CN106450012A - Organic light-emitting device with double hole injection layers and preparation method of organic light-emitting device - Google Patents
Organic light-emitting device with double hole injection layers and preparation method of organic light-emitting device Download PDFInfo
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- H10K50/00—Organic light-emitting devices
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Abstract
The invention provides an organic light-emitting device with double hole injection layers and a preparation method of the organic light-emitting device. The device comprises a substrate, an anode, a metal oxide hole injection layer, a water-soluble hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode which are sequentially arranged from bottom to top. The metal oxide hole injection layer and the water-soluble hole injection layer are constructed in the organic light-emitting device by adopting a solution spin-coating method; the obtained organic light-emitting device is low in cost and also has relatively low drive voltage and relatively high current efficiency.
Description
Technical field
The invention belongs to organic light emitting diode device technical field is and in particular to the Organic Electricity of a kind of pair of hole injection layer
Electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device is because driving voltage is low, actively luminous, fast response time, all solidstate, wide viewing angle, low work(
The advantages of rate, low cost, cause the concern of high degree in terms of display with illumination.In the world electroluminescent organic material with
The extensive research and development of device start from late 1880s, C.W.Tang by U.S.'s Kodak Company in 1987 et al.
（Appl. Phys. Lett., 1987, 51: 913）Et al. invented the organic bilayer film electroluminescent cell of sandwich type
Part, indicates that organic electroluminescent technology enters and breeds the practical epoch.
The structure of organic electroluminescence device is generally：Matrix, anode, organic layer, negative electrode, send out to improve organic electroluminescence
The performance of optical device, can add some organic function layers, such as hole injection layer, hole transmission layer, electron injecting layer and electronics
Transport layer.After applying a forward voltage at negative and positive the two poles of the earth, hole is injected into emission layer from anode, and electronics injects transmitting from negative electrode
Layer, in emission layer, hole and electronics are compounded to form exciton, are will be along with luminous when exciton transits to ground state from excitation state
Phenomenon, as electroluminescent.
For the organic electroluminescence device of one efficient stable of preparation, design a kind of between electrode and luminescent layer
The electric charge injection layer of functional form is most important, and wherein, hole injection layer has played huge in terms of improving the balance of carrier
Effect.As a rule, good hole-injecting material needs to meet following requirement：（1）Possess suitable work content to allow sky
Injection from anode to luminescent layer for the cave and transmission；（2）Have high electrical conductivity to ensure low driving voltage；（3）Have preferably
The injection to improve hole for the Hole injection capacity；（4）Possess preferable electron-blocking capability to stop the leakage current of luminescent layer；
（5）Have preferable exciton blocking ability and the transmitting of exciton is limited in luminescent layer；（6）Have high in whole visible region
Optical transmittance etc..
1996, VanSlyke et al. reported and improves Organic Electricity using CuPc (CuPc) as hole injection layer
The injection of photoluminescence diode hole and the result of study (Appl.Phys.Lett. 1996,69 of working life: 2160)；
In the same year, Tokito et al. reports using molybdenum oxide (MoO3) as organic electroluminescent LED hole injection layer,
Find the MoO of suitable thickness3Hole injection layer can significantly reduce the driving voltage (J.Phys.D of organic electroluminescent LED
1996, 29: 2750)；
2006, Ikeda et al. reported using molybdenum oxide (MoO3) doping amine derivant (NPB) as organic electroluminescence
The hole injection layer of light emitting diode, finds that the hole injection layer of this doping can also effectively reduce organic electroluminescent two pole
The driving voltage (SID 06DIGEST P-185,923,2006) of pipe.
In traditional organic electroluminescence device, water-soluble hole-injecting material（For example：PEDOT:PSS）It is commonly used for
Come modified anode interface as hole injection layer, although having much excellent when water-soluble hole-injecting material is as hole injection layer
Point, as good in processability, transparency is high, electrical conductivity is high, and Hole injection capacity is strong etc., but its in terms of electricity with physical characteristic still
So there are some problems need to be solved, speciality meeting corroding electrode as acid in it, cause electrode interface to stablize sexual involution
(Adv.Mater, 2015, 27: 2930)；Such hole injection layer has poor electron-blocking capability, causes organic electroluminescence
The leakage current of light emitting device is larger, and device efficiency is relatively low（Opt. Express, 2015, 23: A625-A639）.
