CN110277505A - Organic electroluminescence device with mixing coating - Google Patents
Organic electroluminescence device with mixing coating Download PDFInfo
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- CN110277505A CN110277505A CN201810210164.5A CN201810210164A CN110277505A CN 110277505 A CN110277505 A CN 110277505A CN 201810210164 A CN201810210164 A CN 201810210164A CN 110277505 A CN110277505 A CN 110277505A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Abstract
The present invention provides a kind of organic electroluminescence devices including mixing coating, wherein mixing coating includes particle scattering layer and multilayer coating (such as the first covering sub-layer and second covering sub-layer).The particle scattering layer is arranged between the first covering sub-layer and top transparent electrode, is distributed in top transparent electrode in the micro-nano granules shape of endless all standing.First covering sub-layer is contacted with top electrodes and particle scattering layer.The refractive index of first covering sub-layer is higher than the second covering sub-layer.Mixing coating in device of the present invention has the function of promoting light extraction efficiency.
Description
Technical field
The present invention relates to a kind of organic electroluminescence devices (OLED device) with mixing coating, and its preparation side
Method.
Background technique
OLED generally includes substrate, first electrode layer, organic layer and the second electrode lay.OLED can be classified as bottom-emission device
Part, top emission device and two sides luminescent device.In the structure of referred to as bottom emission device, first electrode layer is formed as
Transparent electrode layer, and the second electrode lay is formed as reflection electrode layer；In the structure of referred to as top emission device, first
Electrode layer is formed as reflection electrode layer, and the second electrode lay is formed as transparent electrode layer；And it is sent out in referred to as two sides
In the structure of optical device, first electrode layer and the second electrode lay can be transparent electrode layer.
The luminescence mechanism of OLED refer to device both ends apply voltage when, the electronics or sky that are generated respectively by two electrode layers
Cave is combined into exciton in luminescent material, and the energy transfer of exciton is excited to the electronics in light emitting molecule to light emitting molecule
Excitation state, and excitation state is a unstable state, de-activation process generates visible light.
However, generated light is typically due to the technique in device architecture and loses 70% or more in OLED.This master
If because incidence angle can occur when being greater than or equal to critical angle in complete when light is incident on low-index layer from high refractive index layer
Transmitting.The light of experiences total internal reflection is trapped in high refractive index layer, cannot be transferred into low-index layer.Therefore higher from refractive index
Interface of the light that issues of organic layer by the lower transparent electrode layer of refractive index and transparent substrates when, partially larger than critical angle
Light is run in the guide due to experiences total internal reflection repeatedly between organic layer, transparent electrode layer and transparent substrates, finally by the material of each layer
Material absorbs or these light are issued from device edge, does not play the role of any.The transmitting light conduct of only relatively small amount " can
With " light is output in air.It can be seen that the total internal reflection occurred on these interfaces greatly reduces organic electroluminescence
The light extraction efficiency (also referred to as external quantum efficiency (EQE)) of part.
At present, it has been suggested that a variety of solutions act on to reduce total internal reflection, produce to efficiently extract in organic layer
Raw light.CN102272973A, CN102844904A are outer membrane light extraction structures, positioned at the outside of substrate, and in bottom electricity
Pole side, the structure are optical grating construction and photon crystal structure, are realized by etching method, the nano-particle layer of low-refraction is
Coating process deposition；CN102569667A and CN103531720A is internal light extraction structures, and the structure is located at substrate and electricity
Between pole (such as ITO electrode), including scattering particles, hypothallus, flatness layer.
In existing OLED device, coating is mainly that the single layer structure being set in top transparent electrode and part are double
Layer structure, belongs to external structure；Particle scattering layer is mainly used in the optimization of OLED device internal structure.The present invention passes through general
Grain scattering layer constitutes mixing coating, to promote the light extraction efficiency of OLED in conjunction with multilayer coating.
Summary of the invention
The purpose of the present invention is to provide a kind of with the OLED device for promoting light extraction efficiency.
The purpose of the present invention is by the top transparent electrode of OLED and relative to organic luminescence function layer, setting
It mixes coating and realizes.The external structure that the mixing coating is OLED, including particle scattering layer and multilayer covering
Layer, such as the first covering sub-layer and the second covering sub-layer.The refractive index of first covering sub-layer is higher than the second covering sub-layer.
The present invention relates to a kind of organic electroluminescence devices with mixing coating comprising:
Basal layer；
Reflection electrode layer (first electrode layer), top transparent electrode layer (the second electrode lay)；
Organic luminescence function layer is arranged between reflection electrode layer and top transparent electrode layer；And
Coating is mixed, is arranged on top transparent electrode layer and relative to organic luminescence function layer；And
Encapsulated layer is optionally formed on mixing coating.
Wherein, the organic luminescence function layer includes hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electricity
Sub- implanted layer；The mixing coating includes particle scattering layer and multilayer coating, such as the first covering sub-layer and second is covered
Lid sub-layer.
Wherein, the particle scattering layer is the micro-nano granules shape distribution of endless all standing on top transparent electrode layer,
And it is arranged relative to organic luminescence function layer；First covering sub-layer is covered in top transparent electrode layer and particle scattering layer
On, and contacted with this two layers, i.e., gap between scattering particles and scattering particles in the described particle scattering layer
It is filled by the material of the first covering sub-layer in gap between top transparent electrode layer；Second covering sub-layer is disposed in first and covers
On cap rock, and relative to top transparent electrode layer.
