CN110277504A - Transparent electrode and organic electroluminescence device comprising it - Google Patents
Transparent electrode and organic electroluminescence device comprising it Download PDFInfo
- Publication number
- CN110277504A CN110277504A CN201810209149.9A CN201810209149A CN110277504A CN 110277504 A CN110277504 A CN 110277504A CN 201810209149 A CN201810209149 A CN 201810209149A CN 110277504 A CN110277504 A CN 110277504A
- Authority
- CN
- China
- Prior art keywords
- base material
- layer
- scattering particles
- transparent electrode
- nanometer line
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- H10K50/805—Electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Optics & Photonics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to a kind of transparent electrodes comprising base material, and the metal nanometer line contained in base material, doped with scattering particles in the base material.The invention further relates to a kind of organic electroluminescence devices, it is disposed with substrate, first electrode, organic luminescence function layer, second electrode from bottom to top, it is transparent electrode that it, which neutralizes the adjacent first electrode of substrate, it includes base material, and the metal nanometer line contained in base material, doped with scattering particles in the base material.
Description
Technical field
The present invention relates to photoelectric device technical field, in particular to a kind of transparent electrode and the organic electroluminescent comprising it
Device.
Background technique
Organic electroluminescence device includes cathode, the multilayer organic material of anode and setting between a cathode and an anode
Layer, it includes hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layers etc..Wherein, by organic material
The light that the bed of material generates is issued by transparent electrode.Organic electroluminescence device is commonly divided into top emission type, bottom-emission
Type and dual-side luminescent type.In top emission type or bottom emission type device, a need in two electrodes are transparent electrode；?
In dual-side luminescent type device, two electrodes are both needed to as transparent electrode.
Transparent electrode needs to have high light transmittance in favor of light-output caused by organic material layer.The transparent electrode
Preparation method be usually the metal oxide of transparent and high conductivity is formed in a manner of sputtering, such as indium tin oxide (ITO) or
Indium-zinc oxide (IZO).In general, being used as indium tin oxide (ITO), organic material layer and substrate (the usually glass of transparent electrode
Glass substrate) it is respectively provided with the refractive index of about 2.0,1.8 and 1.5.Due to the relationship of the refractive index, such as in bottom emission type device
In, the photon generated in organic material layer in the interface of organic material layer and first electrode layer or substrate by occurring in complete
It reflects and is captured, and only issue very small amount of photon.In addition, ITO there is a problem of in resistance it is serious.Particularly,
Above-mentioned big resistance is likely to become the huge obstacle of commercialization aspect.
Therefore, it is necessary to continually develop a kind of transparent electrode with excellent characteristics be in current organic electroluminescence device urgently
One of the emphasis that need to be studied.
Summary of the invention
The object of the present invention is to provide a kind of transparent electrode with high conductivity, light transmittance and surface smoothness,
It can be applied to organic electroluminescence device.
In order to achieve the above object, the present invention provides a kind of transparent electrode comprising base material, and contained in base material
Metal nanometer line, wherein in base material doped with scattering particles,
The base material is selected from more resins of card containing fluorenes ring, polyurethane, epoxy resin, polyester, alginate and its mixed
Close object, preferably alginate, especially sodium alginate, potassium alginate, ammonium alginate and its mixture；
The metal nanometer line contained in base material is selected from nanowires of gold, copper nano-wire or silver nanowires；
The scattering particles adulterated in the base material are selected from TiO2、SiN、ZrO2、ZnO、CaO、HfO2And its mixture.
In order to achieve the above object, the present invention also provides a kind of methods for preparing transparent electrode comprising following steps:
(1) by wherein doped with the base material dispersion of scattering particles on substrate, and it is dried to that there is scattering
The base material film of particle；
(2) metal nanometer line dispersion liquid is coated on the base material film with scattering particles, and it is thin to form metal nanometer line
Film, i.e. metal nanometer line transparent electrode.
The present invention also provides a kind of organic electroluminescence devices, are disposed with substrate from bottom to top, first electrode, have
Machine light emitting functional layer, second electrode, neutralizing the adjacent first electrode of substrate is transparent electrode comprising base material, and
Metal nanometer line contained in base material, doped with scattering particles in the base material.
Transparent electrode provided by the present invention can satisfy the basic demand that can be used for the material of organic electroluminescence device
(such as suitable energy level, electrochemical stability and thermal stability), and service life and the light efficiency of device can be greatly improved.
Detailed description of the invention
Using attached drawing, the present invention is further illustrated, but the content in attached drawing is not constituted to any limit of the invention
System.
Fig. 1 shows the sectional view of organic electroluminescence device of the invention, and wherein scattering particles are located at the top of base material
Layer.
Fig. 2 shows the sectional views of organic electroluminescence device of the invention, and wherein scattering particles are located in base material
Layer.
Fig. 3 shows the sectional view of organic electroluminescence device of the invention, and wherein scattering particles are located at the bottom of base material
Layer.
Fig. 4 shows the sectional view of organic electroluminescence device of the invention, wherein undoped scattering particles in base material,
So that interface of the part light between organic luminescence function layer and transparent electrode is totally reflected.
Fig. 5 shows the sectional view of organic electroluminescence device of the invention, and wherein scattering particles are located at the top of base material
Layer, compared to shown in Fig. 4 undoped with the organic electroluminescence device of scattering particles, produced by the organic electroluminescence device
Interface of the light between organic luminescence function layer and transparent electrode be not totally reflected.
Specific embodiment
The present invention is discussed in detail below.
In the present invention, as without opposite explanation, then all operations are implemented in room temperature, condition of normal pressure.
In the present invention, used when describing electrode and organic electroluminescence device and other structures body
"upper", "lower", "top" and "bottom" etc. indicate the word in orientation, are merely represented in the orientation of certain particular state, are not intended to relevant
Structure can only only be existed by the orientation；On the contrary, if structural body can shift one's position, such as it is inverted, then the orientation of structural body
Make corresponding change.Specifically, in the present invention, "bottom", the "lower" side of electrode refer to electrode during the preparation process close to substrate
Side, and far from substrate opposite side be "top", "upper" side.
