CN106356461A - Organic electroluminescence element - Google Patents
Organic electroluminescence element Download PDFInfo
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- CN106356461A CN106356461A CN201610547399.4A CN201610547399A CN106356461A CN 106356461 A CN106356461 A CN 106356461A CN 201610547399 A CN201610547399 A CN 201610547399A CN 106356461 A CN106356461 A CN 106356461A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/157—Hole transporting layers between the light-emitting layer and the cathode
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/166—Electron transporting layers comprising a multilayered structure
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- H10K50/00—Organic light-emitting devices
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- H10K50/18—Carrier blocking layers
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Abstract
The present invention provides an organic electroluminescent device comprising an anode and a cathode and an organic electroluminescent element provided between the anode and the cathode, and an organic electroluminescent element between the cathode and the light emitting layer, a second layer made of sodium fluoride, a second layer made of alkali metal or alkaline earth metal in contact with the first layer, and a third layer containing an organic electron transport material in contact with the second layer.
Description
Technical field
The present invention relates to a kind of organic electroluminescent device (is referred to as " organic el element " in this specification.).
Background technology
It is desirable to the stability of driving voltage and the stability of current efficiency in organic el element.For example, in patent documentation
In 1, disclose following organic el element, what what it had that luminescent layer and this luminescent layer be placed in contact be made up of sodium fluoride
The electron injecting layer being made up of bathocuproine and barium that layer and the layer that is made up of sodium fluoride with this are placed in contact with.
Patent documentation 1: Japanese Unexamined Patent Publication 2013-033872 publication
Content of the invention
Invent problem to be solved
But, when this organic el element preserves in high temperature environments, the stablizing of the stability of driving voltage and current efficiency
Property is not necessarily abundant.
Therefore, it is an object of the invention to, a kind of when preserving in high temperature environments, the stability of driving voltage and electricity are provided
Organic el element of the excellent in stability of stream efficiency.
The present invention provides following [1]～[4].
[1] a kind of organic el element, is to have anode and negative electrode and the luminescent layer between this anode and this negative electrode
Organic el element,
Between this negative electrode and this luminescent layer, be there is the ground floor being made up of sodium fluoride being contacted with this luminescent layer and
One layer contact the second layer being made up of alkali metal or alkaline-earth metal and contact with the second layer contain Organic Electron Transport Material
Third layer.
[2] according to the organic el element described in [1], wherein, in the second layer contained alkali metal or alkaline-earth metal be barium,
Sodium or potassium.
[3] the organic el element according to described in [1] or [2], wherein, the thickness of the second layer is 0.1nm～20nm.
[4] the organic el element according to described in [3], wherein, the thickness of ground floor is 0.1nm～10nm, and the 3rd
The thickness of layer is 1nm～1000nm.
When organic el element of the present invention is under hot environment preservation, the stablizing of the stability of driving voltage and current efficiency
Property is excellent.
Brief description
Fig. 1 is the schematic diagram of the composition of organic el element representing an embodiment of the invention.
Specific embodiment
Hereinafter, while referring to the drawings, embodiments of the present invention are illustrated.Phase is used for identical key element
Same symbol.The repetitive description thereof will be omitted.The dimensional ratios of accompanying drawing are not necessarily consistent with the dimensional ratios of explanation.
As is schematically indicated in figure 1, organic el element is sequentially provided with anode 2, hole injection layer 3, hole biography on substrate 1
Defeated layer 4, luminescent layer 5, ground floor 6a, second layer 6b, third layer 6c, electron injecting layer 7 and negative electrode 8 and constitute.Organic el element
For example it is used for curved or plane illuminator (flat light source for example using), display dress as the light source of scanner
In putting.
First, to substrate 1, anode 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron injecting layer 7 and negative electrode 8
Illustrate.
＜ substrate 1 ＞
Substrate 1 is generally used in the substrate that chemical change will not occur in the manufacturing process of organic el element.As this base
Plate 1, for example, can enumerate the rigid substrates such as glass substrate, silicon substrate；Plastic base, polymeric membrane isowarping substrate.Pass through
Using flexibility substrate, generally speaking can be made as is organic el element of flexibility.It is also possible in advance in substrate 1
Form electrode and the drive circuit for driving organic el element.
＜ anode 2 ＞
Anode 2 is usually used the low film of resistance.At least one party's normally transparent of anode 2 and negative electrode 8.For example, with regard to bottom emitting
For organic el element of type, the anode 2 being configured at substrate 1 side is using transparent and high to the absorbance of the light of visible region
Material.
As the material of anode 2, for example can using have the metal-oxide of electric conductivity, metal, polyaniline or its spread out
Biology, polythiophene or derivatives thereof, because absorbance is good and easily patterns, therefore preferably Indium sesquioxide., zinc oxide, oxidation
Stannum, indium tin oxide (ito), indium-zinc oxide (izo)；Gold, platinum, silver, copper, aluminum or the alloy containing these metals, more preferably
Ito, izo and stannum oxide.