In order to solve this problem, the transition metal oxide of high work function, as cupric oxide CuOx, nickel oxide NiOx, oxidation
Molybdenum MoOx, vanadium oxide V2O5, tungsten oxide WO3, rheium oxide ReO3To replace water-soluble hole note etc. being used as hole injection layer
Enter material, these metal oxide source extensively, low cost, nontoxic it is easy to preparation, ohm can be formed at anodic interface and connect
Touch, improve hole injection and the stability at interface, these metal oxides have higher conduction level, can be effectively simultaneously
Stop electronics, improve combined efficiency in luminescent layer for the carrier, but these metal-oxide film surface defect states can lead to
Serious Exciton quenching effect (Chem.of.Mater, 2015,27:2532-2539), cause device light emitting efficiency relatively low.
Content of the invention
The technical problem solving：Present invention aim to address water-soluble hole-injecting material cause interface stability difference and
Metal oxide causes the technical problem of Exciton quenching effect, provide a kind of pair of hole injection layer organic electroluminescence device and
Its preparation method, the injection of carrier and transmission in this device more balances, and efficiency high, brightness height, low cost.
Technical scheme：The organic electroluminescence device of a kind of pair of hole injection layer, including the base setting gradually from the bottom to top
Piece, anode, metal oxide hole injection layer, water-soluble hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electricity
Sub- implanted layer and negative electrode.
Further, the material of described metal oxide hole injection layer can be cupric oxide CuOx, nickel oxide NiOx, oxygen
Change molybdenum MoOx, vanadium oxide V2O5, tungsten oxide WO3Or rheium oxide ReO3.
Further, the material of described water solubility hole injection layer is polymeric material.
Further, described polymeric material is PEDOT:PSS.
Further, described substrate is clear glass or flexible substrate.
Further, described anode layer can adopt inorganic conductive material or organic conductive polymer.
Further, described luminescent layer can be adulterated using organic molecule luminescent material, polymer luminescent material, dyestuff
Organic molecule luminescent material or polymer luminescent material.
Further, described electron injection and electron transfer layer can be using metal complex or the organic aromatic rings containing double bond N
Compound.
Further, described cathode layer can be using metal, alloy or metal fluoride and metal composite electrode.
The preparation method of the organic electroluminescence device of above-mentioned pair of hole injection layer, comprises the following steps：
Step 1, conductive substrate cleaning pretreatment；
Step 2, the preparation of metal oxide hole injection layer：Using solution processing method by metal oxide hole injection layer solution
It is spin-coated on anode layer surface；
Step 3, the preparation of water-soluble hole injection layer：Water-soluble hole injection layer solution is spin-coated on by gold using solution processing method
Belong to oxide hole injection layer surface；
Step 4, the preparation of luminescent layer：Luminescent layer solution is spin-coated on by water-soluble hole injection layer surface using solution processing method；
The preparation of step 5, electron injecting layer and electron transfer layer：Electron injecting layer and electric transmission are deposited with successively using vapour deposition method
Layer；
Step 6, the preparation of cathode layer：Using vapour deposition method, anode layer is deposited with electron injection layer surface.
Beneficial effect：The present invention adopts the lamination pair hole injection layers of metal oxide and water-soluble hole-injecting material,
Guaranteeing on the premise of anodic interface is stable, to improve the injectability in hole, suppressing metal oxide surface defect state to luminescent layer
Being quenched of middle exciton, the simultaneously effective electron leak electric current in blocking device, obtain the balance of carrier, and then improve Organic Electricity
The performance of electroluminescence device, gained organic electroluminescence device not only low cost, also have relatively low driving voltage with higher
Current efficiency.
