CN102468444B - A kind of organic electroluminescence device and preparation method thereof - Google Patents
A kind of organic electroluminescence device and preparation method thereof Download PDFInfo
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- CN102468444B CN102468444B CN201010546354.8A CN201010546354A CN102468444B CN 102468444 B CN102468444 B CN 102468444B CN 201010546354 A CN201010546354 A CN 201010546354A CN 102468444 B CN102468444 B CN 102468444B
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Abstract
The invention discloses a kind of organic electroluminescence device and preparation method thereof, comprising: a substrate; One anode, it is combined in one of described substrate on the surface; One light scattering layer, it is combined on the described anode surface relative with described substrate; One organic electroluminescence structure, it is combined on the described light scattering layer surface relative with described anode; One negative electrode, it is combined on the described organic electroluminescence structure surface relative with described light scattering layer.Organic electroluminescence device of the present invention has additional light scattering layer in its structure, make organic electroluminescence device send light there is total reflection at this light scattering layer interface, thus significantly enhance luminosity and the efficiency of organic electroluminescence device of the present invention; Light scattering layer can also effectively make light, at its interface, scattering effect occur, thus further enhancing organic electroluminescence device luminosity of the present invention and efficiency; This organic electroluminescence device preparation method operation is simple, improves production efficiency, is suitable for suitability for industrialized production.
Description
Technical field
The invention belongs to electric light source technology field, relate to a kind of organic electroluminescence device and preparation method thereof specifically.
Background technology
Electric light source industry is the focus that countries in the world are competitively studied always, in occupation of very important status in World Economics.Now widely used light source is glow discharge spot lamp, and the principle of this light source is that the inside of lamp is filled with mercurous mist after vacuumizing, and utilizes the ultraviolet excitation light-emitting phosphor that gas discharge luminescence or gas discharge produce.But the pulse color break-up of glow discharge spot lamp easily causes people's visual fatigue, and mercury pollution environment, along with society and scientific and technological progress, the green light source researching and developing energy-conservation environmental protection again carrys out alternative conventional light source, becomes the important topic that various countries are competitively studied.
Organic electroluminescence device is the one in electric light source.1987, C.W.Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.Ultrathin film technology is utilized to prepare high brightness, high efficiency double-deck Small molecular organic electroluminescence device (OLED).In this double-deck device, under 10V, brightness reaches 1000cd/m
2, its luminous efficiency is 1.51lm/W, the life-span is greater than 100 hours.Nineteen ninety, the people such as univ cambridge uk Burronghes propose to make polymer electroluminescence (EL) device with macromolecule conjugated polymer polyphenylene ethylene (PPV) first, subsequently, the experimental group of California university professor Heeger leader confirmed polymer electroluminescence characteristic further in 1991, and improved.From then on the research of organic luminescent device opens a brand-new field-polymer electroluminescent device (PLED).Since then, Organic Light Emitting Diode obtains and develops rapidly within the short more than ten years.
OLED can be divided into bottom emitting type and top emission type by the taking-up mode by light, only taking out from top of top emission type organic electroluminescence device, reach maximum to make the extraction efficiency of light, therefore device generally adopts metal that reflectivity is higher as bottom reflection mirror, top then for ease of light take out transparent or half transflective electrode, but, because part light is transmitted into bottom, always there is certain bottom emergent light loss, mainly caused owing to reflecting.Therefore, how reducing the refraction of light and strengthen the reflection of light, is current urgent problem.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of luminosity and the high organic electroluminescence device of efficiency are provided;
And, the preparation method of above-mentioned organic electroluminescence device.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of organic electroluminescence device, comprising:
One substrate;
One anode, it is combined on a surface of described substrate;
One light scattering layer, it is combined on the surface relative with described substrate of described anode;
One organic electroluminescence structure, it is combined on the surface relative with described anode of described light scattering layer;
One negative electrode, it is combined on the surface relative with described light scattering layer of described organic electroluminescence structure.
And a kind of organic electroluminescence device preparation method, comprises the steps:
Substrate is provided;
Plate anode on the substrate;
At the plated surface light scattering layer relative with described substrate of described anode;
At the plated surface organic electroluminescence structure relative with described anode of described light scattering layer;
At the plated surface negative electrode relative with described light scattering layer of described organic electroluminescence structure, obtain described organic electroluminescence device.