And, in the case of going out light from negative electrode 8 side draw, preferably by light emitting layer in future 5 light to negative electrode 8 lateral reflection
Material (metal more than such as work function 3.0ev, metal-oxide, metal sulfide) formed anode 2.As such sun
Pole 2, such as using can be with the metal film of the thickness of reflected light.
Anode 2 for example can be formed using vacuum vapour deposition, sputtering method, ion plating method, plating.
The thickness of anode 2 can consider the transmittance of light and electrical conductivity and determine, usually 10nm～10 μm, preferably
20nm～1 μm, more preferably 50nm～500nm.
＜ hole injection layer 3 ＞
Hole injection layer 3 is that have the layer improving the function of hole injection efficiency from anode 2.Note as constituting hole
Enter the hole-injecting material of layer 3, for example, can enumerate the oxides such as vanadium oxide, molybdenum oxide, ruthenium-oxide, aluminium oxide；Phenyl amination
Compound, star burst type amines, phthalocyanine compound, amorphous carbon, polyaniline and polyethylene dioxythiophene (pedot) etc.
Polythiofuran derivative.
As hole-injecting material it is also possible to use with known charge transport materials and electron acceptor combination of materials.And
And, charge transport materials are hole mobile material described later and electron transport material.
As electron acceptor material, preferably heteropoly compound, aryl sulfonic acid or combinations thereof.
So-called heteropoly compound, is following polyacid, and it has the chemical constitution table with keggin type or dawson type
Show, hetero atom is located at the structure at the center of molecule, is using the isopolyacid of the oxyacid as vanadium, molybdenum, tungsten etc. and xenogenesis element
Oxyacid condensation form.As the oxyacid of xenogenesis element, for example, can enumerate the oxyacid of silicon, phosphorus or arsenic.
As heteropoly compound, for example, can enumerate phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, phosphotungstomolybdic acid, silico-tungstic acid.
As aryl sulfonic acid, for example, can enumerate benzenesulfonic acid, toluenesulfonic acid, p styrene sulfonic acid, 2- LOMAR PWA EINECS 246-676-2,4- hydroxyl
Benzenesulfonic acid, 5-sulphosalicylic acid, to DBSA, dihexyl benzenesulfonic acid, 2,5- dihexyl benzenesulfonic acid, dibutyl naphthalene sulphur
Acid, 6,7- dibutyl -2- LOMAR PWA EINECS 246-676-2, dodecyl LOMAR PWA EINECS 246-676-2,3- dodecyl -2- LOMAR PWA EINECS 246-676-2, hexyl LOMAR PWA EINECS 246-676-2,4- hexyl -
1-naphthalene sulfonic aicd, octyl group LOMAR PWA EINECS 246-676-2,2- octyl group -1-naphthalene sulfonic aicd, hexyl LOMAR PWA EINECS 246-676-2,7- hexyl -1-naphthalene sulfonic aicd, 6- hexyl -2- naphthalene sulphur
Acid, dinonylnaphthalene sulfonic acid, 2,7- dinonyl -4- LOMAR PWA EINECS 246-676-2, dinonylnaphthalene disulfonic acid, 2,7- dinonyl -4,5- naphthalenedisulfonic acid.
Hole injection layer 3 for example can be formed using the rubbing method employing the coating fluid containing hole-injecting material.
As long as solvent used in coating fluid dissolves the solvent of hole-injecting material, for example, can enumerate chloroform, water, dichloromethane
The chlorine such as alkane, dichloroethanes system solvent；The ether such as oxolane system solvent；The aromatic series hydrocarbon system solvent such as toluene, dimethylbenzene；Acetone, first
The ketone such as ethyl ketone system solvent；The ester such as ethyl acetate, butyl acetate, ethyl cellosolve acetate system solvent.
As rubbing method, for example, can enumerate spin-coating method, the tape casting, micro gravure coating method, gravure coating process, rod painting
Method, rolling method, wire rod rubbing method, dip coating, spraying process, silk screen print method, flexographic plate print process, flexographic printing process and
Ink-jet method.By using these rubbing methods by coating solution on anode 2 it is possible to formed hole injection layer 3.
Furthermore, it is also possible to form hole injection layer 3 using vacuum vapour deposition.Additionally, if being made up of metal-oxide
Hole injection layer 3, then can also be formed using sputtering method or ion plating method.
The thickness of hole injection layer 3 is to consider desired characteristic and determine, usually 1nm～1 μm, preferably 2nm～
500nm, more preferably 5nm～200nm.
＜ hole transmission layer 4 ＞
Hole transmission layer 4 is the layer having and improving the interracial contact from anode 2 side with hole transmission layer 4 (is empty Fig. 1
Cave implanted layer 3) or closer to anode 2 hole transmission layer 4 hole from region to luminescent layer 5 injection function layer.