The particle scattering layer is crystallinity particle scattering layer, can use micro-nano granules single layer or micro-nano granules multilayer
Implement, preferably micro-nano granules single layers.Distribution of the scattering particles in top transparent electrode is in equably endless all standing, institute
The effective area ratio accounted for is 30%-80%, preferably 40%-75%, more preferable 50%-70%.
Scattering particles with good light permeability and crystalline material by forming.The light transmittance of material is excellent 80% or more
Select 80%-90%.Material is selected from metal or nonmetal oxide, preferably SiO2、ZrO2Or SnO2。
The average grain diameter of scattering particles is 50-500nm, preferably 50-200nm.
Introduce scattering particles layer purpose be in order to by first cover the covering sub-layer of sub-layer/second and the second covering sub-layer/
Encapsulated layer or space interface, the light of generated total reflection are scattered, to increase the ranges of incidence angles of light, reduce the boundary
The range being totally reflected at face is conducive to the light extraction efficiency for promoting OLED device.
The multilayer coating includes the first covering sub-layer and the second covering sub-layer.First covering sub-layer is more sub- than the second covering
The refractive index of layer is higher, and the absolute value of specific refractivity should be greater than or be equal to 0.3, preferably 0.3-1.0.It is effectively reflected with organic layer
Rate is compared, the first covering sub-layer refractive index with higher, in 1.8-3.0, preferably 1.9-2.4, more preferable 2.0-2.4 range
It is interior；Second covers the refractive index of sub-layer within the scope of 1.2-1.5, or close with organic layer effective refractive index.
The first covering sub-layer with high index is conducive to extract the light issued from organic luminescence function layer, avoids light
Line is totally reflected in top transparent electrode layer and the first coating interface, to promote the light extraction efficiency of OLED device.
Being formed by multilayer coating enhances the extraction intensity of light by light scattering oscillation, is also beneficial to promote OLED device
The light extraction efficiency of part.
Another aspect of the present invention provides a kind of manufacture OLED device with mixing coating as described above
Method includes the following steps:
A. reflection electrode layer, hole injection layer, hole transmission layer, luminescent layer, electron-transport are sequentially formed on the base layer
Layer, electron injecting layer, top transparent electrode layer；
B. on top transparent electrode layer, then deposited particles scattering layer sequentially forms the first covering sub-layer and second again
Cover sub-layer.
Wherein, reflection electrode layer is made using sputtering method；Hole injection layer, hole transport are made using vacuum thermal evaporation
Layer, luminescent layer, electron transfer layer, electron injecting layer, top transparent electrode layer, the first covering sub-layer and the second covering sub-layer；?
Grain scattering layer can be implemented by chemical vapour deposition technique, physical vaporous deposition.
The present invention by OLED device introduce include particle scattering layer and multilayer coating mixing coating so that
The first covering sub-layer can be effectively extracted to by obtaining the light issued by organic luminescence function layer, then dissipating in micro-nano granules
The effect of penetrating is lower to reduce interface total reflection probability, while in the case where the light of multilayer coating scatters oscillation action, the light for promoting OLED is mentioned
Take efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram according to the common OLED of the prior art.
Fig. 2 is the structural schematic diagram of the OLED device with mixing coating of the invention.
Fig. 3 is the schematic diagram of mixing coating of the invention, and the wherein schematic diagram of light behavior.
Specific embodiment
With reference to the drawings, advantages of the present invention is illustrated in conjunction with specific embodiment.
Light extraction efficiency: also referred to as external quantum efficiency (EQE), to be issued in the structure compared with the number of photons that inside generates
Number of photons.
Total reflection (TIR): being incident on the light on the interface with low refractive index dielectric from high-index material can be all
Incidence angle is greater than critical angle θcIn the case where total reflection (TIR) occurs, the definition of critical angle is θc=sin-1(n2/n1), wherein n1
And n2It is the refractive index of high-refractive-index regions and region of low refractive index respectively.
Term " refractive index " refers to for sodium yellow light (wavelength 5893 × 10-10M), refraction of the material relative to vacuum
Rate, for " absolute index of refraction ".
The accompanying area to top transparent electrode of term " effective area " i.e. scattering particles layer accounts for top transparent electrode face
Long-pending percentage.
Term " organic layer effective refractive index " refers to the organic light emission function that electrode is removed between first electrode and second electrode
The integrated value of the refractive index of ergosphere.
It should be appreciated that when layer or element referred to as two layers or element " between " when, can be two layers or element
Between a layer or element, or the layer or element among one or more also may be present.
It should be appreciated that when layer or element be referred to as another layer or element " on " when, expression is from bottom to top
On direction.
Fig. 1 shows the structural schematic diagram of common OLED 100 according to prior art.Common OLED as shown in Figure 1 is top
Portion's illuminating OLED, including basal layer 110, reflection electrode layer 120, top transparent electrode layer 140, and it is arranged in reflection electrode layer
Organic luminescence function layer 130 between 120 and top transparent electrode layer 140；The organic luminescence function layer 130 has including following
Machine material layer: hole injection layer 131, hole transmission layer 132, luminescent layer 133, electron transfer layer 134, electron injecting layer 135.