Organic electroluminescence device of the present invention has additional light scattering layer in its structure, this light scattering layer can effectively reduce organic electroluminescence device send the critical angle of the total reflection of light, after light scattering layer is combined with anode, the light generation refraction effect at remarkable this light scattering layer interface of minimizing directive, make organic electroluminescence device send light this light scattering layer interface occur total reflection, the light of generation total reflection is returned penetrate from the exiting surface on organic electroluminescence device top, thus significantly enhance luminosity and the efficiency of organic electroluminescence device of the present invention, simultaneously, light scattering layer can also effectively make light, at its interface, scattering effect occur, the light of further this light scattering layer of minimizing directive reflects, improve the recovery rate to light, thus further enhancing organic electroluminescence device luminosity of the present invention and efficiency.This organic electroluminescence device preparation method operation is simple, improves production efficiency, reduces production cost, be suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of organic electroluminescence device of the embodiment of the present invention;
Fig. 2 is the another kind of structural representation of organic electroluminescence device of the embodiment of the present invention;
Fig. 3 is the schematic diagram of the light that sends of the organic electroluminescence device of the embodiment of the present invention in light scattering layer generation total reflection;
Fig. 4 does not arrange the schematic diagram that the light scattering layer time, reflection and refraction occurred in anodic interface in organic electroluminescence device structure;
Fig. 5 is the schematic flow sheet of the organic electroluminescence device preparation method of the embodiment of the present invention;
Fig. 6 be the embodiment of the present invention 1 prepare organic electroluminescence device (its structure is: simple glass/Ag/TiO
2/ MoO
3/ TPD/AlQ
3/ PBD/LiF/Ag) and do not add TiO
2light scattering layer 3 structure organic electroluminescence device (its structure is: simple glass/Ag/MoO
3/ TPD/AlQ
3/ PBD/LiF/Ag) brightness and voltage relationship figure.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Under the principle of luminosity of embodiment of the present invention organic electroluminescence device (OLED) is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.When the light directive substrate sent, light can in substrate or/and the anodic interface be combined with substrate occurs to reflect and reflect, the light that refraction occurs causes organic electroluminescence device to penetrate the loss of light, and the light that reflection occurs reflexes to the exiting surface injection on organic electroluminescence device top, can strengthen organic electroluminescence device send light get optical efficiency.Therefore, change the interfacial characteristics that refraction occurs light, after making former this interface of generation refract light directive, total reflection or reflection occur, thus can strengthen further organic electroluminescence device send light get optical efficiency.
The embodiment of the present invention provides a kind of luminosity and the high organic electroluminescence device of efficiency according to above-mentioned principle.As shown in Figure 1, 2, it comprises a substrate 1; One anode 2, it is combined in one of substrate 1 on the surface; One light scattering layer 3, it is combined on the surface relative with substrate 1 of anode 2; One organic electroluminescence structure 4, it is combined on the surface relative with anode 2 of light scattering layer 3; One negative electrode 5, it is combined on the surface relative with light scattering layer 3 of organic electroluminescence structure 4.Like this, embodiment of the present invention organic electroluminescence device has additional light scattering layer 3 in its structure, this light scattering layer 3 can effectively reduce organic electroluminescence device send the critical angle of the total reflection of light, after light scattering layer 3 is combined with anode 2, the light generation refraction effect at this light scattering layer 3 interface of remarkable minimizing directive, make organic electroluminescence device send light this light scattering layer 3 interface occur total reflection, the light that total reflection occurs returns and penetrates from the exiting surface on organic electroluminescence device top, thus significantly enhance luminosity and the efficiency of organic electroluminescence device of the present invention, simultaneously, light scattering layer 3 can also effectively make light, at its interface, scattering effect occur, the light of further this light scattering layer 3 of minimizing directive reflects, improve the recovery rate to light, thus further enhancing organic electroluminescence device luminosity of the present invention and efficiency.
Particularly, the material of above-mentioned substrate 1 is preferably indium tin oxide (ITO) glass, mixes tin oxide (FTO) glass of fluorine, mixes zinc oxide (AZO) glass of aluminium, mixes zinc oxide (IZO) glass of indium, simple glass or quartz.Wherein, glass is as simple glass etc., and substrate 1 is not particularly limited, and as substrate conventional thickness in this area can be adopted all can to realize, the existence of this substrate 1 effectively can improve the mechanical strength of organic electroluminescence device of the present invention.The material of anode 2 is preferably gold (Au), silver (Ag) or aluminium (Al), and its thickness is preferably 40 ~ 80nm; The material of negative electrode 5 is preferably gold (Au), silver (Ag), platinum (Pt) or aluminium (Al) its thickness and is preferably 10 ~ 30nm.This material is as anode 2 and negative electrode 5, the resistance of electrode can be effectively reduced, reduce the heat release of electrode and the heat dispersion of intensifier electrode, wherein, anode 2 effectively can also play the effect of mirror-reflection, by a small amount of place of appearing being reflexed to organic electroluminescence device by light scattering layer 3 light, its thickness can also effectively reduce the permeability of light, effect stops penetrating of light, and light is reflexed to negative electrode 5, thus strengthen luminous intensity and the brightness of the present embodiment organic electroluminescence device, therefore, this anode 2 is also referred to as reflecting electrode; Negative electrode 5 effectively can also form exiting surface, and the light injection that organic electroluminescence device is sent, negative electrode 2 can effectively ensure penetrating of light, also referred to as transparency electrode.
