.Material of main part is selected from 4,4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq
3), at least one in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB).
The thickness of luminescent layer 144 can be 5nm ~ 30nm.
The material of electron transfer layer 146 is electron transport material.The material of electron transfer layer 146 is selected from oxine aluminium (Alq
3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) and 2, at least one in 9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP).
The thickness of electron transfer layer 146 can be 20nm ~ 40nm.
The material of cathode layer 150 can be silver (Ag) or aluminium (Al).The thickness of cathode layer 150 can be 70nm ~ 200nm.
Above-mentioned organic electroluminescence device 100, light matching layer 120 adopts the inorganic nanoparticles of high index of refraction and the mixture of light-curing adhesive, and the refractive index of inorganic nanoparticles at 550nm place, higher than 2.4, even reaches 4.0.The refractive index of light-curing adhesive is greater than 1.6.After adding the inorganic nanoparticles of high index of refraction in light-curing adhesive, its refractive index can improve 0.1 ~ 0.2 usually, and therefore the refractive index of light matching layer 120 can be increased to more than 1.7 and even reaches 1.8.When light transmits from anode layer 130 to flexible base, board 110 direction, due to refractive index difference, total reflection phenomenon can be produced.And the refractive index difference between the size of the cirtical angle of total reflection and adjacent two layers structure is inversely proportional to, reduces the refractive index difference between flexible base, board 110 and anode layer 130, just can increase the cirtical angle of total reflection, thus increase light output.By arranging light matching layer 120 between flexible base, board 110 and anode layer 130, can make to realize optical match between flexible base, board 110 and anode layer 130, reduce the refractive index difference between adjacent two layers structure, increase the cirtical angle of total reflection, increase light output, thus improve light extraction efficiency.
As shown in Figure 2, the preparation method of the above-mentioned organic electroluminescence device of an execution mode, comprises the steps:
S110, provide flexible base, board.
Flexible base, board cleans up before use.
Flexible base, board can be polymeric transparent film.Such as, PETG (polyethylene terephthalate, PET) film, polyethersulfone resin (Poly (ether sulfones), PES) film, Merlon (Polycarbonate, PC) film or polyimides (Polyimide, PI) film etc.The thickness of flexible base, board can be 0.1mm ~ 0.5mm.
S120, adopt screen printing technique by the mixture printing of light-curing adhesive and inorganic nanoparticles on flexible substrates, then mixture photocuring is formed light matching layer.In mixture, the mass ratio of inorganic nanoparticles and light-curing adhesive is 10 ~ 30:100.The refractive index of light-curing adhesive is greater than 1.6, and light-curing adhesive is epoxy resin or polyacrylate.Inorganic nanoparticles is greater than 2.4 in the refractive index at 550nm place.
The mixture of light-curing adhesive and inorganic nanoparticles is prepared as follows, and by light-curing adhesive and inorganic nanoparticles mixing, ultrasonic disperse 1 hour ~ 5 hours, obtains the mixture of light-curing adhesive and inorganic nanoparticles after mixing.
Inorganic nanoparticles can be vulcanized lead (PbS) particle, zinc sulphide (ZnS) particle or titanium dioxide (TiO
2) particle etc.The particle diameter of inorganic nanoparticles can be 5nm ~ 25nm.
The thickness of light matching layer is 20 μm ~ 100 μm.
S130, employing vacuum thermal resistance vapour deposition method form anode layer on light matching layer.
Vacuum thermal resistance vapour deposition method is adopted to form being operating as of anode layer on light matching layer, vacuum thermal resistance vapour deposition method is adopted to form first medium layer on light matching layer, adopt vacuum thermal resistance vapour deposition method to form metal level on first medium layer, adopt vacuum thermal resistance vapour deposition method to form second dielectric layer on the metal layer.First medium layer, metal level form anode layer together with second dielectric layer.