Brief description
Fig. 1 is the structural representation of organic electroluminescence device in embodiment 1, and wherein 1 is transparent conduction base sheet, 2 is the
One electrode layer（Anode layer）, 3 be metal oxide hole injection layer, 4 be water-soluble hole injection layer, 5 be luminescent layer, 6 be electricity
Sub- transport layer, 7 be the second electrode lay（Cathode layer）, 8 be dc source；
Fig. 2（a）、（b）、（c）It is respectively CuO in embodiment 1xFilm, PEDOT:PSS film, CuOx/ PEDOT:PSS mixing is thin
The surface topography AFM figure of film；
Fig. 3（a）Current density voltage curve for device A, device B, device C in embodiment 1；
Fig. 3（b）Brightness-voltage curve for device A, device B, device C in embodiment 1；
Fig. 3（c）Current efficiency-voltage curve for device A, device B, device C in embodiment 1；
Fig. 4 is individual layer CuO in the embodiment of the present invention 1x, individual layer PEDOT:PSS, mixed layer CuOx/PEDOT:PSS respectively as
Single-electron device performance map during hole injection layer；
Fig. 5 is individual layer CuO in the embodiment of the present invention 1xFilm/luminescent layer, individual layer PEDOT:PSS/ luminescent layer, mixed layer CuOx/
PEDOT:The photoluminescence spectra figure of three samples of PSS/ luminescent layer；
Fig. 6（a）、（b）、（c）It is respectively individual layer NiO in embodiment 2xFilm, NiOx/PEDOT:PSS mixed film, individual layer
PEDOT:The surface topography AFM figure of PSS film
Fig. 7（a）、（b）、（c）It is respectively individual layer NiO in the embodiment of the present invention 2x, individual layer PEDOT:PSS, mixed layer NiOx/
PEDOT:PSS is respectively as current density voltage curve during hole injection layer, brightness-voltage curve, current efficiency-brightness
Curve, energy efficiency-brightness curve；
Fig. 8（a）、（b）It is respectively individual layer NiO in embodiment 2xFilm, individual layer PEDOT:PSS film, NiOx/PEDOT:PSS mixes
Close film as single hole during hole injection layer and single-electron device performance map.
Fig. 9 is individual layer NiO in embodiment 2xFilm/luminescent layer, individual layer PEDOT:PSS film/luminescent layer, mixed layer NiOx/
PEDOT:The photoluminescence spectra figure of three samples of PSS/ luminescent layer.
Specific embodiment
The invention provides the organic electroluminescence device of a kind of pair of hole injection layer, including set gradually from the bottom to top
Substrate, anode, metal oxide hole injection layer, water-soluble hole injection layer, hole transmission layer, luminescent layer, electron transfer layer,
Electron injecting layer and negative electrode.
According to structure above, the preparation process detailed embodiment in conjunction with device is described below：
(1) using hot ultrasonic detergent and deionized water ultrasonic method, transparent conduction base sheet ito glass is carried out, clearly
Place it in after washing and dry under infrared lamp, wherein the ito film above conductive substrate is as the anode layer of device, the side of ito film
Block resistance is 5～100 Ω, and thickness is 80～280 nm；
(2) metal oxide hole injection layer：The ito glass of above-mentioned cleaning, drying is placed on sol evenning machine, with the sky preparing
The solution spin-coating film of hole injection material；Control thickness by adjusting concentration, spin speed and the spin-coating time of solution, then
Make annealing treatment at moderate temperatures, the thickness of metal oxide hole injection layer is 10 ~ 30 nm；
(3) water-soluble hole injection layer：After the substrate cooling of metal oxide hole injection layer in spin coating, it is placed in sol evenning machine
On, the solution spin-coating film of the water-soluble hole-injecting material with preparing；By adjusting concentration, spin speed and the rotation of solution
The painting time controls thickness, then thermal anneal process at moderate temperatures, and the thickness of water-soluble hole injection layer is 20-60 nm；
(4) preparation of luminescent layer：By on the substrate sol evenning machine of hole injection layer water-soluble in spin coating, will prepare necessarily dense
The luminescent substance solution spin-coating film of degree, controls luminescent layer by adjusting concentration, spin speed and the spin-coating time of solution
Thickness, about 20-60 nm, it is dried at moderate temperatures；
(5) preparation of electron transfer layer：By in spin coating luminescent layer substrate be placed in vacuum evaporation within the chamber, one layer of evaporation is about
Thick electron injection/the transport layer of 80nm, evaporation rate is about 0.01 ~ 0.5 nm/s；
(6) preparation of electron injecting layer：The thick electron injecting layer of one layer of about 0.5 ~ 1.0 nm of evaporation；
(7) metal cathode layer：On the electric transmission/implanted layer being deposited with, the thick metal of one layer of about 80 nm of evaporation is as the moon
Pole, evaporation rate is about 0.2 nm/s；
(8) ready-made device is taken out from vacuum chamber, test the current-voltage-brightness characteristic of device under atmospheric environment
And electroluminescent spectrum.