As the hole mobile material constituting hole transmission layer 4, for example can enumerate Polyvinyl carbazole and its derivant,
Polysilane and its derivant, the polysiloxanes in side chain or main chain with aromatic amine structure and its derivant, pyrazoline and
Its derivant, arylamine and its derivant, stilbene and its derivant, triphenyl diamine and its derivant, polyaniline and its
Derivant, polythiophene and its derivant, polyarylamine and its derivant, polypyrrole and its derivant, poly- (to phenylene Asia ethylene
Base) and its derivant, poly- (2,5- sub- thienyl ethenylidene) and its derivant；In Japanese Unexamined Patent Publication 2012-144722 publication
The hole mobile material recorded, preferably polyethylene base carbazole and its derivant, polysilane and its derivant, in side chain or main chain
There is polysiloxanes and its derivant of aromatic amine.In the case of the hole mobile material of low-molecular-weight, it is preferably dispersed in
Use in high polymer binder.
If the hole mobile material of such as low-molecular-weight, then sky can be formed by the mixed solution with high polymer binder
Cave transport layer 4, if the hole mobile material of high molecular, then can form hole transmission layer 4 by solution.
As long as the solvent used when forming hole transmission layer 4 by solution dissolves the solvent of hole mobile material,
The chlorine such as chloroform, dichloromethane, dichloroethanes system solvent for example can be enumerated；The ether such as oxolane system solvent；Toluene, dimethylbenzene etc.
Aromatic series hydrocarbon system solvent；The ketone such as acetone, butanone system solvent；The ester such as ethyl acetate, butyl acetate, ethyl cellosolve acetate system
Solvent.
In the case that hole transmission layer 4 is formed by solution, it is possible to use the formation identical coating with hole injection layer
Method.
As high polymer binder, for example can enumerate will not hinder to heavens electric charge transmission, weak to the absorption of visible ray
Compound, preferably Merlon, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polychlorostyrene
Ethylene, polysiloxanes.
The thickness of hole transmission layer 4 considers that driving voltage and luminous efficiency determine, usually 1nm～1 μm, preferably
2nm～500nm, more preferably 5nm～200nm.
＜ luminescent layer 5 ＞
Luminescent layer 5 usually contains the organic compound sending fluorescence and/or phosphorescence or this organic compound and assists its
Dopant.Dopant e.g. adds to improve luminous efficiency, changing emission wavelength.Because dissolubility is excellent, therefore have
Machine compound is preferably macromolecular compound, and the more preferably number-average molecular weight of polystyrene conversion is 103～108Macromolecule
Compound.As the luminescent material constituting luminescent layer 5, for example, can enumerate pigment system luminescent material, metal complex system lights
Material, macromolecular luminescent material.
As pigment system luminescent material, for example can enumerate cyclopentamine (シ Network ロ ペ Application タ ミ Application) and its derivant, four
Phenyl butadiene and its derivant, triphenylamine and its derivant, diazole and its derivant, pyrazolo quinoline and its derivative
Thing, diphenylethyllene benzene and its derivant, distyrylarylenes and its derivant, pyrroles and its derivant, thiophene chemical combination
Thing, pyridine compounds, purple cyclic ketones and its derivant and its derivant, Oligopoly thiophene and its derivant, diazole dimer,
Pyrazoline dimer, quinacridone and its derivant, coumarin and its derivant.
As metal complex system luminescent material, for example, can enumerate central metal and there is the rare earth eka-gold such as tb, eu, dy
Genus or al, zn, be, pt, ir etc. and part have diazole, thiadiazoles, phenylpyridine, phenylbenzimidazol, quinoline knot
The metal complex of structure etc., preferably iridium complex, platinum complex etc. have the luminous metal complex from triplet excited state；
Aluminium quinolinol complex, benzo hydroxyquinoline beryllium complex, benzoxazolyl group zinc complex, benzothiazole zinc complex, idol
N-methyl zinc complex, porphyrin zinc complex, phenanthroline europium complex.
As macromolecular luminescent material, for example, can enumerate poly (phenylenevinylene) and its derivant, polythiophene
And its derivant, polyparaphenylene and its derivant, polysilane and its derivant, polyacetylene and its derivant, polyfluorene and its derivative
Thing, Polyvinyl carbazole and its derivant；By pigment system luminescent material or metal complex system luminescent material producing high-molecular
Material.
As dopant, for example can enumerate rubrene and its derivant, side's acid inner salt and its derivant, aphthacene and
Its derivant, pyrrolinone and its derivant, decacyclene, phenazinone.