Particularly, the material of above-mentioned light scattering layer 3 is preferably TiO
2, ZnO, MgO, CaO or Al
2o
3, the material of this light scattering layer 3 is preferably stratum granulosum structure, and this grain diameter is preferably 20 ~ 200nm.Light scattering layer 3 thickness is preferably 50 ~ 200nm.The light scattering layer 3 of this material and thickness effectively can increase the refractive index n to light, corresponding reduction is to the critical angle β of light generation total reflection, thus there is refraction effect at light scattering layer 3 interface in the light reducing directive light scattering layer 3, increase light, at light scattering layer 3 interface, reflex occurs, thus the loss reducing time that refraction occurs and cause.Such as, when the material of light scattering layer 3 is TiO
2time, as shown in Figure 3, due to TiO
2refractive index (n=2.5 ~ 2.7), according to formula sin β=l/n, (β is that full critical angle of launching occurs light, n is refractive index), when n increases, the critical angle β of light generation total reflection is relatively little, therefore, when incidence angle θ is greater than critical angle β, then can there is total reflection phenomenon in more light, and the refraction loss of light just greatly reducing, light extraction efficiency increases, and directly shows that the luminance and efficiency of device is significantly improved.Meanwhile, due to nano level TiO
2be granular, specific area is comparatively large, can well carry out the scattering of light, improves the recovery rate of light further.
If when not arranging light scattering layer 3 in organic electroluminescence device structure, when light directive anode 2 interface, because the refractive index n of anode layer 2 is relatively little, just cause critical angle β less.When the incidence angle θ of the incident light at directive anode 2 interface is less than critical angle β, will there is refraction effect at anode 2 interface in incident light, as shown in Figure 4, its refraction angle is α.
Particularly, above-mentioned organic electroluminescence structure 4 comprises luminescent layer; Preferably there is between this luminescent layer and light scattering layer at least one in hole injection layer, hole transmission layer, and/or preferably there is between described luminescent layer and negative electrode at least one in electron transfer layer, electron injecting layer.Therefore, organic electroluminescence structure 4 preferably has following structure: organic electroluminescence structure 4 comprises the hole injection layer 41, hole transmission layer 42, luminescent layer 43, electron transfer layer 44 and the electron injecting layer 45 that combine successively, wherein, this hole injection layer 41 is combined on the surface relative with anode 2 of above-mentioned light scattering layer 3, this electron injecting layer 45 is combined with above-mentioned negative electrode 5, as shown in Figure 1; Or above-mentioned organic electroluminescence structure 4 only comprises luminescent layer 43, this luminescent layer 43 one side is combined with negative electrode 5, and relative another side is combined with light scattering layer 3; Or comprise the electron transfer layer 44, luminescent layer 43, hole transmission layer 42, the hole injection layer 41 that combine successively, this electron transfer layer 44 is combined with negative electrode 5, and hole injection layer 41 is combined with light scattering layer 3; Or comprise the luminescent layer 43, the hole transmission layer 42 that combine successively, this luminescent layer 43 is combined with negative electrode, and hole transmission layer 42 is combined with light scattering layer 3; Or comprise the luminescent layer 43, hole transmission layer 42, the hole injection layer 41 that combine successively, this luminescent layer 43 is combined with negative electrode 5, and hole injection layer 41 is combined with light scattering layer 3, shown in Fig. 2; Or comprise the electron transfer layer 44, luminescent layer 43, the hole injection layer 41 that combine successively, this electron transfer layer 44 is combined with negative electrode 5, and hole injection layer 41 is combined with light scattering layer 3.The organic electroluminescence structure 3 of these Rotating fields also can realize the organic electroluminescence device of the present embodiment.Because organic electroluminescence device is in luminescence process, the transmission rate of hole and electronics is inconsistent, and the recombination probability that often result in electron-hole is on the low side, and the brightness of organic electroluminescence device and efficiency can not get improving.Therefore, the setting of this hole injection layer 41, hole transmission layer 42, luminescent layer 43, electron transfer layer 44 and electron injecting layer 45, the injection in effective adjustment electronics and hole and transmission rate, equilibrium carrier, control recombination region, to obtain desirable luminosity and luminous efficiency, simultaneously, also make embodiment of the present invention organic electroluminescence device not only ensure that organic function layer and the good adhesion between electrode 5 and light scattering layer 3, but also make that the charge carrier from anode and metallic cathode is easier to be injected in organic functional thin film.Such as, hole injection layer 41 is preferably transition metal oxide, this material and organic cavity transmission layer 42 energy level comparison match, the hole of anode 2 is injected and obtains obvious reinforcement, the injection in effective adjustment electronics and hole and transmission rate, equilibrium carrier, controls recombination region, makes embodiment of the present invention organic electroluminescence device obtain desirable luminosity and luminous efficiency.