Embodiment 1
Electroluminescent device is following structure：
Device A：ITO/CuOx/mCP:TAPC(30%):FIrpic(10%)/TmPyPb(60nm)/LiF(0.8nm)/Al
(80nm)；
Device B：ITO/PEDOT:PSS/mCP:TAPC(30%):FIrpic(10%)/TmPyPb(60nm)/LiF(0.8nm)/Al
(80 nm)；
Device C：ITO/CuOx/PEDOT:PSS/mCP:TAPC(30%):FIrpic(10%)/TmPyPb(60nm)/LiF(0.8
nm)/Al(80nm).
Wherein device A, B are respectively with metal oxide CuOx, water-soluble PEDOT:PSS is as hole injection layer, and device
Part C then adopts CuOx/PEDOT:Double hole injection layers of PSS.
（1）It is carved with the cleaning of the glass substrate of ITO in advance：Using the method pair that hot ultrasonic detergent and deionized water are ultrasonic
Transparent conduction base sheet ito glass is carried out, and places it in and dries under infrared lamp, wherein above conductive substrate after cleaning
As the anode layer of device, the square resistance of ito film is 30 Ω to ito film, and thickness is 120 nm；
(2) metal oxide hole injection layer：The ito glass of above-mentioned cleaning, drying is placed on sol evenning machine, with prepare
CuOxAcetic acid copper solution (4 mg/mL) spin-coating film；Spin speed is 4000rpm, and spin-coating time is 60s, metal oxide
CuOxThe thickness of hole injection layer, about 10-30nm, are dried 30min at 300 DEG C, such as Fig. 2（a）It is the CuO of spin coatingxThe surface of film
Pattern AFM schemes；
(3) water-soluble hole injection layer：By metal oxide CuO in spin coatingxAfter the substrate cooling of hole injection layer, it is placed in even
On glue machine, with the water-soluble hole-injecting material PEDOT buying:The original solution of PSS filters spin-coating film；Spin speed is
3000rpm, spin-coating time is 60s, then 20min is dried at 120 DEG C, water-soluble hole injection layer PEDOT:The thickness of PSS
Degree, about 40-60nm, such as Fig. 2（b）It is the PEDOT of spin coating:The surface topography AFM figure of PSS film, Fig. 2（c）Corresponding is double empty
Cave implanted layer CuOx/ PEDOT:The surface topography AFM figure of PSS film；
(4) preparation of luminescent layer：By hole-injecting material PEDOT water-soluble in spin coating:The substrate of PSS is placed in KW-4A spin coating
On machine, by solution (15 mg/mL) spin-coating film of the FIrpic preparing, spin speed is 1500rpm, spin-coating time 30s,
The thickness of luminescent layer, about 30-60 nm, it is vacuum dried 20min at 80 DEG C；
(5) preparation of electron injection/transport layer：After the substrate cooling of FIrpic in spin coating, it is placed in vacuum evaporation within the chamber,
Thick electron injection/transport layer TmPyPb of one layer of 60nm of evaporation, evaporation rate is about 0.01 ~ 0.5nm/s；
(6) cathode layer：Keep with the above that vacuum cavity pressure is constant, in electron injection/transport layer TmPyPb being deposited with, according to
As composite cathode, evaporation rate is about 0.2nm/s to the Al of the LiF and 80nm of secondary evaporation 0.8 nm；
(7) ready-made device is taken out from vacuum chamber, test the current-voltage-brightness characteristic of device under atmospheric environment
And electroluminescent spectrum.
With reference to Fig. 2（a）、（b）、（c）, ITO/CuOxSurface roughness maximum, ITO/PEDOT:The surface of PSS light
Slide it is notable that working as in CuOxUpper introducing PEDOT:The roughness on surface is not affected after PSS, it can be found that ITO/
CuOx/PEDOT:The surface roughness of PSS and ITO/PEDOT:PSS's is almost close.