Luminescent layer 5 can steam using by rubbing method on hole transmission layer 4 for the solution coating containing luminescent material, vacuum
Plating method, transfer printing etc. are forming.In the middle of them, easy to manufacture due to organic el element, therefore carry out shape preferably by rubbing method
Become luminescent layer 5.As solvent used in the solution containing luminescent material, for example, can enumerate as forming hole injection
The solvent that in the coating fluid of layer 3, solvent used illustrates.
In the formation based on the luminescent layer of rubbing method, it is possible to use the formation identical rubbing method with hole injection layer.
And, in the case that luminescent material is the low molecular compound showing sublimability, except can using vacuum vapour deposition with
Outward, transfer or the thermal transfer by laser instrument or friction can also be used.
The thickness of luminescent layer 5 is usually 2nm～200nm.
＜ electron injecting layer 7 ＞
Electron injecting layer 7 is the layer with the function of energy potential barrier of reducing electron injection in the interface with negative electrode.
As electron injection material used in electron injecting layer 7, for example, can enumerate organic electronic injection material, inorganic
Electron donating property material.
As organic electronic injection material, for example, can enumerate metal-organic complex.Metal-organic complex for example may be used
Using enumerate at least one containing alkali metal ion, alkaline-earth metal ions and rare earth ion as metal ion and
As part have hydroxyquinoline, benzo hydroxyquinoline, hydroxy-acridine, phenanthridines alcohol, hydroxy phenyl azoles, hydroxy phenyl thiazole,
Hydroxy diaryl diazole, hydroxy diaryl thiadiazoles, hydroxy phenyl pyridine, hydroxy phenyl benzimidazole, hydroxybenzotriazole,
Hydroxyl boron fluoride (hydroxyfluborane), bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, beta-diketon, azo first
Alkali and the material of their derivant.
As inorganic electron donating property material, for example, can enumerate ba, li, na, k, rb, cs, fr, mg, ca, sr, ra, be etc.
Metal, their slaine, the compound containing these metals, the alloy containing these metals, preferably metal, more preferably ba,
li、cs、mg、ca.
Electron injecting layer 7 can be formed using with hole injection layer 3 identical method.
The thickness of electron injecting layer 7 considers that driving voltage and luminous efficiency determine, usually 0.01nm～1 μm, preferably
For 0.02nm～500nm, more preferably 0.05nm～100nm.
＜ negative electrode ＞
It is little, easily to ground floor 6a, second layer 6b and third layer 6c injection electricity that the material of negative electrode 8 is preferably work function
Son and the high material of electrical conductivity.In the case of going out light from anode 2 side draw, for the light negative electrode 8 of light emitting layer in future 5
To anode 2 lateral reflection, the material of negative electrode 8 is preferably the high material of visible reflectance.
As the material of negative electrode 8, for example, can enumerate alkali metal, alkaline-earth metal, transition metal and periodic chart 13 race's metal,
The preferably metal such as lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, described
In in alloy of more than two kinds in metal, described metal more than a kind and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten a kind
Alloy or graphite or compound between graphite layers.In this specification, include magnesium in alkaline-earth metal.
As alloy, for example, can enumerate magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum conjunction
Gold, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminium alloy.
For going out the element of light from negative electrode 8 side draw, transparent conductive electrode can be used as negative electrode 8.As transparent
The material of conductive electrode, for example, can enumerate the conductive metal oxides such as Indium sesquioxide., zinc oxide, stannum oxide, ito and izo；
The conducting organics such as Polyaniline and its derivative, polythiophene and its derivant.
Negative electrode 8 for example can be formed using the laminating of vacuum vapour deposition, sputtering method and thermo-compression bonding metallic film.
The thickness of negative electrode 8 considers that electrical conductivity and durability determine, usually 10nm～10 μm, preferably 20nm～1 μm,
More preferably 50nm～500nm.
Below, ground floor 6a, second layer 6b and third layer 6c are illustrated.
＜ ground floor 6a ＞
Ground floor 6a is the layer being made up of sodium fluoride contacting with luminescent layer 5, is between negative electrode 8 and luminescent layer 5
Layer.The purity of sodium fluoride be preferably 95 weight % more than, more than more preferably 98 weight %, more preferably 99 weight % with
On, more than particularly preferably 99.9 weight %.
Ground floor 6a for example can be formed using vacuum evaporation, coating, transfer.
With regard to the thickness for ground floor 6a, because the life-span of organic el element and driving voltage are excellent, therefore it is preferably
0.1nm～10nm, more preferably 2.0nm～8.0nm, more preferably 3.0nm～6.0nm.
＜ second layer 6b ＞
Second layer 6b is the layer being made up of alkali metal or alkaline-earth metal contacting with ground floor 6a.Alkali metal or alkaline-earth metal
Purity be preferably 95 mass % more than, more than more preferably 98 weight %, more than more preferably 99 weight %, especially excellent
Elect more than 99.9 mass % as.