Further, the thickness of hole injection layer 41 is preferably 20 ~ 80nm, and its material is preferably transition metal oxide, is more preferably MoO
3, WO
3, VO
xor WO
x.Hole transmission layer 42 thickness is preferably 20 ~ 80nm, that its material is preferably hole transmission layer employing is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (TPD), 1,3,5-triphenylbenzene (TDAPB), CuPc CuPc or P type doping inorganic semiconductor.The thickness of luminescent layer 43 is preferably 20 ~ 80nm, its material is preferably four-tert-butyl group perylene (TBP), 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9, 10-bis--β-naphthylene anthracene (AND), two (2-methyl-oxine)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-isopropyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTI), at least one in dimethylquinacridone (DMQA) or oxine aluminium (Alq3).The thickness of electron transfer layer 44 is preferably 20 ~ 80nm, its material is preferably 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq3), 2,5-(1-naphthyl)-1,3,4-diazole (BND), 1, at least one in 2,4-triazole derivative (as TAZ etc.), N-aryl benzimidazole (TPBI), quinoxaline derivant (TPQ) or N-shaped doping inorganic semiconductor.The thickness of electron injecting layer 45 is preferably 20 ~ 80nm, and its material is preferably LiO
2, Cs
2o, Al
2o
3, LiBO
2, K
2siO
3, chloride or alkali earth metal fluoride, wherein, alkali earth metal fluoride can be NaF, CsF, CaF
2, MgF
2, LiF, chloride can be NaCl, KCl, RbCl.
The embodiment of the present invention additionally provides the preparation method of above-mentioned organic electroluminescence device according to above-mentioned principle, and the method process chart is as Fig. 5 so show, simultaneously see Fig. 1 or 2, the method comprises the steps:
S1., substrate 1 is provided;
S2. anode 2 is plated on the surface in one of substrate 1;
S3. light-plated scattering layer 3 on the surface that anode 2 is relative with substrate 1;
S4. on the surface that light scattering layer 3 is relative with anode 2, organic electroluminescence structure 4 is plated;
S5. on the surface that organic electroluminescence structure 4 is relative with light scattering layer 3, plate negative electrode 5, obtain described organic electroluminescence device.
Particularly, in the S1 step of above-mentioned organic electroluminescence device preparation method, the structure of substrate 1, material and specification are described above, in order to length, do not repeat them here.This substrate 1 also comprises its pre-process, and this pre-process mode comprises cleaning, oxygen plasma treatment etc.Wherein, cleaning way preferably uses each ultrasonic 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively, thoroughly to remove the foreign matter on conductive substrates 1 surface, makes conductive substrates 1 surface farthest clean; Conductive substrates 1 is after clean, carry out oxygen plasma treatment again, the time of this oxygen plasma treatment oxygen plasma treatment is preferably 5-15min, power is preferably 10-50W, its Main Function is the roughness and the contact angle that reduce conductive glass surface, be beneficial to wettability and the adsorptivity of improving conductive glass surface, and by the organic pollution on its surface can be removed after surface treatment further.The preparation method of this conductive substrates 1 plates one deck conductive layer 12 on the surface at substrate 11, and the mode of plating conductive layer 12 comprises the modes such as evaporation, sputtering or spraying plating.Wherein, substrate 11 preferably carries out aforesaid pre-process, as clean and oxygen plasma treatment.
In the S2 step of above-mentioned organic electroluminescence device preparation method, the mode of plating anode 2 is preferably evaporation, sputtering or spraying plating.The material of anode 2 and the thickness of plating, to set forth hereinbefore, do not repeat them here.
In the S3 step of above-mentioned organic electroluminescence device preparation method, the mode of light-plated scattering layer 3 is preferably evaporation, sputtering or spraying plating.The material of light scattering layer 3 and the thickness of plating are set forth hereinbefore, do not repeat them here.