On the one hand, the present invention provides a kind of transparent electrode comprising base material, and the metal contained in base material are received
Rice noodles, doped with scattering particles in the base material.
In one embodiment of the invention, can be used as base material is such as polyimides, the card containing fluorenes ring
More resins, polyurethane, epoxy resin, polyester or alginate.Preferred base material is alginate, such as sodium alginate, sea
Potassium alginate or ammonium alginate.Preferably, the number-average molecular weight of base material especially alginate be 8,000-700,000, it is excellent
It is selected as 10,000-80,000, more preferably 30,000-75,000.
Term " scattering particles " used herein refer to such as refractive index from solidify after base material is different and size
Suitable particle, thus can scatter, reflect or diffracting incident light.As scattering particles, can be used for example comprising materials described below
Particle: organic material, such as polystyrene or derivatives thereof, acrylic resin or derivatives thereof, silicone resin or derivatives thereof or
Phenolic resin or derivatives thereof；Or inorganic material, such as TiO2、SiN、ZrO2, ZnO, CaO or HfO2Deng.The partial size of scattering particles
(particle diameter) can be 50-1000nm, preferably 100-900nm, more preferable 400-700nm, more particularly 550-650nm.
It in one embodiment, is 2-25 μm doped with the thickness range of the substrate material layer of scattering particles, preferably
5-20 μm, more preferably 7.5-15 μm.Preferably, the scattering particles are located at top layer, middle layer or the bottom of base material, wherein
Top layer, middle layer or bottom are respectively 1/3 thickness of substrate material layer, are preferably placed at the top layer of base material.In another embodiment party
In case, content of the scattering particles in base material is 0.01-1mg, and preferably 0.1-0.8mg, more preferable 0.2-0.5mg are based on
1mg base material meter.
In one embodiment of the invention, metal nanometer line be nanowires of gold, copper nano-wire, silver nanowires or its
His any suitable metal nanometer line.The diameter of metal nanometer line is 60-120nm, and length is 10-20 μm.In another implementation
In scheme, the content of metal nanometer line is 0.1-10mg, preferably 0.5-5mg, based on 1mg doped with the base material of scattering particles
Meter.
In one embodiment of the invention, transparent electrode of the invention is in 400-800nm, preferably in the wave of 550nm
Strong point, light transmittance are greater than 70%, preferably greater than 80%, more preferably greater than 85%, more particularly 90% or more.
Transparent electrode of the invention can be needed according to situation as the anode or cathode in organic electroluminescence device, and can
It applied to display or needs on the device of transparent electrode, such as liquid crystal display (LCD), light emitting diode (LED) or organic
Electroluminescent device (OLED) etc., but not limited to this.
On the other hand, the present invention also provides a kind of methods for preparing transparent electrode comprising following steps:
(1) by wherein doped with the base material dispersion of scattering particles on substrate, and it is dried to that there is scattering
The base material film of particle；
(2) metal nanometer line dispersion liquid is coated on the base material film with scattering particles, and it is thin to form metal nanometer line
Film, i.e. metal nanometer line transparent electrode.
In one embodiment of the invention, substrate can be any commonly employed substrate in organic electroluminescence device, example
Such as, opaque substrate, such as silicon or stainless steel；Transparent substrate, such as glass or transparent plastic.The example of substrate can also be flexibility PI
Film, but it is not limited to these.Preferably, the surface of substrate is smooth, and its thickness range can be 50-700 μm.
In one embodiment of the invention, scattering particles are configured to concentration by solvent or diluent is 0.05-
The dispersion liquid of 0.2mg/ml.Suitable solvent or diluent can be alcohols, for example, substituted or unsubstituted methanol, ethyl alcohol, propyl alcohol,
Isopropanol, butanol etc. and their any mixture, preferably C1-C6The propyl alcohol or isopropanol that alkoxy replaces, especially 1-
Methoxy-2-propanol.
In one embodiment of the invention, base material is configured to concentration by solvent or diluent is 0.3-
0.5mg/ml, the dispersion liquid specifically for 0.4mg/ml.Suitable solvent or diluent are all suitable inert organic solvents, example
Such as aliphatic hydrocarbon or aromatic hydrocarbon (such as petroleum ether, toluene, hexamethylene), halogenated hydrocarbons (such as chlorotoluene, dichloro-benzenes, methylene chloride, chlorine
Imitative, 1,2- dichloroethanes), ether (such as ether, dioxane, tetrahydrofuran, 1,2- dimethoxy-ethane), ester (such as
Ethyl acetate or methyl acetate), nitro hydro carbons (such as nitromethane, nitroethane, nitrobenzene), nitrile (such as acetonitrile, propionitrile,
Butyronitrile, benzonitrile), amides (such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl formyl aniline, N- methyl
Pyrrolidones, hexamethyl phosphoramide) and dimethyl sulfoxide；Or water；Or the mixture of the solvent.
In one embodiment of the invention, the scattering particles dispersion liquid of various concentration can be doped in base material point
In dispersion liquid, the base material dispersion liquid wherein doped with the scattering particles of different content is thus prepared.Particularly, in base material
In dispersion liquid, the contents of scattering particles is 0-1mg, preferably 0.01-1mg, more preferable 0.1-0.8mg, especially 0.2-0.5mg,
Based on 1mg base material.
In one embodiment of the invention, metal nanometer line is configured to concentration by organic solvent is 1-6mg/
The dispersion liquid of ml, preferably 3-6mg/ml, more particularly 5mg/ml.Organic solvent used in the present invention can be alcohols, such as first
Alcohol, ethyl alcohol, propyl alcohol, isopropanol, butanol etc. and their any mixture, preferred alcohol or isopropanol.Metal nanometer line is special
Be not that silver nanowires has a preferable dispersibility in ethanol, and by metal nanometer line dispersion in base material
After surface, ethyl alcohol is volatile, and is easy to form a film.