For contained alkali metal or alkaline-earth metal in second layer 6b, from the viewpoint of reproducibility, preferably barium, sodium,
Or, potassium, more preferably barium.
In addition, for contained alkali metal or alkaline-earth metal in second layer 6b, from the viewpoint of electron injection, preferably
It is less than the metal of 2.8ev for work function, more preferably work function is the metal of 2.2ev～2.6ev.
For alkali-metal work function, lithium is 2.93ev, and sodium is 2.36ev, and potassium is 2.28ev, and rubidium is 2.16ev, and caesium is
1.95ev.For the work function of alkaline-earth metal, magnesium is 3.70ev, and calcium is 2.9ev, and strontium is more than 2.0ev and is below 2.5ev.
The thickness of second layer 6b is usually 0.1～20nm, preferably 0.5nm～10nm, more preferably 1nm～8nm.
＜ third layer 6c ＞
Third layer 6c is the layer containing Organic Electron Transport Material contacting with second layer 6b.
As Organic Electron Transport Material, it is possible to use the material belonging to organic compound in known electron transport material
Material, for example, can enumerate compound and its derivant that naphthalene, anthracene etc. have fused-aryl ring；4,4- double (diphenylethlenes
Base) the styrene base system aromatic rings derivant such as biphenyl；And its derivant, purple cyclic ketones and its derivant, coumarin and its derivative
The quinone such as thing, naphthalimide and its derivant, anthraquinone, naphthoquinone, diphenoquinone, anthraquinone bismethane, four cyano anthraquinone bismethane spreads out
Biological；Phosphorous oxide and its derivant, carbazole and its derivant and indole and its derivant；Three (8-hydroxyquinoline) aluminum (iii)
Deng hydroxyquinoline complex；The hydroxyl azoles complex such as hydroxy phenyl azoles complex；Azomethine complex, tropolone
Metal complex and flavonol metal complex；Comprise the compound with the heteroaryl ring of electron acceptor nitrogen.
So-called electron acceptor nitrogen, refers to form the nitrogen-atoms of multiple bond between adjacent atom.
As the compound comprising the heteroaryl ring with electron acceptor nitrogen, for example, can enumerate benzimidazole and its derive
Thing, benzothiazole and its derivant, diazole and its derivant, thiadiazoles and its derivant, triazole and its derivant, pyridine and
Its derivant, pyrazine and its derivant, phenanthroline and its derivant, quinoxaline and its derivant, quinoline and its derivates, benzo
The oligomeric pyridine and its derivatives such as quinoline and its derivates, bipyridyl, terpyridyl, quinoxaline and its derivant and naphthyridines
And its derivant, phenanthroline and its derivant.
As Organic Electron Transport Material, preferably lowest unoccupied molecular orbital (lumo) is less than the material of 3.0ev, more preferably
The material of 2.0ev～2.8ev.
Third layer 6c can be made up of Organic Electron Transport Material, but can also contain beyond Organic Electron Transport Material
Other materials.In the case of other materials beyond third layer 6c contains Organic Electron Transport Material, the containing of other materials
Amount can be 0.1～100 parts by volume or 0.1～30 parts by volume with respect to Organic Electron Transport Material 100 parts by volume,
It can also be 0.1～10 parts by volume.For example, Organic Electron Transport Material can also be used in combination with described inorganic electron donating material.?
In the case that third layer 6c contains inorganic electron donating material, the content of inorganic electron donating material is with respect to Organic Electron Transport Material
100 parts by volume are preferably 0.1～100 parts by volume, more preferably 0.1～30 parts by volume, more preferably 0.1～10 volume
Part.
In the case that third layer 6c uses the Organic Electron Transport Material of low-molecular-weight, can be by vacuum vapour deposition, molten
Liquid or molten condition are formed, in the case of the Organic Electron Transport Material using high molecular, can be by solution or molten
State is formed.It is also possible to and use high polymer binder in the case that third layer 6c is formed by solution or molten condition.
The thickness of third layer 6c is usually 1nm～1000nm, preferably 2nm～500nm, more preferably 3nm～200nm.
＜ ground floor 6a, second layer 6b, relation ＞ of third layer 6c
In organic el element of the present invention, for the thickness of ground floor 6a, second layer 6b and third layer 6c, by
When the thickness of one layer of 6a is set to 1, the thickness of second layer 6b is preferably 0.1～5.0, more preferably 0.2～2.0, third layer 6c
Thickness is preferably 0.1～100, more preferably 0.5～50.
Organic el element of the present invention for example can be by sequentially forming anode 2, hole injection layer 3, hole on substrate 1
Transport layer 4, luminescent layer 5, ground floor 6a, second layer 6b, third layer 6c, electron injecting layer 7 and negative electrode 8 and manufacture.