In the S4 step of above-mentioned organic electroluminescence device preparation method, the mode of plating organic electroluminescence structure 4 is preferably evaporation, sputtering, spraying plating or chemical deposition mode.As when this organic electroluminescence structure 3 preferably comprises the hole injection layer 41, hole transmission layer 42, luminescent layer 43, electron transfer layer 44 and the electron injecting layer 45 that combine successively, adopt evaporation, sputtering, spraying plating or chemical deposition mode on anode 2, plate hole injection layer 41, hole transmission layer 42, luminescent layer 43, electron transfer layer 44 and electron injecting layer 45 successively.Wherein, evaporation, sputtering, spraying plating or chemical deposition mode any one all can form above-mentioned hole injection layer 41, hole transmission layer 42, luminescent layer 43, electron transfer layer 44 and electron injecting layer 45.The situations such as the structure of organic electroluminescence structure 4, to set forth hereinbefore, do not repeat them here.
In the S5 step of above-mentioned organic electroluminescence device preparation method, the mode of plating negative electrode 5 is as the mode of plating anode 2, and the thickness material of negative electrode 5 is described above.
The preparation of this organic electroluminescence device only needs in conductive substrates 1, plate each Rotating fields successively just can obtain final products, and method operation is simple, improves production efficiency, reduces production cost, be suitable for suitability for industrialized production.
Now in conjunction with instantiation, the present invention is further elaborated.
Embodiment 1
The organic electroluminescence device structure of the present embodiment as shown in Figure 1, this organic electroluminescence device comprise combine successively substrate 1, anode 2, light scattering layer 3, hole injection layer 41, hole transmission layer 42, luminescent layer 43, electron transfer layer 44 and electron injecting layer 45 and negative electrode 5.Wherein, substrate 1 be the simple glass of 200nm thick (lower with), anode 2 is the Ag layer that 40nm is thick, light scattering layer 3 for thickness be 100nm, particle diameter is the TiO of 20nm
2layer, hole injection layer 41 is the MoO that 10nm is thick
3layer, hole transmission layer 42 is the TPD layer that 40nm is thick, and luminescent layer 43 is the AlQ that 70nm is thick
3layer, electron transfer layer 44 is the PBD layer that 50nm is thick, and electron injecting layer 45 is the LiF layer that 50nm is thick, and negative electrode 5 is the Ag layer that 20nm is thick.
Its preparation method is as follows:
(1) simple glass is carried out photoetching treatment, be cut into required light-emitting area, then each ultrasonic 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol is used successively, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 15min, and power is 10W, to reduce roughness and the contact angle of conductive glass surface, improve wettability and the adsorptivity on its surface, remove the organic pollution of conductive glass surface, obtained substrate 1;
(2) obtained substrate 1 is put into inside vacuum film coating chamber carry out vacuum moulding machine layer of metal Ag, as anode 2;
(3) sputter at metal A g outer surface the TiO that one deck particle diameter is 20nm
2layer, as light scattering layer 3;
(4) evaporation is adopted to plate MoO successively at light scattering layer 3 outer surface
3layer 41, TPD layer 42, AlQ
3layer 43, PBD layer 44, LiF layer 45, form organic electroluminescence structure 4;
(5) at LiF layer 45 outer surface evaporation layer of metal Ag layer, as negative electrode 5, thus described organic electroluminescence device is obtained.
(its structure is the organic electroluminescence device prepared of the present embodiment: simple glass/Ag/TiO
2/ MoO
3/ TPD/AlQ
3/ PBD/LiF/Ag) and do not add TiO
2light scattering layer 3 structure organic electroluminescence device (its structure is: simple glass/Ag/MoO
3/ TPD/AlQ
3/ PBD/LiF/Ag) brightness and voltage relationship as shown in Figure 6.
As seen from Figure 6, the present embodiment is prepared the cut-in voltage of organic electroluminescence device and current density and is obtained for and significantly improves.At voltage after 7V, the current density that the current density that the present embodiment prepares organic electroluminescence device does not add the existing organic electroluminescence device of light scattering layer 3 relatively obtains significant raising.Also can draw thus, the present embodiment prepares the luminosity of organic electroluminescence device and efficiency is high is significantly improved.