When adopting vacuum thermal resistance vapour deposition method to form first medium layer on flexible substrates, vacuum degree can be 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate can be 0.1nm/s ~ 1nm/s.The material of first medium layer can be tungstic acid (WO
3), molybdenum trioxide (MoO
3) or zinc sulphide (ZnS), certainly, the material of first medium layer also can have hole injection efficiency for other, and the material that light transmission is good.The thickness of first medium layer can be 40nm ~ 80nm.
When adopting vacuum thermal resistance vapour deposition method to form metal level on first medium layer, vacuum degree can be 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate can be 0.1nm/s ~ 1nm/s.The material of metal level can be silver (Ag), magnesium (Mg), aluminium (Al) or gold (Au), and certainly, the material of metal level also can be other metal materials.The thickness of metal level can be 15nm ~ 30nm.
When adopting vacuum thermal resistance vapour deposition method to form second dielectric layer on the metal layer, vacuum degree can be 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate can be 0.1nm/s ~ 1nm/s.The material of second dielectric layer can be WO
3, MoO
3or ZnS.Certainly, the material of second dielectric layer also can have hole injection efficiency for other, and the material that light transmission is good.The thickness of second dielectric layer can be 40nm ~ 80nm.
In the present embodiment, the structure of the anode layer of formation can be WO
3layer/Ag layer/WO
3layer.The structure of anode layer can also be MoO
3layer/Al layer/MoO
3layer.
S140, employing vacuum vapour deposition form luminescence unit on the anode layer, and luminescence unit comprises the hole transmission layer, luminescent layer, the electron transfer layer that stack gradually on the anode layer.
Vacuum vapour deposition is adopted to form being operating as of luminescence unit on the anode layer, vacuum vapour deposition is adopted to form hole transmission layer on the anode layer, vacuum vapour deposition is adopted to form luminescent layer on hole transmission layer, adopt vacuum vapour deposition to form electron transfer layer on luminescent layer, hole transmission layer, luminescent layer form luminescence unit together with electron transfer layer.
When adopting vacuum vapour deposition to form hole transmission layer on the anode layer, vacuum degree can be 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate can be 0.1nm/s ~ 1nm/s.The material of hole transmission layer can be N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD) or N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD).The thickness of hole transmission layer can be 20nm ~ 60nm.
When adopting vacuum vapour deposition to form luminescent layer on hole transmission layer, vacuum degree can be 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate can be 0.01nm/s ~ 1nm/s.The material of luminescent layer is the mixture of luminescent material and material of main part.The mass ratio of luminescent material and material of main part can be 5:100 ~ 30:100.Luminescent material can be fluorescent material or phosphor material.Fluorescent material is selected from 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), dimethylquinacridone (DMQA), 5, 6, 11, 12-tetraphenyl naphthonaphthalene (Rubrene), 2, 3, 6, 7-tetrahydrochysene-1, 1, 7, 7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9, 9A, 1GH] cumarin (C545T), 4, 4'-bis-(2, 2-diphenylethyllene)-1, 1'-biphenyl (DPVBi), 4, 4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) and 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl (BCzVBi).Phosphor material is selected from two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (FIrpic), two (4,6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid conjunction iridium (FIr6), two (4,6-bis-fluoro-5-cyano-phenyl pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium (FIrN4), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq)
2(acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) and three (2-phenylpyridines) close iridium (Ir (ppy)
3) at least one.Material of main part is selected from 4,4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq
3), at least one in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB).The thickness of luminescent layer can be 5nm ~ 30nm.
When adopting vacuum vapour deposition to form electron transfer layer on luminescent layer, vacuum degree can be 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate can be 0.1nm/s ~ 1nm/s.The material of electron transfer layer is electron transport material.The material of electron transfer layer 146 is selected from oxine aluminium (Alq
3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) and 2, at least one in 9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP).The thickness of electron transfer layer can be 20nm ~ 40nm.
S150, employing vacuum vapour deposition form cathode layer on luminescence unit.