Other ＞ of ＜
The composition of organic el element of the present invention is not limited to the composition shown in Fig. 1, for example, can also be following
A)～f) composition.Again, for convenience's sake, ground floor, the second layer and third layer are referred to as multilamellar stack-type electronics to hand over
Connect layer (being crossed by け).
A) anode/hole injection layer/luminescent layer/multilamellar stack-type electronics handing-over layer/negative electrode
B) anode/hole injection layer/hole transmission layer/luminescent layer/multilamellar stack-type electronics handing-over layer/negative electrode
C) anode/luminescent layer/multilamellar stack-type electronics handing-over layer/negative electrode
D) anode/hole injection layer/luminescent layer/multilamellar stack-type electronics handing-over layer/electron injecting layer/negative electrode
E) anode/hole injection layer/hole transmission layer/luminescent layer/multilamellar stack-type electronics handing-over layer/electron injecting layer/the moon
Pole
F) anode/luminescent layer/multilamellar stack-type electronics handing-over layer/electron injecting layer/negative electrode
It is to engage that mark "/" represents between the layer of the both sides of mark "/".
Ground floor～third layer any one layer have hinder hole transmission function in the case of, this layer sometimes by
It is referred to as hole blocking layer.The organic el element flowing only through hole current for example can be made, according to the current value being determined
Reduce and to confirm this function.
In addition, in a) and b), there is in hole injection layer and/or hole transmission layer the function of the transmission hindering electronics
In the case of, these layers are sometimes referred to as electronic barrier layer.The organic el element flowing only through electronic current for example can be made, according to
The minimizing of the current value being determined is confirming this function.Furthermore, it is also possible to it is discrete with hole injection layer and/or hole transmission layer
Ground arranges electronic barrier layer between anode and luminescent layer.
Additionally, described a)～f) composition in any one in, if the stacking between anode and negative electrode will be configured at
Body is set to " stepped construction a ", then organic el element of the present invention can also be set to following g) layer constitute that (2 layers luminous organic
El element).The composition with stepped construction a of 2 both can be the same or different.
G) anode/stepped construction a/ charge generating layer/stepped construction a/ negative electrode
Here, so-called charge generating layer, it is to produce the layer of hole and electronics because applying electric field.As in charge generating layer
Material used, for example, can enumerate vanadium oxide, ito, molybdenum oxide.
If " stepped construction a/ charge generating layer " is set to " stepped construction b ", organic el element of the present invention can also
Be set to following h) layer constitute (more than 3 layers light organic el element).
H) anode/stepped construction b/ stepped construction a/ negative electrode
Here, stepped construction b can also repeat to arrange multiple identical or different stepped constructions.
Furthermore, it is also possible to be not provided with charge generating layer, and multiple luminescent layers are directly laminated.
In organic el element of the present invention, in above-mentioned each layer, material used both can also may be used using individually a kind of
With and with two or more.In addition, in organic el element of the present invention, anode, hole injection layer, hole transmission layer, luminescent layer,
Electron injecting layer and negative electrode both can be monolayer or multilamellar.
In organic el element of the present invention, not only can be in the example of substrate-side by above-mentioned anode arrangement, also may be used
With by cathode arrangement in substrate-side.Should in the case of, for example, as long as on substrate make a)～h) layer constitute organic el element
When, respectively it is laminated on layer by layer on substrate successively from negative electrode.
[embodiment]
Hereinafter, based on embodiment and comparative example, the present invention is specifically described, however the present invention be not limited to
Under embodiment.
＜ embodiment 1 ＞
As shown in figure 1,1 on substrate, stack gradually anode 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5,
One layer of 6a, second layer 6b, third layer 6c, electron injecting layer 7 and negative electrode 8, after producing organic el element, are entered using glass
Row sealing, thus produces glass capsulation organic el element (hereinafter referred to as " organic el element 1 ".).
On the glass substrate, as anode, ito thin film is formed with given pattern.Using sputtering method so that thickness is 45nm
Mode form ito thin film.Glass substrate organic solvent, alkalis and the ultra-pure water of ito thin film will be formed with surface
After carrying out ultrasound wave cleaning, boil in organic solvent 10 minutes, be allowed to drying.Then, using ultraviolet and ozone (uv-o3) dress
Put the ultraviolet and ozone face being formed with ito thin film being carried out about 15 minutes to process.
Using spin-coating method, the hole injection material with charge transport materials and electron acceptor combination of materials is coated with ito thin film
Material, thus forms film in the way of the thickness reaching 35nm.By this film in an atmosphere, on hot plate with 80 DEG C heat 4 minutes, then
Heat 15 minutes at 230 DEG C and be allowed to drying, be consequently formed hole injection layer.