Embodiment 2
The organic electroluminescence device structure of the present embodiment is as shown in embodiment 1 and Fig. 1.Its preparation method is as follows:
(1) simple glass is carried out photoetching treatment, be cut into required light-emitting area, then each ultrasonic 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol is used successively, clean up and rear oxygen plasma treatment is carried out to it, the oxygen plasma treatment time is 15min, power is 10W, obtained substrate 1;
(2) obtained substrate 1 is put into inside vacuum film coating chamber and carry out the thick metal A g of vacuum moulding machine one deck 50nm, as anode 2;
(3) sputter at metal A g outer surface that one deck particle diameter is 20nm, thickness is the TiO of 50nm
2layer, as light scattering layer 3;
(4) evaporation is adopted to plate the thick MoO of 20nm successively at light scattering layer 3 outer surface
3the AlQ that the NPB layer 42,20nm that layer 41,20nm is thick is thick
3the LiF layer 45 that the PBD layer 44,20nm that layer 43,20nm is thick is thick, forms organic electroluminescence structure 4;
(5) at the metal A g layer that LiF layer 45 outer surface evaporation one deck 10nm is thick, as negative electrode 5, thus described organic electroluminescence device is obtained.
Organic electroluminescence device performance prepared by test the present embodiment is similar to organic electroluminescence device performance prepared by embodiment 1.
Embodiment 3
The organic electroluminescence device structure of the present embodiment is as shown in embodiment 1 and Fig. 1.Its preparation method is as follows:
(1) simple glass is carried out photoetching treatment, be cut into required light-emitting area, then each ultrasonic 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol is used successively, clean up and rear oxygen plasma treatment is carried out to it, the oxygen plasma treatment time is 15min, power is 10W, obtained substrate 1;
(2) by metal A g thick for obtained substrate 1 one side sputtering one deck 60nm, as anode 2;
(3) metal A g outer surface spraying plating one deck particle diameter be 200nm, thickness is the MgO layer of 200nm, as light scattering layer 3;
(4) evaporation is adopted to plate the thick MoO of 20nm successively at light scattering layer 3 outer surface
3the K that the TPQ layer 44,20nm that the DCJTB layer 43,20nm that the TDAPB layer 42,20nm that layer 41,20nm is thick is thick is thick is thick
2siO
3layer 45, forms organic electroluminescence structure 4;
(5) at K
2siO
3the metal A u layer that layer 45 outer surface evaporation one deck 15nm are thick, as negative electrode 5, thus obtains described organic electroluminescence device.
Organic electroluminescence device performance prepared by test the present embodiment is similar to organic electroluminescence device performance prepared by embodiment 1.
Embodiment 4
The organic electroluminescence device structure of the present embodiment is as shown in embodiment 1 and Fig. 1.Its preparation method is as follows:
(1) simple glass is carried out photoetching treatment, be cut into required light-emitting area, then use each ultrasonic 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively, clean up rear drying, obtained substrate 1;
(2) obtained substrate 1 is put into inside vacuum film coating chamber and carry out the thick metal A g of vacuum moulding machine one deck 80nm, as anode 2;
(3) metal A g outer surface spraying plating one deck particle diameter be 100nm, thickness is the MgO layer of 200nm, as light scattering layer 3;
(4) spraying plating is adopted to plate the thick MoO of 80nm successively at light scattering layer 3 outer surface
xthe Al that the TPQ layer 44,60nm that the DCJTB layer 43,50nm that the TDAPB layer 42,80nm that layer 41,80nm is thick is thick is thick is thick
2o
3layer 45, forms organic electroluminescence structure 4;
(5) at Al
2o
3the metal Al layer that layer 45 outer surface evaporation one deck 20nm are thick, as negative electrode 5, thus obtains described organic electroluminescence device.
Organic electroluminescence device performance prepared by test the present embodiment is similar to organic electroluminescence device performance prepared by embodiment 1.
Embodiment 5
The organic electroluminescence device structure of the present embodiment is as shown in embodiment 1 and Fig. 1.Its preparation method is as follows:
(1) IZO glass is carried out photoetching treatment, be cut into required light-emitting area, then use each ultrasonic 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively, clean up rear drying, obtained substrate 1;
(2) obtained substrate 1 is put into inside vacuum film coating chamber and carry out the thick metal A l of vacuum moulding machine one deck 70nm, as anode 2;
(3) metal A l outer surface spraying plating one deck particle diameter be 50nm, thickness is the ZnO layer of 70nm, as light scattering layer 3;
(4) evaporation is adopted to plate the thick MoO of 80nm successively at light scattering layer 3 outer surface
xthe RbCl layer 45 that the TPQ layer 44,80nm that the DCJTB layer 43,80nm that the TDAPB layer 42,50nm that layer 41,70nm is thick is thick is thick is thick, forms organic electroluminescence structure 4;
(5) at the Pt metal layer that RbCl layer 45 outer surface evaporation one deck 30nm is thick, as negative electrode 5, thus described organic electroluminescence device is obtained.
Organic electroluminescence device performance prepared by test the present embodiment is similar to organic electroluminescence device performance prepared by embodiment 1.