The current density voltage curve of the device A in the present embodiment 1, device B, with device C, luminance voltage curve,
Current efficiency-voltage curve is respectively as Fig. 3（a）、（b）、（c）Shown it can be seen that adopting CuOx/PEDOT:PSS's is double empty
The high-high brightness of device C of cave implanted layer and maximum current efficiency respectively reach 17180 cd/m2,28.6 cd/A.All than device
Part A（With CuOxAs hole injection layer）With device B（With PEDOT:PSS is as hole injection layer）High-high brightness and maximum effect
Rate high it can be seen that, introduce the performance that double hole injection layers can effectively improve device.
With reference to the single-electron device I-E characteristic of Fig. 4, device architecture is respectively：
Device D：ITO/CuOx/TmPyPb(80 nm)/LiF(1.2 nm)/Al(80 nm)
Device E：ITO/PEDOT:PSS/TmPyPb(80 nm)/LiF(1.2 nm)/Al(80 nm)
Device F：ITO/CuOx/PEDOT:PSS/TmPyPb(80 nm)/LiF(1.2 nm)/Al(80 nm)
It can be found that：PEDOT:The stop electronic capability of PSS is worst, CuOxStop electronic capability stronger, observe mixed
Close layer CuOx/PEDOT:Single hole of PSS and single-electron device are it is found that it effectively improves PEDOT:PSS stops electricity
The shortcoming of sub- ability.
Electroluminescent light spectrogram with reference to Fig. 5 can be found that：CuOxLarger to being quenched of exciton, and PEDOT:PSS is to sharp
Sub is quenched very little, mixed layer CuOx/PEDOT:PSS then effectively improves CuOxThe shortcoming big to Exciton quenching.
Embodiment 2
Electroluminescent device is following structure：
Device G：ITO/NiOx/ TCTA:26DCzPPy (3:7):FIrpic(10%)/TmPyPb(60nm)/LiF(0.8nm)/
Al(80nm)；
Device H：ITO/PEDOT:PSS/ TCTA:26DCzPPy(3:7):FIrpic(10%)/TmPyPb(60nm)/LiF
(0.8nm)/Al(80 nm);
Device I：ITO/NiOx/PEDOT:PSS/ TCTA:26DCzPPy (3:7):FIrpic(10%)/TmPyPb(60nm)/
LiF(0.8 nm)/Al(80nm)；
Wherein device G, H are respectively with metal oxide NiOx, water-soluble PEDOT:PSS is as hole injection layer, and device I is then
Using NiOx/PEDOT:Double hole injection layers of PSS.
For metal oxide hole injection layer, it is that the ito glass of above-mentioned cleaning, drying is placed on sol evenning machine, with preparing
Nickel acetate solution (5 mg/mL) spin-coating film of good NiOx；Spin speed is 3000 rpm, and spin-coating time is 60 s, metal
The thickness of oxide NiOx hole injection layer, about 10 nm, thermal anneal process 30 min at 380 DEG C, the system of other each functional layers
Standby condition and method all with examples of implementation 1 in as.
With reference to 6（a）、（b）、（c）, ITO/ NiOxSurface roughness maximum, ITO/PEDOT:The surface of PSS is the most smooth,
It should be noted that in the same manner as in Example 1, when in NiOxUpper introducing PEDOT:The roughness on surface is not affected after PSS, permissible
Find ITO/NiOx/PEDOT:The surface roughness of PSS and ITO/PEDOT:PSS's is almost close.
Individual layer NiO in the present embodiment 2x, individual layer PEDOT:PSS, and mixed layer NiOx/PEDOT:PSS is respectively as sky
The current density voltage curve during implanted layer of cave, brightness-voltage curve, current efficiency-brightness curve, energy efficiency-brightness is bent
Line is respectively Fig. 7（a）、（b）、（c）、（d）Shown, still as can be seen that adopting NiOx/PEDOT:Double hole injection layers of PSS
The performance of device be best, compare and PEDOT:PSS device, its high-high brightness and maximum current efficiency are respectively from 23.6
Cd/A, 13.2 lm/W bring up to 30.5 cd/A and 18.5 lm/W.Therefore double-decker part is improved to OLEDs device performance
Arrive important function.