When adopting vacuum vapour deposition to form cathode layer on luminescence unit, vacuum degree can be 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate can be 0.01nm/s ~ 1nm/s.
The material of cathode layer 150 can be silver (Ag) or aluminium (Al).The thickness of cathode layer 150 can be 70nm ~ 200nm.
The preparation method of above-mentioned organic electroluminescence device, preparation technology is simple, and easily operate, the light extraction efficiency of the organic electroluminescence device prepared is high.
Be specific embodiment part below.
Embodiment 1
There is provided thickness to be the pet substrate of 0.1mm, and clean up.
The PbS of mass ratio 10:100 is mixed with epoxy resin.The particle diameter of PbS is 5nm.Then ultrasonic oscillation disperses 1 hour, obtains mixture.Then adopt screen printing technique, meshcount is 1000 orders, said mixture is printed on flexible base, board surface, forms the film that thickness is 20 μm.Then adopt process for photocuring, by above-mentioned film hardening, form light matching layer.
Vacuum thermal resistance vapour deposition method is adopted to form first medium layer on light matching layer.The material of first medium layer is WO
3, thickness is 40nm.Vacuum thermal resistance vapour deposition method is adopted to form metal level on first medium layer.The material of metal level is Ag, and thickness is 18nm.Vacuum thermal resistance vapour deposition method is adopted to form second dielectric layer on the metal layer.The material of second dielectric layer is WO
3, thickness is 40nm.The first medium layer stacked gradually, metal level form anode layer together with second dielectric layer.It is all 1 × 10 in vacuum degree that vacuum thermal resistance evaporation forms first medium layer, metal level and second dielectric layer
-5carry out in the vacuum coating system of Pa, evaporation rate is 0.1nm/s.
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt vacuum vapour deposition, in second dielectric layer, form hole transmission layer with the evaporation rate of 0.1nm/s.The material of hole transmission layer is TPD, and thickness is 20nm.
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt vacuum vapour deposition, hole transmission layer forms luminescent layer.The material of luminescent layer is doped with Ir (piq)
2(acac) NPB, wherein, Ir (piq)
2(acac) be 10:100 with the mass ratio of NPB.The thickness of luminescent layer is 20nm.Ir (piq)
2(acac) evaporation rate is the evaporation rate of 0.1nm/s, NPB is 1nm/s.
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt vacuum vapour deposition, with the evaporation rate of 0.1nm/s, luminescent layer forms electron transfer layer.The material of electron transfer layer is Bphen, and thickness is 20nm.
Be 1 × 10 in vacuum degree
-5in the vacuum coating system of Pa, adopt vacuum vapour deposition, with the evaporation rate of 0.1nm/s, form negative electrode on the electron transport layer.The material of negative electrode is Al, and thickness is 70nm.Obtain organic electroluminescence device.
Embodiment 2
There is provided thickness to be the PES substrate of 0.5mm, and clean up.
Be that the ZnS of 20:100 mixes with polyacrylate by mass ratio.The particle diameter of ZnS is 25nm.Then ultrasonic oscillation disperses 5 hours, obtains mixture.Then adopt screen printing technique, meshcount is 600 orders, said mixture is printed on flexible base, board surface, forms the film that thickness is 100 μm.Then adopt process for photocuring, by above-mentioned film hardening, form light matching layer.
Vacuum thermal resistance vapour deposition method is adopted to form first medium layer on light matching layer.The material of first medium layer is MoO
3layer, thickness is 80nm.Vacuum thermal resistance vapour deposition method is adopted to form metal level on first medium layer.The material of metal level is Al, and thickness is 30nm.Vacuum thermal resistance vapour deposition method is adopted to form second dielectric layer on the metal layer.The material of second dielectric layer is MoO
3layer, thickness is 80nm.The first medium layer stacked gradually, metal level form anode layer together with second dielectric layer.It is all 1 × 10 in vacuum degree that vacuum thermal resistance evaporation forms first medium layer, metal level and second dielectric layer
-3carry out in the vacuum coating system of Pa, evaporation rate is 1nm/s.