The hole mobile material of high molecular is mixed with dimethylbenzene, the concentration obtaining hole mobile material is 0.6 weight
The hole transmission layer formation compositionss of amount %.Using spin-coating method, hole transmission layer formation compositionss are coated on hole injection
On layer, in the way of the thickness reaching 20nm, thus form film.By by be provided with the glass substrate of this film under nitrogen atmosphere, in heat
Heated 60 minutes with 180 DEG C on plate, and after so that solvent is evaporated, naturally cool to room temperature, be consequently formed hole transmission layer.
By fluorenes-amine copolymer thing (macromolecular luminescent material (blue)) and dimethylbenzene mixing, obtain the dense of fluorenes-amine copolymer thing
Spend the luminescent layer formation compositionss for 1.3 weight %.Using spin-coating method, luminescent layer formation compositionss are coated on hole to pass
On defeated layer, in the way of the thickness reaching 50nm, thus form film.By by be provided with the glass substrate of this film under nitrogen atmosphere,
After so that solvent is evaporated on hot plate, naturally cool to room temperature, thus obtain luminescent layer.
The glass substrate being formed with luminescent layer is transferred to deposited chamber, being vented to the indoor vacuum of evaporation is 1.0 × 10- 5Below pa.Then, using vacuum vapour deposition on luminescent layer in the way of the thickness reaching 3nm with evaporation rateShape
Become the film of sodium fluoride, be consequently formed the ground floor being made up of sodium fluoride.
Then, indoor in evaporation, utilize vacuum vapour deposition to be deposited with barium, in the way of the thickness reaching 2nm on the first layer
With evaporation rateForm the second layer.
Then, indoor in evaporation, utilize vacuum vapour deposition to be deposited with Organic Electron Transport Material, to reach on the second layer
The mode of the thickness of 10nm is with evaporation rateFilm forming, is consequently formed third layer.
Then, indoor in evaporation, third layer utilize vacuum vapour deposition be deposited with lithium fluoride, to reach the thickness of 0.5nm
Mode with evaporation rateFilm forming, is consequently formed electron injecting layer.
Then, indoor in the special evaporation of metal, electron injecting layer utilizes vacuum vapour deposition AM aluminum metallization, to reach
The mode film forming of the thickness of 100nm, is consequently formed negative electrode.
Thereafter, the glass substrate defining negative electrode is not exposed in air be transported to sealing processing chamber from deposited chamber,
Under nitrogen atmosphere, fit with the seal glass being coated with ultraviolet curable resin around, and irradiating ultraviolet light makes ultraviolet solid
Change resin solidification, thus produce organic el element 1.
Using organic el element 1, have rated the stability of driving voltage and current efficiency.
Driving voltage is with 10ma/cm2Constant current drive organic el element 1 when voltage.Current efficiency is organic el
The brightness of element 1 is 1000cd/m2When value.For their stability, organic el element 1 is saved in and can protect at 80 DEG C
In the preservation storehouse of temperature, determine driving voltage behind 0 hour, 24 hours, 48 hours, 168 hours for the holding time and electric current
Efficiency.
The current efficiency (0 hour holding time) of organic el element 1 is 9.9cd/a, driving voltage (0 hour holding time)
For 3.4v.In addition, for the current efficiency of organic el element 1, if the holding time is 24 hours, being 10.1cd/a, if 48 is little
Shi Zewei 10.1cd/a, if 168 hours is then 10.2cd/a, for driving voltage, if the holding time is 24 hours, be
3.4v, if being then within 48 hours 3.4v, if 168 hours be then 3.4v.The result of gained is shown in table 1.
＜ comparative example 1 ＞
Except in embodiment 1, replacing the second layer and third layer, and arrange and be mixed with barium and Organic Electron Transport Material
Beyond the layer of (material same as Example 1), produce glass capsulation organic el element (hereinafter referred to as same as Example 1ly
Make " organic el element c1 ".), have rated the stability of driving voltage and current efficiency.
Specifically, it is mixed with barium and the layer of Organic Electron Transport Material is formed as follows, i.e. in embodiment 1, to formation
There is the glass substrate of ground floor, indoor in evaporation, on the first layer, using vacuum vapour deposition, barium is deposited with 10:90 (volume ratio)
And Organic Electron Transport Material, with evaporation rate in the way of the thickness reaching 10nmAndBecome
Film, is consequently formed mixed layer.In addition, same as Example 1.
The current efficiency (0 hour holding time) of organic el element c1 is 9.0cd/a, and (holding time 0 is little for driving voltage
When) it is 4.2v.In addition, if the holding time is 24 hours, the current efficiency of organic el element c1 is 7.3cd/a, if 48 is little
Shi Zewei 7.1cd/a, if being then within 168 hours 6.9cd/a, if the holding time is 24 hours, driving voltage is 4.9v, if
It is then within 48 hours 5.0v, if being then within 168 hours 5.0v.The result of gained is shown in table 1.
＜ comparative example 2 ＞
Beyond in embodiment 1, being not provided with ground floor and the second layer, produce glass same as Example 1ly
Seal organic el element (hereinafter referred to as " organic el element c2 ".), have rated the stability of driving voltage and current efficiency.