In one embodiment of the invention, solution coating process such as spin-coating method can be used to coat on substrate and wherein adulterate
There are the base material dispersion liquid or metal nanometer line dispersion liquid of the scattering particles of different content.In another embodiment, may be used
The base material dispersion liquid and the metal nanometer line of the scattering particles with different content are repeatedly coated on substrate
Dispersion liquid, so that top layer, middle layer or the bottom of base material (such as alginate) have the scattering particles of different content, and
The metal nanometer line of different content.
Preferably, scattering particles are located at the top layer of base material.Preferably, metal nanometer line is located at the top of base material
Surface.Particularly, the content of metal nanometer line is 0.1-10mg, preferably 0.5-5mg, based on 1mg doped with the base of scattering particles
Bottom material meter.
Preferably, the drying and forming-film can carry out at normal temperatures and pressures.
Preferably, clean smooth cover plate is affixed on the metal nanowire thin-films prepared, drains cover plate and is received with metal
Air between rice noodles film, and apply pressure compaction on cover plate.
In one embodiment of the invention, cover plate can be cover glass.In another embodiment, on cover plate
Pressure applied range is 7-15MPa, preferably 10-15MPa, more particularly 12MPa.
Preferably, metal nanometer line transparent electrode is subjected to immersion treatment in neutral salt solution.In an embodiment
In, the neutral salt solution for carrying out immersion treatment can be concentration be 3-7mg/ml, specifically for 5mg/ml NaCl solution or
CaCl2Solution.
It is further preferred that being impregnated after first tabletting.
Preferably, the metal nanometer line transparent electrode after immersion treatment is cleaned and dried, obtains the transparent electricity of metal nanometer line
Pole.
The present invention also provides a kind of organic electroluminescence devices, are disposed with substrate from bottom to top, first electrode, have
Machine light emitting functional layer and second electrode, which is characterized in that and the first electrode of substrate adjoining is transparent electrode comprising substrate material
Expect, and the metal nanometer line contained in base material, doped with scattering particles in the base material.
The substrate can be selected optionally, i.e., if it is desire to forming top emission type device, then the substrate can be for not
Transparent substrate, such as silicon or stainless steel；If it is desire to forming dual-side luminescent type device, then the substrate can be transparent substrate, such as glass
Or transparent plastic.The example of substrate can be also flexibility PI film, but be not limited to these, and can be any commonly employed in organic electroluminescent
The substrate of device.The thickness range of substrate can be 50-700 μm.
First electrode can be anode, and second electrode can be cathode.
Alternatively, first electrode can be cathode, second electrode can be anode.
Anode material is preferably the material with high work function, so that hole is readily injected into organic layer.The present invention is used as
The specific example of anode material includes, but are not limited to gold, silver, copper, vanadium, chromium, zinc and its alloy.
Cathode material is preferably the material with low work function, so that electronics is readily injected into organic layer.Cathode material
Specific example includes, but are not limited to, metal for example gold, silver, copper, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminium, silver, tin and
Lead or its alloy；And multilayer material such as LiF/Al or LiO2/Al。
To the thickness of above-mentioned electrode layer, there is no particular limitation, but in view of factors such as resistance of above-mentioned electrode interlayer,
It can have the thickness of for example, about 1-300nm, preferably 5-200nm.
In one embodiment of the invention, the organic luminescence function layer being set between first electrode and second electrode
It can be one or more layers organic material layer, the overwhelming majority is the compound of pure organic material or organic material and metal.With
Organic material in organic electroluminescence device can be divided into hole injection layer, hole transmission layer, electronic blocking according to its purposes
Layer, luminescent layer, hole blocking layer, electron transfer layer or electron injecting layer.However, the structure of organic electroluminescence device is not limited to
This, may include lesser amount of organic material layer.In general, the thickness range of organic luminescence function layer is 120-500nm, preferably
150-350nm。
In general, the organic material --- its be easily oxidized and electrochemically stable when it is oxidized --- with p-type property
It is mainly used as hole-injecting material or hole mobile material.Meanwhile with N-shaped property organic material --- its be easily reduced and
It is electrochemically stable when being reduced --- it is mainly used as electron injection material or electron transport material.It is excellent as emitting layer material
Choosing not only with p-type property but also had the material of N-shaped property, when its be oxidized and when it is reduced it is stable.Further preferably when
It is with higher for converting exciton to the material of the luminous efficiency of light when forming exciton.
The material of hole injection layer is usually preferably with the material of high work function, so that hole is easily injected into organic material
In the bed of material.The specific example of the material of hole injection layer includes, but are not limited to having for metalloporphyrin, Oligopoly thiophene and arylamine class
Machine material, six azepine Benzophenanthrenes (such as HAT-CN) and the organic material of quinacridine ketone, anthraquinone, gather the organic material of class
Phenyl amines and the conducting polymer of polythiophene class etc..
The material of hole transmission layer is preferably the material with high hole mobility, this can make hole from anode or hole
Implanted layer is transferred to luminescent layer.The specific example of the material of hole transmission layer includes, but are not limited to the organic material of arylamine class (such as
NPB), conducting polymer and the block copolymer with conjugation effect part and non-conjugated effect part.
Electronic barrier layer is to stop to pass through luminescent layer from cathode injected electrons and enter anode, thus extends the longevity of device
The layer of the efficiency of device is ordered and improves, also, if necessary, electronic barrier layer can be used known materials (such as TCTA) and be formed in hair
Appropriate part between photosphere and hole injecting electrode layer.