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt vacuum vapour deposition, in second dielectric layer, form hole transmission layer with the evaporation rate of 1nm/s.The material of hole transmission layer is NPB, and thickness is 60nm.
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt vacuum vapour deposition, hole transmission layer forms luminescent layer.The thickness of luminescent layer is 5nm.The material of luminescent layer is C545T and Alq
3mixture, C545T and Alq
3mass ratio be 5:100.The evaporation rate of C545T is 0.05nm/s, Alq
3evaporation rate be 0.2nm/s.
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt vacuum vapour deposition, with the evaporation rate of 1nm/s, luminescent layer forms electron transfer layer.The material of electron transfer layer is TPBi, and thickness is 40nm.
Be 1 × 10 in vacuum degree
-3in the vacuum coating system of Pa, adopt vacuum vapour deposition, with the evaporation rate of 1nm/s, form negative electrode on the electron transport layer.The material of negative electrode is Ag, and thickness is 200nm.Obtain organic electroluminescence device.
Embodiment 3
There is provided thickness to be the PI substrate of 0.2mm, and clean up.
Be the TiO of 30:100 by mass ratio
2mix with polyacrylate, TiO
2particle diameter be 15nm, then ultrasonic oscillation disperses 2 hours, obtains mixture.Then adopt screen printing technique, meshcount is 800 orders, said mixture is printed on flexible base, board surface, forms the film that thickness is 50 μm.Then adopt process for photocuring, by above-mentioned film hardening, form light matching layer.
Vacuum thermal resistance vapour deposition method is adopted to form first medium layer on light matching layer.The material of first medium layer is ReO
3layer, thickness is 60nm.Vacuum thermal resistance vapour deposition method is adopted to form metal level on first medium layer.The material of metal level is Au, and thickness is 20nm.Vacuum thermal resistance vapour deposition method is adopted to form second dielectric layer on the metal layer.The material of second dielectric layer is ReO
3, thickness is 60nm.The first medium layer stacked gradually, metal level form anode layer together with second dielectric layer.It is all 1 × 10 in vacuum degree that vacuum thermal resistance evaporation forms first medium layer, metal level and second dielectric layer
-4carry out in the vacuum coating system of Pa, evaporation rate is 0.5nm/s.
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt vacuum vapour deposition, in second dielectric layer, form hole transmission layer with the evaporation rate of 1nm/s.The material of hole transmission layer is TPD, and thickness is 50nm.
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt vacuum vapour deposition, hole transmission layer forms luminescent layer.The thickness of luminescent layer is 15nm.The material of luminescent layer is the CBP doped with FIrpic, and wherein the mass ratio of FIrpic and CBP is 30:100.The evaporation rate of FIrpic is the evaporation rate of 0.15nm/s, CBP is 1nm/s.
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt vacuum vapour deposition, with the evaporation rate of 0.5nm/s, luminescent layer forms electron transfer layer.The material of electron transfer layer is BCP, and thickness is 15nm.
Be 1 × 10 in vacuum degree
-4in the vacuum coating system of Pa, adopt vacuum vapour deposition, with the evaporation rate of 0.5nm/s, form negative electrode on the electron transport layer.The material of negative electrode is Ag, and thickness is 100nm.Obtain organic electroluminescence device.
Comparative example 1
The organic electroluminescence device of comparative example 1 is substantially identical with the preparation method of the organic electroluminescence device of embodiment 1, and difference is, does not prepare the step of light matching layer in comparative example 1, and first medium layer is formed directly on flexible base, board.
The structure of the organic electroluminescence device that organic electroluminescence device prepared by comparative example 1 is prepared with embodiment 1 is substantially identical.Difference is, do not have light matching layer between the flexible base, board of the organic electroluminescence device of comparative example 1 and first medium layer, first medium layer is set directly on flexible base, board.