Basal layer
Basal layer 110 can by such as glass, quartz, ceramics, plastics, polyethylene terephthalate (" PET ") and
The materials such as polyethylene naphthalate (" PEN ") are constituted, which provides enough mechanical supports and thermal stability for device.
Basal layer also optionally serves as barrier layer, and the barrier layer can effectively stop or help to prevent oxygen and water penetration from arriving
Device layers, especially organic luminescence function layer.
Reflection electrode layer
Reflection electrode layer 120 includes multiple first electrode sub-layers, also may include reflecting layer.Preferably, by reflecting layer cloth
Set between first electrode layer and basal layer 110, and at least one organic material layer phase in organic luminescence function layer 130
It is right, that is, first electrode layer is arranged between reflecting layer and at least one organic material layer.
Reflecting layer has the advantages that increase organic luminescent device efficiency, because reflecting layer is conducive to organic luminescence function layer
The light of generation is reflected towards the direction of top transparent electrode layer (the second electrode lay).Particularly, aluminium is used as the reflecting layer of OLED
Suitable material, it can easily be handled with common procedure of processing, and be lower cost materials.In addition, aluminium is easy to be located
Manage and show high refractive index, so if with described in the WO 03/055275 that is for example incorporated herein by reference certain
Mode handles surface, then is suitable for providing while may be used as the reflecting layer of the electrode of OLED.By using electrode reflecting layer, with
Transmitting penetrates the OLED of transparent first electrode, i.e., the so-called OLED through bottom emission is compared, and the efficiency of top emitting OLED can
To increase to higher value.
First electrode layer thickness depends on the material used, and thickness range is usually 5nm to 1 μm, preferably 10nm to 1 μ
M, more preferable 10nm to 500nm, particularly preferred 10nm to 300nm, most preferably 10nm to 250nm.
Preferably, first electrode layer includes tin indium oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), aluminum zinc oxide
(AZO) and indium oxide (In2O3At least one of), they have relatively high work function.
Top transparent electrode layer
Top transparent electrode layer 140 includes multiple second electrode sub-layers.Top transparent electrode layer 140 can be by lithium, calcium, fluorine
Change lithium/calcium, lithium fluoride/aluminium, aluminium, silver, magnesium or its alloy and the film with low work content is made.Further, top transparent electrode
Layer 140 can by including that silver and the alloy of at least one metal be made, at least one metal include aluminium, platinum, ytterbium, chromium or
Magnesium.Also, weight ratio of the Ag in the alloy can weights identical with other metal ratios, more than or less than other metals
Amount.Such as: top transparent electrode layer 140 can be formed by Ag-Mg alloy, and wherein the mass ratio of Ag and Mg can be for 90:10 extremely
10:90.Alternatively, top transparent electrode layer 140 may include as silver, gold, platinum, copper, nickel or tungsten at least one metal and as ytterbium,
The alloy of at least one metal of indium, magnesium or chromium is formed.These metal films can be formed transparent or half by the thickness of adjusting film
Transparent electrode.Therefore, the light generated by organic luminescence function layer 130 can be launched by top transparent electrode layer 140.
Organic luminescence function layer
Organic luminescence function layer 130 is between reflecting electrode 120 and top transparent electrode 140.Organic luminescence function layer
130 are formed in various structures, and the structure can further comprise various functions layers known in the art, as long as it includes shining
Unit.Organic luminescence function layer 130 with a thickness of 50nm-1000nm.As organic luminescence function layer 130 can be contained in
In organic material layer, can be hole injection layer 131, hole transmission layer 132, luminescent layer 133, electron transfer layer 134, electronics
Implanted layer 135.