Embodiment 6
The organic electroluminescence device structure of the present embodiment is as shown in embodiment 1 and Fig. 1.Its preparation method is as follows:
(1) quartz is carried out photoetching treatment, be cut into required light-emitting area, then use each ultrasonic 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol successively, clean up rear drying, obtained substrate 1;
(2) obtained substrate 1 is put into inside vacuum film coating chamber and carry out the thick metal A g of vacuum moulding machine one deck 70nm, as anode 2;
(3) metal A g outer surface evaporation one deck particle diameter be 20nm, thickness is the Al of 50nm
2o
3layer, as light scattering layer 3;
(4) spraying plating mode is adopted to plate the thick VO of 60nm successively at light scattering layer 3 outer surface
xthe NaCl layer 45 that the N-shaped doping inorganic semiconductor layer 44,80nm that the BALQ layer 43,70nm that the CuPc layer 42,50nm that layer 41,40nm is thick is thick is thick is thick, forms organic electroluminescence structure 4;
(5) at the Pt metal layer that NaCl layer 45 outer surface evaporation one deck 20nm is thick, as negative electrode 5, thus described organic electroluminescence device is obtained.
Organic electroluminescence device performance prepared by test the present embodiment is similar to organic electroluminescence device performance prepared by embodiment 1.
Embodiment 7
The organic electroluminescence device structure of the present embodiment is as shown in embodiment 1 and Fig. 1.Its preparation method is as follows:
(1) AZO glass is carried out photoetching treatment, be cut into required light-emitting area, then each ultrasonic 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol is used successively, clean up and rear oxygen plasma treatment is carried out to it, the oxygen plasma treatment time is 10min, power is 30W, obtained substrate 1;
(2) obtained substrate 1 is put into inside vacuum film coating chamber and carry out the thick metal A u of vacuum moulding machine one deck 70nm, as anode 2;
(3) sputter at metal A u outer surface that one deck particle diameter is 20nm, thickness is the TiO of 80nm
2layer, as light scattering layer 3;
(4) electrochemical means is adopted to plate the thick MoO of 30nm successively at light scattering layer 3 outer surface
3the NaCl layer 45 that the N-shaped doping inorganic semiconductor layer 44,70nm that the BALQ layer 43,150nm that the CuPc layer 42,20nm that layer 41,20nm is thick is thick is thick is thick, forms organic electroluminescence structure 4;
(5) at the Pt metal layer that NaCl layer 45 outer surface evaporation one deck 25nm is thick, as negative electrode 5, thus described organic electroluminescence device is obtained.
Organic electroluminescence device performance prepared by test the present embodiment is similar to organic electroluminescence device performance prepared by embodiment 1.
Embodiment 8
The organic electroluminescence device structure of the present embodiment as shown in Figure 2, this organic electroluminescence device comprise combine successively substrate 1, anode 2, light scattering layer 3, hole injection layer 41, hole transmission layer 42, luminescent layer 43 and negative electrode 5.Wherein, substrate 1 is the simple glass that 150nm is thick, and anode 2 is the Ag layer that 60nm is thick, light scattering layer 3 be graininess and its particle diameter be 20nm, thickness is the TiO of 100nm
2layer, hole injection layer 41 is the MoO that 10nm is thick
3layer, hole transmission layer 42 is the NPB layer that 40nm is thick, and luminescent layer 43 is the AlQ that 70nm is thick
3layer, negative electrode 5 is the Au layer that 15nm is thick.
Its preparation method is as follows:
(1) simple glass is carried out photoetching treatment, be cut into required light-emitting area, then each ultrasonic 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl alcohol is used successively, clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 15min, and power is 10W, to reduce roughness and the contact angle of conductive glass surface, improve wettability and the adsorptivity on its surface, remove the organic pollution of conductive glass surface, obtained substrate 1;
(2) obtained substrate 1 is put into inside vacuum film coating chamber carry out vacuum moulding machine layer of metal Ag, as anode 2;
(3) sputter at metal A g outer surface the TiO that one deck particle diameter is 20nm
2layer, as light scattering layer 3;
(4) evaporation is adopted to plate MoO successively at light scattering layer 3 outer surface
3layer 41, NPB layer 42, AlQ
3layer 43, forms organic electroluminescence structure 4;
(5) at AlQ
3layer 43 outer surface evaporation layer of metal Au layer, as negative electrode 5, thus obtain described organic electroluminescence device.