The current efficiency (0 hour holding time) of organic el element c2 is 8.5cd/a, and (holding time 0 is little for driving voltage
When) it is 3.7v.In addition, if the holding time is 24 hours, the current efficiency of organic el element c1 is 3.8cd/a, if 48 is little
Shi Zewei 2.4cd/a, if being then within 168 hours 1.5cd/a, if the holding time is 24 hours, driving voltage is 4.0v, if
It is then within 48 hours 4.0v, if being then within 168 hours 4.2v.The result of gained is shown in table 1.
＜ comparative example 3 ＞
Except in embodiment 1, being not provided with beyond the second layer, produce glass capsulation organic same as Example 1ly
El element is (hereinafter referred to as " organic el element c3 ".), have rated the stability of driving voltage and current efficiency.
The current efficiency (0 hour holding time) of organic el element c3 is 6.6cd/a, and (holding time 0 is little for driving voltage
When) it is 4.7v.In addition, if the holding time is 24 hours, the current efficiency of organic el element c1 is 5.6cd/a, if 48 is little
Shi Zewei 5.7cd/a, if being then within 168 hours 5.9cd/a, if the holding time is 24 hours, driving voltage is 5.2v, if
It is then within 48 hours 5.3v, if being then within 168 hours 5.5v.The result of gained is shown in table 1.
＜ comparative example 4 ＞
Except in embodiment 1, being not provided with beyond ground floor, produce glass capsulation organic same as Example 1ly
El element is (hereinafter referred to as " organic el element c4 ".), have rated the stability of driving voltage and current efficiency.
The current efficiency (0 hour holding time) of organic el element c4 is 1.1cd/a, and (holding time 0 is little for driving voltage
When) it is 5.9v.In addition, if the holding time is 24 hours, the current efficiency of organic el element c1 is 0.5cd/a, if 48 is little
Shi Zewei 0.5cd/a, if being then within 168 hours 0.5cd/a, if the holding time is 24 hours, driving voltage is 6.0v, if
It is then within 48 hours 6.0v, if being then within 168 hours 6.1v.The result of gained is shown in table 1.
[table 1]
[table 1]
The explanation of symbol
1 ... substrate, 2 ... anodes, 3 ... hole injection layers, 4 ... hole transmission layers, 5 ... luminescent layers, 6a ... ground floor, 6b ...
The second layer, 6c ... third layer, 7 ... electron injecting layers, 8 ... negative electrodes.
Claims (4)
1. a kind of organic electroluminescent device, is to have anode and negative electrode and the luminescent layer between this anode and this negative electrode
Organic electroluminescent device,
Between this negative electrode and this luminescent layer, be there is the ground floor being made up of sodium fluoride being contacted with this luminescent layer and ground floor
The second layer being made up of alkali metal or alkaline-earth metal of contact and contact with the second layer containing Organic Electron Transport Material the
Three layers.
2. organic electroluminescent device according to claim 1, wherein, contained alkali metal or alkaline-earth metal in the second layer
For barium, sodium or potassium.
3. organic electroluminescent device according to claim 1 and 2, wherein, the thickness of the second layer is 0.1nm～20nm.
4. organic electroluminescent device according to claim 3, wherein, the thickness of ground floor is 0.1nm～10nm, and
The thickness of third layer is 1nm～1000nm.
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| JP2015-140230 | 2015-07-14 | ||
| JP2015140230A JP2017022299A (en) | 2015-07-14 | 2015-07-14 | Organic EL element |
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| JP (1) | JP2017022299A (en) |
| KR (1) | KR20170008683A (en) |
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| CN108417736A (en) * | 2018-01-29 | 2018-08-17 | 天津大学 | A kind of preparation method of transition metal oxide as hole injection layer |
| CN111224004A (en) * | 2019-11-08 | 2020-06-02 | 深圳市华星光电半导体显示技术有限公司 | OLED display panel and OLED display device |
| CN111279507A (en) * | 2017-11-02 | 2020-06-12 | 住友化学株式会社 | Organic electroluminescent element |
| CN111384254A (en) * | 2018-12-27 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot light-emitting diode |
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| US20220278281A1 (en) * | 2017-05-25 | 2022-09-01 | Nissan Chemical Corporation | Method for producing charge transporting thin film |
| KR101856426B1 (en) | 2017-11-27 | 2018-06-20 | 세종대학교산학협력단 | 3D geometry enhancement method and apparatus thereof |
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| CN111384254A (en) * | 2018-12-27 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot light-emitting diode |
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| Publication number | Publication date |
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| KR20170008683A (en) | 2017-01-24 |
| TW201712920A (en) | 2017-04-01 |
| JP2017022299A (en) | 2017-01-26 |
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