Hole injection layer 131 or hole transmission layer 132 can be used such as electronics give organic compound and formed.Herein,
As electronics give organic compound, such as N, N ', N can be used ' 4,4 '-diamino-phenyl of-tetraphenyl-, N, N '-hexichol
Base-N, N '-two (3- aminomethyl phenyl) -4,4 '-benzidines, 2,2- bis- (bis--p-methylphenyl of 4- aminophenyl) propane, N, N,
N ', N '-four-p-methylphenyl -4,4 '-benzidine, bis- (bis--p-methylphenyl of 4- aminophenyl) phenylmethanes, N, N '-hexichol
Base-N, N '-two (4- methoxyphenyl) -4,4 '-benzidines, N, N, N ', N '-tetraphenyl -4,4 '-diamino-diphenyl
Ether, 4,4 '-bis- (diphenyl amino) tetraphenyls, 4-N, N- diphenyl amino-(2- diphenylacetylene) benzene, 3- methoxyl group -4 ' -
Bis- (4- bis--is to the triamido phenyl) hexamethylenes of N, N- diphenylaminostyrene base benzene, N- phenyl carbazole, 1,1-, the bis- (4- of 1,1-
Two-to triamido phenyl) -4- cyclohexylbenzene, bis- (4- dimethylamino -2- aminomethyl phenyl) phenylmethanes, N, N, N- tri- be (right
Tolyl) amine, 4- (two-p-methylphenyl amino) -4 '-[4- (two-p-methylphenyl amino) styryl] talan, N, N,
N ', N '-tetraphenyl -4,4 '-benzidine, N- phenyl carbazole, 4,4 '-bis- [N- (1- naphthalene)-N- phenyl-amino] biphenyl,
4,4 "-bis- [N- (1- naphthalene)-N- phenyl amino] para-terpheny, 4,4 '-bis- [N- (2- naphthalene)-N- phenyl amino] biphenyl, 4,
4 '-bis- [N- (3- acenaphthenyl)-N- phenyl amino] biphenyl, 1,5- bis- [N- (1- naphthalene)-N- phenyl amino] naphthalenes, 4,4 '-bis- [N-
(9- anthryl)-N- phenyl amino] xenyl phenyl amino] biphenyl, 4,4 "-bis- [N- (1- anthryl)-N- phenyl aminos]-are to three
Benzene, 4,4 '-bis- [N- (2- phenanthryl)-N- phenyl amino] biphenyl, 4,4 '-bis- [N- (8- fluoranthene base)-N- phenyl amino] biphenyl, 4,
It is 4 '-bis- [N- (2- pyrenyl)-N- phenyl amino] biphenyl, 4,4 '-bis- [N- (2- pyrenyl)-N- phenyl amino] biphenyl, 4,4 '-bis-
[N- (1- guan base)-N- phenyl amino] biphenyl, bis- (two-p-methylphenyl amino) naphthalenes of 2,6-, 2,6- bis- [two-(1- naphthalene) amino]
Bis- [N- (1- naphthalene)-N- (2- naphthalene) amino] naphthalenes of naphthalene, 2,6-, 4,4 "-bis- [N, N- bis- (2- naphthalene) amino] terphenyls, 4,
4 '-bis- { N- phenyl-N- [4- (1- naphthalene) phenyl] amino } biphenyl, 4,4 '-bis- [N- phenyl-N- (2- pyrenyl) amino] biphenyl,
Bis- [N, N- bis--(2- naphthalene) amino] fluorenes of 2,6- or 4,4 "-bis- (bis--p-methylphenyl of N, N- amino) terphenyls, or aryl amination
Object such as bis- (N-1- naphthalenes) (N-2- naphthalene) amine is closed, but the application is without being limited thereto.
The material of luminescent layer 133 is not particularly limited, and fluorescence with various launching centres can be used or phosphorescence is organic
Material is formed, such as the material based on Alq, such as three (4- methyl -8- quinoline) aluminium (III) (Alg3), 4-MAlq3 or Gaq3；Ring
Pentadiene derivant, such as C-545T (C26H26N2O2S), DSA- amine, TBSA, BTP, PAP-NPA, loop coil-FPA, PhTDAOXD
(Ph3) or five phenyl -1,3- cyclopentadiene (PPCP) of 1,2,3,4,5- Si；4,4 '-bis- (2,2 '-diphenylacetylenes) -1,1 ' -
Diphenyl (DPVBi), diphenylethyllene benzene or derivatives thereof；4- (dicyano methylene) -2- tert-butyl -6- (1,1,7,7,-four
Methyl julolidine groups -9- alkenyl) -4H- pyrans (DCJTB), DDP, AAAP or NPAMLI；Or phosphor material, such as Firpic, m-
Firpic、N-Firpic、bon2Ir(acac)、(C6)2Ir(acac)、bt2Ir(acac)、dp2Ir(acac)、bzq2Ir
(acac)、bo2Ir(acac)、F2Ir(bpy)、F2Ir(acac)、op2Ir(acac)、ppy2Ir(acac)、tpy2Ir(acac)、
Fac- tri- [2- (4,5 '-difluorophenyl) pyridine-C ' 2, N] iridium (III) (FIrppy) or bis- (2- (2 '-benzos [4,5-a] thiophene
Base) pyridine-N, C3 ') iridium (acetylacetone,2,4-pentanedione) (Btp2Ir (acac)), but the application is without being limited thereto.Luminescent layer may also include above-mentioned
Material is as main body and host-dopant system (host-dopant system) comprising, distyryl biphenyl,
DPT, quinacridone, rubrene, BTX, ABTX or DCJTB are as dopant.
Electron transfer layer 134 or electron injecting layer 135, which can be used such as electronics and receive organic compound, to be formed.Herein,
As this kind of organic compound, such as polycyclic compound can be used, such as para-terpheny or quaterphenyl or derivatives thereof；Polycyclic hydrocarbon
Compound, as naphthalene, aphthacene (tetracene), pyrene (pyrene), guan (coronene),(chrysene), anthracene, diphenyl
Anthracene, aphthacene (naphthacene) or phenanthrene or derivatives thereof；Or heterocyclic compound, such as phenanthroline, bathophenanthroline, phenanthridines, a word used for translation
Pyridine, quinoline, quinoxaline or azophenlyene or derivatives thereof.In addition, can be used following substances as including electronics in forming low-refractive-index layer
Receive organic compound: fluorescein, phthalein (phthaloperylene), naphthalene (naphthaloperylene), ketone
(perynone), phthalein ketone (phthaloperynone), naphthalenone (naphthaloperynone), diphenyl diethylene, four
Phenyl butadiene, oxadiazoles, aldazine, dibenzo oxazoline, distyrene, pyrazine, cyclopentadiene, 8-hydroxyquinoline
(oxine), aminoquinoline, imines, diphenylethlene, vinyl anthracene, diaminocarbazole, pyrans, thio-pyrylium, polymethine, portion
Cyanine, quinacridone, rubrene or derivatives thereof, but the application is without being limited thereto.