The material of luminescent layer is a kind of hole and electronics by being received respectively from hole transmission layer and electron transfer layer,
And by received hole and electronics in conjunction with and the material of visible light can be issued, preferably there is high quantum to imitate fluorescence and phosphorescence
The material of rate.According to its luminescent color, luminescent material is divided into blue, green and red illuminating material, furthermore more in order to realize
Self-colored needs, are in addition divided into yellow and orange light emitting materials.Its specific example includes 8- Hydroxy-quinolin-aluminium complex
(Alq3)；Carbazolyl compound；Two polystyrene compounds；BAlq；10- hydroxy benzo quinoline-metallic compound；Based on benzo
The compound of oxazole, benzothiazole and benzimidazole；Polymer based on poly- (to phenylene vinylidene) (PPV)；Spirocyclization
Close object；Polyfluorene and rubrene；Phosphorescence host CBP [[4,4'- bis- (9- carbazyl) biphenyl] etc., but not limited to this.
In addition, in order to improve fluorescence or phosphorescent characteristics, luminescent material may also include phosphorescent dopants or fluorescent dopants.Phosphorus
The specific example of photodopant includes Ir (ppy)3[three (2- phenylpyridines) close iridium], F2Irpic [bis- (4,6- difluorophenyl pyrroles
Pyridine-N, C2) pyridinecarboxylic conjunction iridium (III)] etc..For fluorescent dopants, can be used it is as known in the art those.
Hole blocking layer is to stop to pass through luminescent layer from anode injected holes and enter cathode, thus extends the longevity of device
The layer of the efficiency of device is ordered and improves, also, if necessary, hole blocking layer can be used known materials and be formed in luminescent layer and electricity
Appropriate part between sub- injecting electrode layer.
The material of electron transfer layer is a kind of easy electronics for receiving cathode and by received electronics transfer to luminescent layer
Material.It is preferred that the material with high electron mobility.The specific example of the material of electron transfer layer includes, but are not limited to 8- hydroxyl
Base aluminium quinolinol complex, organic free radical compound and flavonol-metal complex, especially TPBi.
The material of electron injecting layer is usually preferably with the material of low work function, so that electronics is easily injected into organic material
In the bed of material.The specific example of electron injection material includes: metal, as magnesium, calcium, sodium, potassium, titanium, indium, iridium, lithium, gadolinium, aluminium, silver, tin,
Lead or its alloy or aforementioned various mixture；Sandwich, such as LiF/Al or Li2O/Al etc., but not limited to this.
Organic electroluminescence device may also include encapsulating structure.The encapsulating structure can be to prevent external substance such as moisture
Enter the protection structure of the organic layer of organic electroluminescence device with oxygen.The encapsulating structure can be such as tank, such as glass jar
Or metal can；Or the film of covering organic layer whole surface.
Fig. 1-5 illustrates the structure of organic electroluminescence device of the invention, but its is without being limited thereto.Such as Fig. 1-5
It is shown, in organic electroluminescence device of the invention, it is disposed with substrate (10), first electrode, organic from bottom to top
Light emitting functional layer and second electrode (1).It is wherein transparent electrode with the adjacent first electrode of substrate comprising base material
(9), the metal nanometer line (8) of the top surface and positioned at base material, doped with scattering particles, institute in the base material
Stating scattering particles can be located separately top layer, middle layer or the bottom of base material, and the top layer, middle layer or bottom are respectively base material
In 1/3 thickness of layer.Wherein, for the organic material of organic luminescence function layer according to its purposes can be divided into hole injection layer (7),
Hole transmission layer (6), electronic barrier layer (5), luminescent layer (4), electron transfer layer (3) or electron injecting layer (2).
During preparing organic electroluminescence device, vacuum deposition method, vacuum vapour deposition, solution coating process can be used
Above compound is used to form organic luminescence function layer.About this point, solution coating process means spin-coating method, dip coating, injection
Print process, screen printing method, spray-on process and rolling method etc., it is not limited to this.
In addition, can for example be prepared by being laminated first electrode, organic luminescence function layer and second electrode in succession on substrate
Organic electroluminescence device of the invention.About this point, physical gas-phase deposite method can be used, such as sputtering method or Electron Beam Vapor
Method, but the method is without being limited thereto.
Organic electroluminescence device of the invention, there is no limit for the thickness of each layer film, it is however generally that, if lepthymenia
The defects of being then easy to produce pin hole needs high application voltage if blocked up and makes deterioration of efficiency, therefore generally preferable 0.1-
The range of 1000nm.
Embodiment
It is that in order to preferably explain the present invention, the scope of protection of the present invention is not limited to this that embodiment, which is described below,.
Test method
(1) sheet resistivity
Sheet resistivity is measured using four-point probe (TZ24-RTS-8).
(2) light transmittance
Light transmittance is measured using visible ultraviolet spectrophotometer (MAPADA UV-3100PC).
(3) surface smoothness
Surface smoothness is measured using atomic force microscope (Nanonavi E-Sweep).
(4) external quantum efficiency and chromaticity coordinates
Outer quantum is measured using voltage and current source (Keithley 2400) and luminescent chromaticity meter (BM-7A, Topcon) to imitate
Rate and chromaticity coordinates.
(5) the LT90 service life (h)
The LT90 service life is measured using OLED life-span tester (M6000).
Influence of the scattering particles to light transmittance
1. influence of the partial size of scattering particles to light transmittance
Respectively by 1.0mg meso-position radius D50(particle diameter when i.e. the cumulative frequency of particle diameter distribution is equal to 50% weight) such as table
TiO shown in 12Particle is dissolved in 10mL 1- methoxy-2-propanol, thus to obtain a kind of white paste dispersion liquid.And it will be described
Dispersion liquid is doped in 5mL 0.4mg/ml sodium alginate, and (number-average molecular weight 30,000-75,000, spinning chemical industry purchased from Qingdao hundred million has
Limit company) in aqueous solution, it is coated in by spin-coating method then and is handled on clean glass substrate (having a size of 5cm × 5cm),
And the film with a thickness of 15 μm is dried under room temperature environment, wherein repeatedly being coated so that TiO2Particle is located at sodium alginate top
Layer, the top layer thickness of sodium alginate are 5 μm.The light transmittance at the wavelength of 550nm is measured using visible ultraviolet spectrophotometer,
The results are shown in Table 1.