The organic electroluminescence device of the organic electroluminescence device of embodiment 1 ~ 3 and comparative example 1 is carried out luminosity and luminous efficiency test, and test result is as shown in table 1.Luminous efficiency is carried out under the driving voltage of 6V.As can be seen from Table 1, the organic electroluminescence device of embodiment 1 ~ 3 by forming light matching layer between flexible base, board and anode layer, and its luminosity significantly improves, and luminous efficiency have also been obtained and significantly improves.Relative to the organic electroluminescence device of comparative example 1, the luminosity of the organic electroluminescence device of embodiment 1 adds 80%, and luminous efficiency improves 68%.
Table 1
| Luminosity (cd/m 2） | Luminous efficiency (Lm/W) | |
| Embodiment 1 | 6798 | 15.8 |
| Embodiment 2 | 8254 | 17.9 |
| Embodiment 3 | 6125 | 14.2 |
| Comparative example 1 | 3784 | 9.4 |
Fig. 3 is the luminance-current density characteristic curve figure of the organic electroluminescence device of embodiment 1 and the organic electroluminescence device of comparative example 1.Under identical drive current, embodiment 1 has the luminosity higher than comparative example 1.Be such as 65mA/cm at drive current
2time, the luminosity that embodiment 1 obtains reaches 6798cd/m
2, and comparative example 1 only has 3714cd/m
2.The luminosity of embodiment 1 improves 80% relative to comparative example 1.Brightness is improved and has benefited from the raising of light extraction efficiency, because the present invention have employed light matching layer between substrate and anode, have matched the refractive index between anode and substrate, the cirtical angle of total reflection of bright dipping is increased, therefore the probability of light emission total reflection reduces, and the light therefore sent increases.
Above-mentioned vacuum coating system is purchased from scientific instrument development center, Shenyang Co., Ltd.The electrical performance testing of organic electroluminescence device adopts the Keithley2400 of Keithley company of the U.S..The luminosity test of organic electroluminescence device adopts the CS-100A colorimeter of Japanese Konica Minolta company.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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. an organic electroluminescence device, comprise the flexible base, board stacked gradually, light matching layer, anode layer, luminescence unit and cathode layer, described luminescence unit comprises the hole transmission layer be sequentially laminated on described anode layer, luminescent layer, electron transfer layer, it is characterized in that, the material of described smooth matching layer is mass ratio is the inorganic nanoparticles of 10 ~ 30:100 and the mixture of light-curing adhesive, the refractive index of described light-curing adhesive is greater than 1.6, described light-curing adhesive is epoxy resin or polyacrylate, described inorganic nanoparticles is greater than 2.4 in the refractive index at 550nm place.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described smooth matching layer is 20 μm ~ 100 μm.
3. organic electroluminescence device according to claim 1, is characterized in that, described inorganic nanoparticles is vulcanized lead particle, zns particle or titanium dioxide granule.
4. organic electroluminescence device according to claim 1, is characterized in that, the particle diameter of described inorganic nanoparticles is 5nm ~ 25nm.
5. organic electroluminescence device according to claim 1, is characterized in that, described anode layer comprises the first medium layer, metal level and the second dielectric layer that stack gradually, and described first medium layer directly contacts with described smooth matching layer;
The material of described first medium layer is tungstic acid, molybdenum trioxide or zinc sulphide, and the thickness of described first medium layer is 40nm ~ 80nm;
The material of described metal level is silver, magnesium, aluminium or gold, and the thickness of described metal level is 15nm ~ 30nm;
The material of described second dielectric layer is tungstic acid, molybdenum trioxide or zinc sulphide, and the thickness of described second dielectric layer is 40nm ~ 80nm.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Flexible base, board is provided;
Screen printing technique is adopted to be printed on described flexible base, board by the mixture of light-curing adhesive and inorganic nanoparticles, then described mixture photocuring is formed light matching layer, the mass ratio of inorganic nanoparticles and described light-curing adhesive described in described mixture is 10 ~ 30:100, the refractive index of described light-curing adhesive is greater than 1.6, described light-curing adhesive is epoxy resin or polyacrylate, and described inorganic nanoparticles is greater than 2.4 in the refractive index at 550nm place;
Vacuum thermal resistance vapour deposition method is adopted to form anode layer on described smooth matching layer;
Adopt vacuum vapour deposition to form luminescence unit on described anode layer, described luminescence unit comprises the hole transmission layer, luminescent layer, the electron transfer layer that are sequentially laminated on described anode layer; And
Vacuum vapour deposition is adopted to form cathode layer on described luminescence unit.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the mixture of light-curing adhesive and inorganic nanoparticles is printed in the step on described flexible base, board by described employing screen printing technique, and the silk screen of employing is 600 order ~ 1000 object silk screens.