Fig. 2 is the structural schematic diagram of the OLED device with mixing coating of the invention.In the present embodiment,
It will mix on the top transparent electrode 140 that coating 250 is arranged in common OLED 100 as shown in Figure 1.The mixing
Coating 250 includes that particle scattering layer 251, first covers sub-layer 252 and the second covering sub-layer 253.Optionally, it is covered in mixing
Encapsulated layer 260 is formed on layer 250.
Mix coating
As shown in Fig. 2, particle scattering layer 251 is in the micro-nano granules of endless all standing on top transparent electrode layer 140
Shape distribution, and be arranged relative to organic luminescence function layer 130；First covering sub-layer 252 is covered in top transparent electrode layer
140 and particle scattering layer 251 on, and contacted with this two layers, i.e., the scattering particles in the described particle scattering layer 251 it
Between gap and scattering particles and top transparent electrode layer 140 between gap by first covering sub-layer material fill；The
Two covering sub-layers 253 are disposed in the first covering sub-layer 252, and relative to top transparent electrode layer 140.
The particle scattering layer 251 is crystallinity particle scattering layer, and thickness is not particularly limited, and only requires it equably
It is distributed between the first covering sub-layer and top transparent electrode, and is covered for imperfection.The particle scattering layer can be used
Micro-nano granules single layer or micro-nano granules multilayer are implemented, preferably micro-nano granules single layer.
The level of coverage of scattering particles on the top electrode successively decreases with the increase (red shift) of visible wavelength, at top
Shared effective area ratio is 30%-80%, preferably 40%-75%, more preferable 50%-70% on electrode.Scattering particles can make
It is formed with the material with good light permeability and good crystallinity.The light transmittance of scattering particles is in 80% or more, preferably 80%-
90%.The average grain diameter of scattering particles is 50-500nm, preferably 50-200nm.
The shape of scattering particles is not particularly limited, and can be hexagon, positive tetrahedron shape, prismatic, cube shaped
Deng being also possible to other irregular shapes.It is preferred that the shape of scattering particles be irregular shape because this structure for
The spread of light is most wide, can reduce the total reflection probability of interface light.As scattering particles, can be used for example comprising under
State the particle of material: organic material, as polystyrene or derivatives thereof, acrylic resin or derivatives thereof, silicone resin or its spread out
Biology or phenolic resin or derivatives thereof；Or inorganic material, such as silica, aluminium oxide, tin oxide or zirconium oxide, there are also poly-
Close object ceramics etc..As scattering particles, hollow particle or the particle with core/shell structure, such as hollow silica also can be used.
In embodiments, by chemical vapor deposition, the depositing crystalline on the top transparent electrode layer 140 as cathode
The preferable particle scattering layer of property.Particle scattering layer 251 be uniformly distributed in the first covering sub-layer 252 and top transparent electrode 140 it
Between, it is distributed in top transparent electrode 140 in the micro-nano granules shape of endless all standing.Scattering in particle scattering layer 251
Grain can effectively scatter the light of total reflection caused by the first covering 252/ second coating of sub-layer, 253 interface.
Multilayer tectum structure is to the absorptivity of light
Wherein n1And n2Respectively first covering sub-layer and the second covering sub-layer refractive index, (refractive index of the second covering sub-layer
It is less than the refractive index of the first covering sub-layer), the absolute value │ n of refractive index difference1-n2│ >=0.3, preferably 0.3-1.0 can drop
Low multilayer coating is to the absorption effect for taking out light.
First covering sub-layer 252 is formed using the material with high index and good light transmittance.It is effective with organic layer
Refractive index is compared, first covering sub-layer 252 refractive index it is higher, for example, ranges of indices of refraction be 1.8-3.0, preferably 1.9-2.4,
More preferable 2.0-2.4.It in this way can be to avoid the light issued by organic luminescence function layer 130 in top transparent electrode layer 140 and
One covering 252 interface of sub-layer is totally reflected, and is conducive to the light extraction efficiency for promoting OLED device.First covering sub-layer 252
Light transmittance in 80% or more, preferably 80%-90%.First covering sub-layer 252 with a thickness of 50-1000nm, preferably 50-500nm,
More preferable 60-400nm.
The material of first covering sub-layer 252 may include for example organic or organo metallic material or inorganic material.It is described organic
Or organo metallic material can be selected from 2- xenyl -4,6- two [to (N- phenylbenzimidazol) phenyl] -1,3,5- triazole (ZCP),
Poly- (3,4- ethene-dioxythiophene) (PEDOT), 4,4 '-bis- [N- (3- methylphenyl-N-phenyl amino)] biphenyl (TPD),
4,4 ', 4 "-three [N- (3- methylphenyl-N-phenyl amino)] triphenylamines (m-MTDATA), [bis- (the 2- first of N, N- of 1,3,5- tri-
Base phenyl-amino)]-benzene (o-MTDAB), 1,3,5- tri- [N, N- bis- (3- aminomethyl phenyls-amino)]-benzene (m-MTDAB), 1,3,
5- tri- [N, N- bis- (4- aminomethyl phenyls-amino)]-benzene (p-MTDAB), 4,4 '-three [bis- (3- the aminomethyl phenyl)-amino of N, N-]-two
Phenylmethane (BPPM), 2,2 ', 2 "-(three base of 1,3,5- benzene) three-[1- phenyl -1H- benzimidazole] (TPBI) and/or 3- (connection
Phenyl) -5 tert-butyl-phenyl -1,2,4- triazole (TAZ) etc. of -4- phenyl；Inorganic material can be selected from zinc oxide, titanium oxide, oxidation
Zirconium, niobium oxide, tantalum oxide, tin oxide, silica, nickel oxide, silica, indium oxide and/or gallium oxide etc..