Table 1
| Number | Meso-position radius D50 | Light transmittance (%)@550nm |
| 1 | 100nm | 88 |
| 2 | 200nm | 89 |
| 3 | 300nm | 89 |
| 4 | 400nm | 90 |
| 5 | 500nm | 91 |
| 6 | 600nm | 93 |
| 7 | 700nm | 90 |
| 8 | 800nm | 89 |
| 9 | 900nm | 88 |
| 10 | 1000nm | 86 |
As shown in table 1, work as TiO2The meso-position radius D of particle50When for 600nm, it is able to achieve up to 93% light transmittance.And with
TiO2Particle meso-position radius D50Reduction and increase, light transmittance has downward trend.Therefore, it in following examples, chooses
Meso-position radius D50For the TiO of 600nm2Particle.
2. content and its position influence to light transmittance of the scattering particles in sodium alginate
Respectively by meso-position radius D50For the TiO of 600nm2Particle is dissolved in 10mL 1- methoxyl group -2- third with content shown in table 2
In alcohol, thus to obtain a kind of white paste dispersion liquid.And it is water-soluble that the dispersion liquid is doped in 5mL 0.4mg/ml sodium alginate
In liquid, it is coated in by spin-coating method then and is handled on clean glass substrate, and be dried under room temperature environment with a thickness of
15 μm of film, wherein repeatedly being coated so that TiO2Particle is located at top layer, middle layer and the bottom of sodium alginate, alginic acid
Top layer, middle layer and the underlayer thickness of sodium are respectively 5 μm.The light transmittance at the wavelength of 550nm is measured, the results are shown in Table 2.
Table 2
From Table 2, it can be seen that in the sodium alginate prepared on the glass substrate, compared to no TiO2The seaweed of particle
For sour sodium, there is TiO2The sodium alginate of particle light transmittance with higher, main cause are TiO2Particle is increased to light
Scattering process, so that light transmittance is increased.Meanwhile TiO2The content of particle and its location of in sodium alginate it is also right
The light transmittance of sodium alginate generates large effect.From Table 2, it can be seen that adulterating the TiO of 1.0mg in sodium alginate2?
Grain has biggish promotion for the light transmittance of sodium alginate, by originally not mixed with TiO2The 88% of the sodium alginate of particle increases
To 92% or more, and work as TiO2When particle is located at the top layer of sodium alginate with good light transmittance, reach 93%.
Prepare transparent electrode
Embodiment 1
Respectively by 1.0mg meso-position radius D50For the TiO of 600nm2Particle is dissolved in 10mL 1- methoxy-2-propanol, is thus obtained
Obtain a kind of white paste dispersion liquid.And the dispersion liquid is doped in 5mL 0.4mg/ml sodium alginate aqueous solution, then will
It is coated in by spin-coating method and is handled on clean glass substrate, and the film with a thickness of 15 μm is dried under room temperature environment,
It is middle repeatedly to be coated so that TiO2Particle is located at the top layer of sodium alginate.
By 1mL 1mg/ml silver nanowires, (diameter 60-120nm, length are 10-20 μm, are purchased from Nanjing Xian Feng nanometers of material
Expect Science and Technology Ltd.) dispersion liquid in ethanol is coated on sodium alginate by spin-coating method, is dried under room temperature environment
With a thickness of the film of 200nm；
Clean smooth cover glass is affixed on the silver nanowires film prepared, cover glass and silver nanowires are drained
Between air, and on cover glass apply 12MPa pressure compaction；
Cover glass is removed, the transparent silver nanowires electrode obtained after tabletting will be removed and be placed in 5mg/ml CaCl2Solution
Middle progress immersion treatment 10min；
Transparent silver nanowires electrode after immersion treatment is cleaned and dried by ultrapure water, obtains transparent silver nanowires electricity
Pole.
Embodiment 2-6
Transparent electrode is prepared in the same manner as in Example 1, the difference is that respectively by 1mL silver nanowires in ethyl alcohol
In dispersion liquid with concentration shown in embodiment 2-6 in table 3 be coated on sodium alginate on.
Embodiment 7
Transparent electrode is prepared in method same as Example 5, the difference is that by 1.0mg TiO2Particle is doped in
In 5mg aliphatic epoxy resin UVR-6128 (epoxide equivalent 190-210g/mol is purchased from Xin Jing chemical industry Co., Ltd),
Rather than in sodium alginate.
Comparative example 1
Transparent electrode is prepared in the same manner as in Example 1, the difference is that 1mL 1mg/ml silver nanowires is existed
Dispersion liquid in ethyl alcohol is directly coated on glass substrate, rather than on sodium alginate.
Comparative example 2-6
Transparent electrode is prepared in method identical with comparative example 1, the difference is that respectively by 1mL silver nanowires in ethyl alcohol
In dispersion liquid with concentration shown in comparative example 2-6 in table 3 be coated on glass substrate on.
Comparative example 7
The transparent conductive film with a thickness of 200nm is prepared by ion beam sputtering on the glass substrate.
Sheet resistivity, the light transmittance at the wavelength of 550nm, surfacing of the transparent electrode of above-mentioned preparation are measured respectively
Degree, test data are as shown in table 3.