With reference to Fig. 8（a）Single hole Device current-voltage characteristic, device architecture is respectively：
Device J：ITO/NiOx/NPB(85 nm)/Al(80 nm)
Device K：ITO/NiOx/PEDOT:PSS/NPB(85 nm)/Al(80 nm)
Device L：ITO/PEDOT:PSS/NPB(85 nm)/Al(80 nm)
It can be found that：NiOxFilm contributes positively to the injection in hole it is contemplated that its band gap width is 3.6ev, and has higher
Carrier mobility, according to uncertainty principle, meeting can banding pattern transport condition.And NiOx/PEDOT:Double holes injection of PSS
Layer also embodies with respect to PEDOT:PSS injection more advantage.
With reference to Fig. 8（b）Single-electron device I-E characteristic, device architecture is respectively：
Device M：ITO/ NiOx/TmPyPb(80 nm)/LiF(0.8 nm)/Al(80 nm)
Device N：ITO/ NiOx/ PEDOT:PSS/TmPyPb(80 nm)/LiF(0.8 nm)/Al(80 nm)
Device O：ITO/ PEDOT:PSS/TmPyPb(80 nm)/LiF(0.8 nm)/Al(80 nm)
It can be found that：PEDOT:PSS shows higher current density, and this shows：PEDOT:The stop electronic capability of PSS is
Difference, and make electronics easily propagate through organic layer and bury in oblivion to anode, and mixed layer NiOx/PEDOT:PSS then embodies relatively
Good electron-blocking capability, effectively stops electronics and passes through anode, it effectively improves PEDOT:PSS stops electronic capability
The shortcoming of difference.
Electroluminescent light spectrogram with reference to Fig. 9 can be found that：NiOxLarger to being quenched of exciton, and PEDOT:PSS is to sharp
Sub is quenched very little, mixed layer NiOx/PEDOT:PSS then effectively improves NiOxThe shortcoming big to Exciton quenching.
Claims (10)
1. a kind of pair of hole injection layer organic electroluminescence device it is characterised in that：Including the base setting gradually from the bottom to top
Piece, anode, metal oxide hole injection layer, water-soluble hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electricity
Sub- implanted layer and negative electrode.
2. according to claim 1 pair of hole injection layer organic electroluminescence device it is characterised in that：Described metal oxygen
The material of compound hole injection layer can be cupric oxide CuOx, nickel oxide NiOx, molybdenum oxide MoOx, vanadium oxide V2O5, tungsten oxide WO3
Or rheium oxide ReO3.
3. according to claim 1 pair of hole injection layer organic electroluminescence device it is characterised in that：Described water solubility
The material of hole injection layer is polymeric material.
4. according to claim 3 pair of hole injection layer organic electroluminescence device it is characterised in that：Described polymer
Material is PEDOT:PSS.
5. according to claim 1 pair of hole injection layer organic electroluminescence device it is characterised in that：Described substrate is
Clear glass or flexible substrate.
6. according to claim 1 pair of hole injection layer organic electroluminescence device it is characterised in that：Described anode layer
Inorganic conductive material or organic conductive polymer can be adopted.
7. according to claim 1 pair of hole injection layer organic electroluminescence device it is characterised in that：Described luminescent layer
Can be using organic molecule luminescent material, polymer luminescent material, the organic molecule luminescent material of dyestuff doping or polymer
Luminescent material.
8. according to claim 1 pair of hole injection layer organic electroluminescence device it is characterised in that：Described electronics note
Entering can be using metal complex or the organic aromatic compound containing double bond N with electron transfer layer.
9. according to claim 1 pair of hole injection layer organic electroluminescence device it is characterised in that：Described cathode layer
Can be using metal, alloy or metal fluoride and metal composite electrode.
10. the organic electroluminescence device of double hole injection layers described in claim 1 preparation method it is characterised in that：Bag
Include following steps：
Step 1, conductive substrate cleaning pretreatment；
Step 2, the preparation of metal oxide hole injection layer：Using solution processing method by metal oxide hole injection layer solution
It is spin-coated on anode layer surface；
Step 3, the preparation of water-soluble hole injection layer：Water-soluble hole injection layer solution is spin-coated on by gold using solution processing method
Belong to oxide hole injection layer surface；
Step 4, the preparation of luminescent layer：Luminescent layer solution is spin-coated on by water-soluble hole injection layer surface using solution processing method；
The preparation of step 5, electron injecting layer and electron transfer layer：Electron injecting layer and electric transmission are deposited with successively using vapour deposition method
Layer；
Step 6, the preparation of cathode layer：Using vapour deposition method, anode layer is deposited with electron injection layer surface.
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