In embodiments, the first covering of deposition sub-layer 252 on particle scattering layer 251 is steamed by Vacuum Heat.First covers
The material of cap rock is filled with the gap between the gap and scattering particles and top transparent electrode between scattering particles, therefore first
Covering sub-layer 252 is contacted with top transparent electrode layer 140 and particle scattering layer 250.
Second covering sub-layer 253 is formed using the material for having refractive index relatively low.With the folding of the first covering sub-layer 252
The rate of penetrating is compared, and the refractive index of the second covering sub-layer 253 is lower, and the absolute value of the specific refractivity of the two is greater than or equal to 0.3,
It is preferred that 0.3-1.8.Second covers the refractive index of sub-layer 253 within the scope of 1.2-1.5, or close with organic layer effective refractive index.
The material such as LiF, MgF2, resinous polymer etc..Second covering sub-layer 253 is with a thickness of 50-1000nm, preferably 50-
500nm, more preferable 60-200nm.
In embodiments, it in the first covering sub-layer 252, is deposited by the method that Vacuum Heat steams, such as LiF, MgF2Deng,
The second covering sub-layer 253 can also be constructed by the method (such as epoxy resin, acrylic resin) of photo-thermal curing after blade coating, the
Two covering sub-layers 253 are contacted with the first covering sub-layer 252.
Encapsulated layer
Encapsulated layer 260 includes thin-film encapsulation layer.It is sub- that encapsulated layer optionally can be present in the second covering in mixing coating
On layer.
Thin-film encapsulation layer may include one or more inorganic encapsulated layers, and one or more organic encapsulation layers.Film
Encapsulated layer can have the structure with inorganic encapsulated layer and organic encapsulation layer alternatively laminated.In this case, inorganic encapsulated layer can
It is arranged in the lowest portion of laminar structure.For example, inorganic encapsulated layer may be arranged at the position for being close to the second coating.
Inorganic encapsulated layer may include one or more inorganic material, such as Al2O3、TiO2、ZrO、SiO2、AlON、AlN、
SiON、Si3N4, ZnO and Ta2O5.Inorganic encapsulated layer can be used such as chemical vapor deposition or atomic layer deposition method and shape
At.
Organic encapsulation layer may include, such as the material based on polymerization.Such as acrylic resin, epoxy resin, polyamides are sub-
Amine and polyethylene.Organic encapsulation layer can be formed for example, by heat deposition technique.It is used to form the heat deposition work of organic encapsulation layer
Skill can execute within the temperature range of can not damage OLED.
Inorganic encapsulated layer and organic encapsulation layer with highdensity film can help to prevent or effectively reduce such as water
Point or oxygen infiltration, also act as buffer layer, and there is planarization property.Thin-film encapsulation layer can have about 10 μm or below
Thickness.
Mixing coating through the invention can promote the light extraction efficiency of OLED.As shown in figure 3, for from organic hair
The light that light functional layer issues, by the first covering sub-layer 252 extraction, (the first covering sub-layer with a high refractive index makes interface first
Place is without total reflection)；Then light can occur partially to be totally reflected when entering the second covering sub-layer 253, remain in part light
First covering sub-layer, after particle of this part light through being located between the first covering sub-layer and top transparent electrode dissipates the scattering of chromatograph 251,
It is scattered as multiple directions, which increases the ranges of incidence angles for being again incident on the second covering sub-layer, reduce total reflection
The probability of light promotes light and takes efficiency.Meanwhile it being formed by multilayer coating and passing through the extraction of light scattering oscillation also enhancing light
Intensity.
To sum up, OLED device of the invention comprising the mixing coating containing scattering particles layer and multilayer coating, tool
Play the role of promoting light extraction efficiency.
Embodiment
It will be hereinafter described in more detail by exemplary implementation scheme of the embodiment to the application.However, this Shen
Range please is not limited to following disclosed embodiment.
1. measurement method
Detection method:
Using IVL (current-voltage-brightness) test macro (Japanese シ ス テ ムJi Yan Co., Ltd.), software is selected
EILV20060707 tests the OLED device in following embodiments and comparing embodiment, while obtaining special about the IVL of the device
The data such as linearity curve, efficiency and current density relation curve, chromaticity coordinates position, must be in the dark under covering device in test process
Environment carries out.With@10mA/cm2Under the conditions of data on the basis of (i.e. test current density reach 10mA/cm2When corresponding items
Performance number).
Service life: using LT95 as standard, i.e., light emission luminance by being initially down to original intensity 95% when time experienced, it is single
Position is h.