Table 3
From table 3 it is observed that with the raising of silver nanowires dispersion liquid concentration, prepared silver nanowires transparent electrode
Sheet resistivity constantly reduce, surface smoothness constantly rises, and light transmittance constantly reduces.It is dense when silver nanowires dispersion liquid
When degree is 5mg/L, prepared silver nanowires transparent electrode sheet resistivity has reached 2.3 Ω/sq on sodium alginate, much small
Reach 82% in 12 Ω of sheet resistivity/sq of ITO conductive film, and in incident wavelength for the light transmittance at 550nm, surfacing
Degree reaches 36nm, has been more than the standard for preparing OLED.And directly prepared silver nanowires electrode has on the glass substrate
There are higher sheet resistivity, lower light transmittance surface smoothness.Even if when the concentration of silver nanowires dispersion liquid is 6mg/L,
Sheet resistivity still reaches 40 Ω/sq, and surface roughness reaches 286nm, and light transmittance is only 56%, does not meet far and prepares device
Standard.
Prepare organic electroluminescence device
Embodiment 1:
By 0.5mg meso-position radius D50For the TiO of 600nm2Particle is dissolved in 10mL 1- methoxy-2-propanol, thus to obtain one
Kind white paste dispersion liquid.And the dispersion liquid is doped in 5mL 0.4mg/ml sodium alginate aqueous solution, then led to
It crosses spin-coating method to be coated on the clean glass substrate of processing, and is dried to the film with a thickness of 15 μm under room temperature environment, wherein into
Row repeatedly coats so that TiO2Particle is located at top layer, middle layer and the bottom of sodium alginate, the top layer of sodium alginate, middle layer and
Underlayer thickness is respectively 5 μm.
The silver nanowires dispersion liquid of 1mL 5mg/L is coated in the sodium alginate substrate prepared by spin-coating method, and
Drying at room temperature 1 hour.The cover glass for cleaning up surfacing is attached to the silver nanowires with a thickness of 200nm prepared
On film, the air between cover glass and silver nanowires is drained, and uniformly applies on cover glass the pressure of 12MPa and holds
It is 30 minutes continuous.Later, from transparent silver nanowires sur-face peeling cover glass, continue drying 2 hours at room temperature, obtain transparent silver
Nano-electrode.Further, silver nanowires transparent electrode is etched into the figure of demand.
Later, transparent electrode is moved in vacuum cavity, hole injection layer material HAT- is deposited by vacuum evaporation mode
CN, with a thickness of 10nm, this layer is as hole injection layer 7；On hole injection layer 7, hole is deposited by vacuum evaporation mode and is passed
Defeated material NPB, with a thickness of 90nm, which is hole transmission layer 6；On hole transmission layer 6, electricity is deposited by vacuum evaporation mode
Sub- barrier material TCTA, with a thickness of 10nm, which is electronic barrier layer 5；Luminescent layer 4 is deposited on electronic barrier layer 5, with
CBP is as material of main part, Ir (ppy)3As dopant material, Ir (ppy)3Mass ratio with CBP is 12:100, with a thickness of 20nm；
On luminescent layer 4, electron transport material TPBi is deposited by vacuum evaporation mode, with a thickness of 35nm, this layer of organic material is made
For the use of electron transfer layer 3；On electron transfer layer 3, vacuum evaporation electron injecting layer LiF, with a thickness of 1nm, which is electricity
Sub- implanted layer 2；On electron injecting layer 2, vacuum evaporation cathode Al, with a thickness of 100nm, which is cathode layer.
In the above-mentioned methods, the organic material is the compound for the formula that has following structure:
Embodiment 2-4
Organic electroluminescence device is prepared in the same manner as in Example 1, the difference is that respectively by meso-position radius D50
For the TiO of 600nm2Particle is doped in sodium alginate with content shown in embodiment 2-4 in table 4.
Comparative example 1
The organic electroluminescence device of comparative example 1 is prepared in the same manner as in Example 1, the difference is that will not mix
Miscellaneous TiO2The sodium alginate aqueous solution of particle, which is coated in, to be handled on clean glass substrate.
As the test result of organic electroluminescence device prepared in the above embodiments is described in the following table 4.
Table 4
As can be seen from Table 4, the TiO in sodium alginate2The performance of device, and TiO can be substantially improved in particle2Particle
When content in sodium alginate is 1mg, there is maximum lift to device performance, reach 22% or more.With TiO2Particle contains
The reduction and increase of amount, the performance of device have downward trend.Main cause is in TiO2When granule content is smaller, light is scattered not
Sufficiently, part light is scattered out in electrode and sodium alginate interface, a part of light is still from reflected at interfaces to device
It causes damages inside part.And work as TiO2When the content of particle is larger, certain mist degree can be generated to sodium alginate, makes its light transmittance
It reduces, leads to the decline of device performance.
Meanwhile as can be seen from Table 4, in TiO2When particle is located at the top layer of sodium alginate, device performance is best.Mainly
The reason is that electrode and sodium alginate interface can be effectively reduced due to total reflection when scattering particles are located at the top layer of sodium alginate
The loss of caused device light efficiency can not play such effect positioned at sodium alginate middle layer and bottom.From above-mentioned device count
According to can be seen that in 10mA/cm2In the case where, the device performance with scattering particles is compared to the device for not having scattering particles
Part performance obtains twice or more of promotion, is promoted by original 11.5% to 24.6%.
From above-mentioned CIE chromaticity coordinates can be seen that no matter TiO2Particle whether there is the color in organic electroluminescence device
Coordinate is stable not to be changed significantly in (0.32,0.62), illustrates the organic electroluminescent prepared by such method
Device has preferable color stability.
Embodiment 5-10
The organic electroluminescence device of embodiment 5-10 is prepared in method same as Example 2, wherein scattering particles position
In the top layer of sodium alginate, the difference is that by 1mL silver nanowires dispersion liquid respectively with dense shown in embodiment 5-10 in table 6
Degree is coated on sodium alginate.
Embodiment 11
With the organic electroluminescence device of method preparation embodiment 11 same as Example 9, the difference is that will
1.0mg TiO2Particle is doped in 5mg aliphatic epoxy resin UVR-6128, rather than in sodium alginate.