8. the preparation method of organic electroluminescence device according to claim 6; it is characterized in that; the mixture of described light-curing adhesive and inorganic nanoparticles is prepared as follows; by described light-curing adhesive and the mixing of described inorganic nanoparticles; ultrasonic disperse 1 hour ~ 5 hours, obtains the mixture of described light-curing adhesive and inorganic nanoparticles after mixing.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, adopt vacuum thermal resistance vapour deposition method to be formed in the step of anode layer on described smooth matching layer, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is 0.1nm/s ~ 1nm/s;
Adopt vacuum vapour deposition to be formed in the step of cathode layer on described luminescence unit, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is 0.01nm/s ~ 1nm/s.
10. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, described employing vacuum thermal resistance vapour deposition method forms being operating as of anode layer on described smooth matching layer, vacuum thermal resistance vapour deposition method is adopted to form first medium layer on described smooth matching layer, the material of described first medium layer is tungstic acid, molybdenum trioxide or zinc sulphide, the thickness of described first medium layer is 40nm ~ 80nm, vacuum thermal resistance vapour deposition method is adopted to form metal level on described first medium layer, the material of described metal level is silver, magnesium, aluminium or gold, the thickness of described metal level is 15nm ~ 30nm, vacuum thermal resistance vapour deposition method is adopted to form second dielectric layer on described metal level, the material of described second dielectric layer is tungstic acid, molybdenum trioxide or zinc sulphide, the thickness of described second dielectric layer is 40nm ~ 80nm, described first medium layer, described metal level forms described anode layer together with described second dielectric layer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057863A (en) * | 2016-08-15 | 2016-10-26 | 深圳市华星光电技术有限公司 | Multi-primary-color OLED display device |
| CN111180500A (en) * | 2020-02-26 | 2020-05-19 | 京东方科技集团股份有限公司 | Display substrate and electroluminescent display device |
| CN111755632A (en) * | 2020-07-30 | 2020-10-09 | 河南工程学院 | Flexible organic electroluminescent device and preparation method thereof |
| CN113054116A (en) * | 2019-12-28 | 2021-06-29 | Tcl集团股份有限公司 | Light emitting diode |
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2014
- 2014-04-03 CN CN201410134556.XA patent/CN104979491A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057863A (en) * | 2016-08-15 | 2016-10-26 | 深圳市华星光电技术有限公司 | Multi-primary-color OLED display device |
| CN106057863B (en) * | 2016-08-15 | 2019-05-31 | 深圳市华星光电技术有限公司 | More primary colors OLED displays |
| CN113054116A (en) * | 2019-12-28 | 2021-06-29 | Tcl集团股份有限公司 | Light emitting diode |
| CN111180500A (en) * | 2020-02-26 | 2020-05-19 | 京东方科技集团股份有限公司 | Display substrate and electroluminescent display device |
| CN111180500B (en) * | 2020-02-26 | 2023-10-24 | 京东方科技集团股份有限公司 | Display substrate and electroluminescent display device |
| CN111755632A (en) * | 2020-07-30 | 2020-10-09 | 河南工程学院 | Flexible organic electroluminescent device and preparation method thereof |
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