Embodiment 1: OLED device of the invention is manufactured
On substrate of glass (basal layer 110), the ITO opaque layer (reflection electrode layer of 200nm is formed in a manner of sputtering
120), and it is etched into the figure of demand, is cleaned each 15 minutes with deionized water, acetone, EtOH Sonicate respectively, then in plasma
It is handled 2 minutes in body washer；ITO electrode layer is that sky is deposited by vacuum evaporation mode on ito anode layer in anode herein
Layer material HAT-CN is injected in cave, and with a thickness of 10nm, this layer is as hole injection layer 131；On hole injection layer 131, by true
Hole transport layer material NPB is deposited in empty vapor deposition mode, and with a thickness of 60nm, which is hole transmission layer 132；In hole transmission layer
Green light emitting layer 133 is deposited on 132, CBP is as material of main part, Ir (ppy)3As dopant material, Ir (ppy)3With CBP's
Weight ratio is 1:9 (CBP of 90wt%), with a thickness of 30nm；On luminescent layer 133, electronics is deposited by vacuum evaporation mode
Transmission material TPBI, with a thickness of 40nm, this layer of organic material is used as electron transfer layer 134；Electron transfer layer 134 it
On, vacuum evaporation electron injecting layer material LiF, with a thickness of 1nm, which is electron injecting layer 135；Electron injecting layer 135 it
On, vacuum evaporation cathode Mg:Ag mixed metal electrode (Mg:Ag weight ratio is 1:9, the Mg of 10wt%), thickness 15nm, this layer of shape
At top transparent electrode layer 140, as cathode；On top transparent electrode layer 140, sunk by way of chemical vapor deposition
Product particle scatters layer material SiO2, average grain diameter 120nm, effective area ratio 60%, which is particle scattering layer 251；?
On particle scattering layer 251, the first covering layer material ZCP is deposited by vacuum evaporation mode, with a thickness of 350nm, refractive index is
2.18, form the first coating 252；On the first coating 252, the second covering layer material is deposited by vacuum evaporation mode
MgF2, with a thickness of 85nm, refractive index 1.38 forms the second coating 253.
Organic material structural formula involved in above-mentioned implementation process is as follows:
Comparative example 1:
The device is manufactured in the way of embodiment 1, wherein the material of each layer, thickness are identical with production method, it is different
It is device architecture.
Device architecture: 131/ hole transmission layer of basal layer 110/ reflection electrode layer, 120/ hole injection layer, 132/ luminescent layer
133/ electron transfer layer, 134/ electron injecting layer, 135/ top transparent electrode layer, 140/ particle scattering layer, 251/ first coating 252
Comparative example 2
The device is manufactured in the way of embodiment 1, wherein the material of each layer, thickness are identical with production method, it is different
It is device architecture.
Device architecture: 131/ hole transmission layer of basal layer 110/ reflection electrode layer, 120/ hole injection layer, 132/ luminescent layer
133/ electron transfer layer, 134/ electron injecting layer, 135/ top transparent electrode layer, 140/ particle scattering layer, 251/ second coating 253
Comparative example 3
The device is manufactured in the way of embodiment 1, wherein the material of each layer, thickness are identical with production method, it is different
It is device architecture.
Device architecture: 131/ hole transmission layer of basal layer 110/ reflection electrode layer, 120/ hole injection layer, 132/ luminescent layer
133/ electron transfer layer, 134/ electron injecting layer, 135/ top transparent electrode layer, 140/ first coating, 252/ second coating 253
Comparative example 4
The device is manufactured in the way of embodiment 1, wherein the material of each layer, thickness are identical with production method, it is different
It is device architecture.
Device architecture: 131/ hole transmission layer of basal layer 110/ reflection electrode layer, 120/ hole injection layer, 132/ luminescent layer
133/ electron transfer layer, 134/ electron injecting layer, 135/ top transparent electrode layer 140
The performance test of device is in@10mA/cm2Under the conditions of carry out, it is as a result shown in table 1.
Table 1:
As shown in table 1, the device of the present invention in terms of the brightness of device, current efficiency, external quantum efficiency, in embodiment 1
It is superior to comparative example 1-4.Therefore, OLED device of the invention, including contain scattering particles layer and multilayer coating
Mixing coating, have the function of promoted light extraction efficiency, while also improve device brightness, current efficiency etc..
Illustrative embodiments disclosed herein, although and using specific term, they are only with general and description
Property meaning uses and illustrates, not for purposes of limitation.Moreover, it will be understood by those skilled in the art that can be without departing from right
The various change of form and details is made under the spirit and scope of the present invention described in claim.
Claims (10)
1. a kind of organic electroluminescence device including mixing coating, comprising:
Basal layer (110)；
Reflection electrode layer (120) and top transparent electrode layer (140)；
Organic luminescence function layer (130) is arranged between reflection electrode layer (120) and top transparent electrode layer (140)；And
It mixes coating (250), is arranged on top transparent electrode layer (140) and relative to organic luminescence function layer (130)；
Wherein, the organic luminescence function layer (130) include hole injection layer, hole transmission layer, luminescent layer, electron transfer layer,
Electron injecting layer (131-135)；The mixing coating (250) includes particle scattering layer (251) and multilayer coating；
Wherein, the multilayer coating includes the first covering sub-layer (252) and the second covering sub-layer (253).