As the test result of organic electroluminescence device prepared in the above embodiments is described in the following table 5.
Table 5
As can be seen from Table 5, the device with higher device prepared when silver nanowires concentration is 5mg/ml
Can, wherein in 10mA/cm2In the case where, external quantum efficiency reaches 11.5%, and the service life reaches 112h.With silver nanowires concentration
Continuous reduction and raising, prepared device performance is on a declining curve.Main cause is to use the lower silver nanoparticle of concentration
The sheet resistivity with higher of transparent electrode prepared by line causes carrier injection more difficult, and device performance is poor.With
The concentration of silver nanowires dispersion liquid is continuously increased, and the light transmittance of silver nanowires electrode constantly reduces, and device performance is caused to reduce.?
When silver nanowires dispersion liquid concentration is 5mg/ml, reach certain balance in light transmittance and sheet resistivity, has compared with high light transmission
There is lesser sheet resistivity while rate.
Comparative example 2
With the organic electroluminescence device of method identical with comparative example 1 preparation comparative example 2, the difference is that not mixing
The transparent conductive film with a thickness of 200nm is prepared by ion beam sputtering on the sodium alginate top layer of miscellaneous scattering particles.
Comparative example 3
The organic electroluminescence device of comparative example 3 is prepared in the same manner as in Example 1, the difference is that by 1mL
5mg/ml silver nanowires dispersion liquid is directly coated on glass substrate, rather than is coated in the sodium alginate doped with scattering particles
On.
The test data of the organic electroluminescence device of above-mentioned preparation and the Comparative result of embodiment 2 are as shown in table 6.
Table 6
As can be seen from Table 6, silver nanowires is directly coated on glass substrate come when preparing device, with poor
Device performance.In 10mA/cm2In the case where, external quantum efficiency is only 2.2%, and the service life only has 10h.Main cause is will be silver-colored
The electrode that nano wire is directly coated on glass substrate and prepares has biggish roughness and sheet resistivity, easily causes device
The short circuit of part.By preparing silver nanowires electrode in sodium alginate top layer, surface roughness can be effectively reduced, device is improved
Stability, the voltage of device obtain certain promotion.In 10mA/cm2In the case where, the external quantum efficiency of device reaches
11.5%, the service life of device reaches 112h.By mixing scattering particles in sodium alginate top layer, device performance is significantly mentioned
It rises.Scattering process mainly due to scattering particles to light effectively reduces device inside to the reflex of light.May be used also simultaneously
To find out, silver nanowires electrode is compared to the transparent prepared by sodium alginate top layer prepared by sodium alginate top layer
Electrode has better device performance, and main cause is because prepared silver nanowires transparent electrode has smaller surface side
Resistance, hole injection is more easy, and device inside carrier balance degree is more preferable, so the performance of device is higher.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Art technology
Personnel without departing from the objective and range of technical solution of the present invention, to technical solution of the present invention carry out modification or
Person's equivalent substitute, is intended to be within the scope of the claims of the invention.
Claims (13)
1. a kind of transparent electrode, including base material, and the metal nanometer line contained in base material, wherein mix in base material
It is miscellaneous to have scattering particles,
The base material is selected from the more resins of card, polyurethane, epoxy resin, polyester, alginate and its mixture containing fluorenes ring,
It is preferred that alginate, especially sodium alginate, potassium alginate, ammonium alginate and its mixture；
The metal nanometer line contained in base material is selected from nanowires of gold, copper nano-wire or silver nanowires；
The scattering particles adulterated in the base material are selected from TiO2、SiN、ZrO2、ZnO、CaO、HfO2And its mixture.
2. transparent electrode according to claim 1, wherein scattering particles are located at top layer, middle layer or the bottom of base material,
The top layer, middle layer or bottom are respectively to be preferably placed at the top layer of base material in 1/3 thickness of substrate material layer；And wherein,
Metal nanometer line is located at the top surface of base material.
3. transparent electrode according to claim 1, wherein content of the scattering particles in base material is 0.01-1mg, excellent
0.1-0.8mg, more preferable 0.2-0.5mg are selected, based on 1mg base material.
4. transparent electrode according to claim 1, wherein the partial size of scattering particles is 50-1000nm, preferably 100-
900nm, more preferable 400-700nm, more particularly 550-650nm.
5. transparent electrode according to claim 1, wherein the content of metal nanometer line is 0.1-10mg, preferably 0.5-5mg,
Based on base material of the 1mg doped with scattering particles.
6. transparent electrode according to claim 5, wherein the diameter of metal nanometer line is 60-120nm, and length is 10-20 μ
m。
7. a kind of method for the transparent electrode for preparing any one of claim 1-6 comprising following steps:
(1) it by wherein doped with the base material dispersion of scattering particles on substrate, and is dried to scattering particles
Base material film；
(2) metal nanometer line dispersion liquid is coated on the base material film with scattering particles, forms metal nanowire thin-films, i.e.,
Metal nanometer line transparent electrode.
8. according to the method described in claim 7, wherein base material dispersion liquid is that base material passes through solvent or diluent
The concentration being configured to is 0.3-0.5mg/ml, the dispersion liquid specifically for 0.4mg/ml.
9. according to the method described in claim 8, wherein the scattering particles of different content are doped in base material dispersion liquid,
So that the content of scattering particles is 0-1mg, preferably 0.01-1mg, more preferable 0.1-0.8mg, spy in base material dispersion liquid
It is not 0.2-0.5mg, based on 1mg base material.
10. according to the method described in claim 7, wherein metal nanometer line dispersion liquid is that metal nanometer line passes through organic solvent
The concentration being configured to is the dispersion liquid of 1-6mg/ml, preferably 3-6mg/ml, more particularly 5mg/ml, and preferred organic solvent is
Alcohols, such as methanol, ethyl alcohol, more particularly ethyl alcohol.
11. method according to claim 9 or 10, wherein the repeatedly coating scattering with different content on substrate
The base material dispersion liquid of particle and the metal nanometer line dispersion liquid, so that the top layer of base material, middle layer or bottom tool
There are the scattering particles of different content and the metal nanometer line of different content, it is preferable that scattering particles are located at the top of base material
Layer, and metal nanometer line is located at the top surface of base material.
12. a kind of organic electroluminescence device, be disposed with from bottom to top substrate, first electrode, organic luminescence function layer,
Second electrode neutralizes the transparent electrode that the adjacent first electrode of substrate is any one of claim 1-7.
13. organic electronic device according to claim 12, wherein the organic luminescence function layer further comprises one layer
Or multilayer is selected from the layer of hole transmission layer, hole blocking layer, electronic barrier layer, electron transfer layer and electron injecting layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810209149.9A CN110277504A (en) | 2018-03-14 | 2018-03-14 | Transparent electrode and organic electroluminescence device comprising it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810209149.9A CN110277504A (en) | 2018-03-14 | 2018-03-14 | Transparent electrode and organic electroluminescence device comprising it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110277504A true CN110277504A (en) | 2019-09-24 |
Family
ID=67958369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810209149.9A Pending CN110277504A (en) | 2018-03-14 | 2018-03-14 | Transparent electrode and organic electroluminescence device comprising it |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110277504A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112736166A (en) * | 2019-10-14 | 2021-04-30 | 中国科学院金属研究所 | Manufacturing method of high-efficiency light-emitting diode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004084323A1 (en) * | 2003-03-19 | 2004-09-30 | Osram Opto Semiconductors Gmbh | Organic led with improved light efficiency |
| CN102527621A (en) * | 2011-12-27 | 2012-07-04 | 浙江科创新材料科技有限公司 | Preparation method for haze-adjustable flexible transparent conductive film |
| CN102569667A (en) * | 2011-01-31 | 2012-07-11 | 南京第壹有机光电有限公司 | Electroluminescent device with high efficiency luminescence |
| CN102834923A (en) * | 2009-12-04 | 2012-12-19 | 凯博瑞奥斯技术公司 | Nanostructure-based transparent conductors having increased haze and devices comprising the same |
| US20140356527A1 (en) * | 2013-06-04 | 2014-12-04 | Corning Precision Materials Co., Ltd. | Method of fabricating light-scattering substrate |
-
2018
- 2018-03-14 CN CN201810209149.9A patent/CN110277504A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004084323A1 (en) * | 2003-03-19 | 2004-09-30 | Osram Opto Semiconductors Gmbh | Organic led with improved light efficiency |
| CN102834923A (en) * | 2009-12-04 | 2012-12-19 | 凯博瑞奥斯技术公司 | Nanostructure-based transparent conductors having increased haze and devices comprising the same |
| CN102569667A (en) * | 2011-01-31 | 2012-07-11 | 南京第壹有机光电有限公司 | Electroluminescent device with high efficiency luminescence |
| CN102527621A (en) * | 2011-12-27 | 2012-07-04 | 浙江科创新材料科技有限公司 | Preparation method for haze-adjustable flexible transparent conductive film |
| US20140356527A1 (en) * | 2013-06-04 | 2014-12-04 | Corning Precision Materials Co., Ltd. | Method of fabricating light-scattering substrate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112736166A (en) * | 2019-10-14 | 2021-04-30 | 中国科学院金属研究所 | Manufacturing method of high-efficiency light-emitting diode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100511759C (en) | Organic light emitting device and manufacturing method thereof | |
| CN104321898B (en) | Substrate for organic electronic device | |
| CN104170113B (en) | Electroluminescent devices and applications thereof | |
| JP5658913B2 (en) | Organic electroluminescence device | |
| JP4723555B2 (en) | Electronic device manufacturing method and coating solution suitable for the manufacturing method | |
| Zang et al. | Organic–inorganic hybrid thin film light-emitting devices: interfacial engineering and device physics | |
| Yu et al. | Molding hemispherical microlens arrays on flexible substrates for highly efficient inverted quantum dot light emitting diodes | |
| TW201345013A (en) | Metal oxide charge transport material doped with organic molecules | |
| CN103943784A (en) | Organic light-emitting device | |
| TW201301612A (en) | Organic electroluminescence device | |
| CN103403912A (en) | Organic electronic device for lighting | |
| TWI506836B (en) | Transparent conducting film and organic light emitting device comprising the same | |
| CN104218154A (en) | Organic light emission diode device and fabrication method thereof | |
| Du et al. | Inkjet printing multilayer OLEDs with high efficiency based on the blurred interface | |
| CN101373816B (en) | Method for preparing organic electroluminescent device | |
| TW200915905A (en) | Luminescence device and manufacturing method thereof and illuminator | |
| CN102044633B (en) | Organic light-emitting device | |
| CN106848104A (en) | Top emission type luminescent device | |
| CN101540379A (en) | Method for producing organic electroluminescence device | |
| CN110277504A (en) | Transparent electrode and organic electroluminescence device comprising it | |
| CN104466010A (en) | Organic electroluminescence device and manufacturing method thereof | |
| CN102195004A (en) | Organic electroluminescence element and light-emitting apparatus having the same | |
| CN101989646B (en) | Flexible passive organic electroluminescent device and production method thereof | |
| US10651410B2 (en) | Organic light emitting device | |
| Wang et al. | Highly efficient green TADF organic light-emitting diodes by simultaneously manipulating hole and electron transport |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 214112 No. 210, Xinzhou Road, Wuxi, Jiangsu Applicant after: Jiangsu March Technology Co.,Ltd. Address before: 214112 No. 210, Xinzhou Road, Wuxi, Jiangsu Applicant before: JIANGSU SUNERA TECHNOLOGY Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190924 |