2. organic electroluminescence device according to claim 1, wherein particle scattering layer (251) is crystallinity particle scattering layer,
It is distributed on top transparent electrode (140) in the micro-nano granules shape of endless all standing, shared effective area is 30%-
80%, preferably 40%-75%, more preferable 50%-70%.
3. organic electroluminescence device according to claim 1, wherein the first covering sub-layer (252) and top transparent electrode
(140) it is contacted with particle scattering layer (251).
4. organic electroluminescence device according to claim 1, wherein the scattering particles in scattering particles scattering layer (251) is flat
Equal partial size is 50-500nm, preferably 50-200nm；The preferred SiO of scattering particles2、ZrO2Or SnO2。
5. organic electroluminescence device according to claim 1 covers wherein the refractive index of the first covering sub-layer (252) is higher than second
The absolute value of lid sub-layer (253), specific refractivity is greater than or equal to 0.3, preferably 0.3-1.0.
6. organic electroluminescence device according to claim 1, wherein first covering sub-layer (252) ranges of indices of refraction, is 1.8-
3.0 preferably 1.9-2.4, more preferable 2.0-2.4.
7. organic electroluminescence device according to claim 1, wherein the first covering sub-layer (252) with a thickness of 50-1000nm,
It is preferred that 50-500nm, more preferable 60-400nm.
8. organic electroluminescence device according to claim 1, wherein the ranges of indices of refraction of the material of the second covering sub-layer (253)
For 1.2-1.5.
9. organic electroluminescence device according to claim 1, wherein the second covering sub-layer (253) with a thickness of 50-1000nm,
It is preferred that 50-500nm, more preferable 60-200nm.
10. a kind of method for the organic electroluminescence device for being used to prepare any one of claim 1-9, comprising:
A. sequentially formed on basal layer (110) reflection electrode layer (120), hole injection layer (131), hole transmission layer (132),
Luminescent layer (133), electron transfer layer (134), electron injecting layer (135), top transparent electrode layer (140)；
B. on top transparent electrode layer (140), deposited particles scattering layer (251) then sequentially forms the first covering sub-layer again
(252) and second covers sub-layer (253)；
Reflection electrode layer is wherein made using sputtering method；Hole injection layer, hole transmission layer, hair are made using vacuum thermal evaporation
Photosphere, electron transfer layer, electron injecting layer, top transparent electrode layer, the first covering sub-layer and the second covering sub-layer；Using chemistry
Vapour deposition process makes particle scattering layer.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911459A (en) * | 2019-11-13 | 2020-03-24 | 清华大学 | Color conversion organic electroluminescent device |
| CN112259694A (en) * | 2020-10-14 | 2021-01-22 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
| CN112259693A (en) * | 2020-10-14 | 2021-01-22 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
| CN113248462A (en) * | 2021-05-12 | 2021-08-13 | 长春海谱润斯科技股份有限公司 | Organic electroluminescent device |
| US11985841B2 (en) | 2021-12-07 | 2024-05-14 | Oti Lumionics Inc. | Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544334A (en) * | 2011-01-19 | 2012-07-04 | 南京第壹有机光电有限公司 | Highly efficiently luminescent electroluminescent device |
| CN102683606A (en) * | 2011-03-08 | 2012-09-19 | 株式会社东芝 | Organic electroluminescent light emitting device and method for manufacturing the same |
| CN204179112U (en) * | 2014-11-18 | 2015-02-25 | 京东方科技集团股份有限公司 | Organic illuminating element and display unit, lighting device |
| CN104766927A (en) * | 2015-04-30 | 2015-07-08 | 京东方科技集团股份有限公司 | Organic light emitting diode device and manufacturing method thereof |
-
2018
- 2018-03-14 CN CN201810210164.5A patent/CN110277505A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544334A (en) * | 2011-01-19 | 2012-07-04 | 南京第壹有机光电有限公司 | Highly efficiently luminescent electroluminescent device |
| CN102683606A (en) * | 2011-03-08 | 2012-09-19 | 株式会社东芝 | Organic electroluminescent light emitting device and method for manufacturing the same |
| CN204179112U (en) * | 2014-11-18 | 2015-02-25 | 京东方科技集团股份有限公司 | Organic illuminating element and display unit, lighting device |
| CN104766927A (en) * | 2015-04-30 | 2015-07-08 | 京东方科技集团股份有限公司 | Organic light emitting diode device and manufacturing method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911459A (en) * | 2019-11-13 | 2020-03-24 | 清华大学 | Color conversion organic electroluminescent device |
| CN110911459B (en) * | 2019-11-13 | 2022-05-13 | 清华大学 | Color conversion organic electroluminescent device |
| CN112259694A (en) * | 2020-10-14 | 2021-01-22 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
| CN112259693A (en) * | 2020-10-14 | 2021-01-22 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
| CN113248462A (en) * | 2021-05-12 | 2021-08-13 | 长春海谱润斯科技股份有限公司 | Organic electroluminescent device |
| CN113248462B (en) * | 2021-05-12 | 2022-03-25 | 长春海谱润斯科技股份有限公司 | Organic electroluminescent device |
| US11985841B2 (en) | 2021-12-07 | 2024-05-14 | Oti Lumionics Inc. | Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating |
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Application publication date: 20190924 |