The organic electroluminescence device performance that organic electroluminescence device performance prepared by test the present embodiment is prepared as embodiment 1.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. an organic electroluminescence device, comprising:
One substrate;
One anode, it is combined on a surface of described substrate; The material of described anode is gold, silver or aluminium;
One light scattering layer, it is combined on the surface relative with described substrate of described anode; The material of described light scattering layer is TiO
2, MgO, CaO or Al
2o
3, the thickness of described light scattering layer is 50 ~ 200nm;
One organic electroluminescence structure, it is combined on the surface relative with described anode of described light scattering layer; Described organic electroluminescence structure comprises luminescent layer; There is between described luminescent layer and light scattering layer hole injection layer or hole injection layer and hole transmission layer, and/or there is between described luminescent layer and negative electrode at least one in electron transfer layer, electron injecting layer;
One negative electrode, it is combined on the surface relative with described light scattering layer of described organic electroluminescence structure.
2. organic electroluminescence device according to claim 1, is characterized in that: described light scattering layer is stratum granulosum structure, and described grain diameter is 20 ~ 200nm.
3. organic electroluminescence device according to claim 1, is characterized in that:
The material of described substrate is indium tin oxide glass, mixes the tin oxide glass of fluorine, mixes the zinc oxide glass of aluminium, mixes the zinc oxide glass of indium, simple glass or quartz; The thickness of described anode is 40 ~ 80nm; The material of described negative electrode is gold, silver, platinum or aluminium, and the thickness of described negative electrode is 10 ~ 30nm.
4. organic electroluminescence device according to claim 3, is characterized in that: the thickness of described electron injecting layer is 20 ~ 80nm; The thickness of electron transfer layer is 20 ~ 80nm; The thickness of described luminescent layer is 20 ~ 80nm; The thickness of described hole transmission layer is 20 ~ 80nm; The thickness of described hole injection layer is 20 ~ 80nm.
5. the organic electroluminescence device according to claim 3 or 4, is characterized in that: the material of described electron injecting layer is LiO
2, Cs
2o, Al
2o
3, LiBO
2, K
2siO
3, chloride or alkali earth metal fluoride;
The material of described electron transfer layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 2,5-bis-(1-naphthyl)-1,3, at least one in 4-diazole, 1,2,4-triazole derivative, N-aryl benzimidazole, quinoxaline derivant or N-shaped doping inorganic semiconductor;
The material of described luminescent layer is four-tert-butyl group perylene, 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, two (2-methyl-oxine)-(4-xenol) aluminium, 4-(dintrile methene)-2-isopropyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl) at least one in-4H-pyrans, dimethylquinacridone or oxine aluminium;
The material of described hole transmission layer is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine, 1, at least one in 3,5-triphenylbenzene, CuPc or P type doping inorganic semiconductor;
The material of described hole injection layer is transition metal oxide.
6. an organic electroluminescence device preparation method as claimed in claim 1, comprises the steps:
Substrate is provided;
Plate anode on the substrate; The material of described anode is gold, silver or aluminium;
Light-plated scattering layer on the surface relative with described substrate of described anode; The material of described light scattering layer is TiO
2, MgO, CaO or Al
2o
3;
Organic electroluminescence structure is plated on the surface relative with described anode of described light scattering layer; Described organic electroluminescence structure comprises luminescent layer; There is between described luminescent layer and light scattering layer hole injection layer or hole injection layer and hole transmission layer, and/or there is between described luminescent layer and negative electrode at least one in electron transfer layer, electron injecting layer;
Negative electrode is plated on the surface relative with described light scattering layer of described organic electroluminescence structure, obtains described organic electroluminescence device.
7. organic electroluminescence device preparation method according to claim 6, is characterized in that: the mode of the plated surface light scattering layer that described anode is relative with substrate is evaporation, sputtering or spraying plating.
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| CN104009165B (en) * | 2013-02-26 | 2016-06-08 | 国家电网公司 | The preparation method of a kind of organic electroluminescence device |
| CN104009176A (en) * | 2013-02-26 | 2014-08-27 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method |
| CN104009182A (en) * | 2013-02-26 | 2014-08-27 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN104009181A (en) * | 2013-02-26 | 2014-08-27 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method |
| CN104009174A (en) * | 2013-02-26 | 2014-08-27 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method |
| CN104051644A (en) * | 2013-03-12 | 2014-09-17 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and manufacturing method thereof |
| CN104051666A (en) * | 2013-03-12 | 2014-09-17 | 海洋王照明科技股份有限公司 | Composite anode, preparation method of composite anode, organic electroluminescent device and preparation method of organic electroluminescent device |
| CN104051662A (en) * | 2013-03-12 | 2014-09-17 | 海洋王照明科技股份有限公司 | Composite anode and manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof |
| CN104124395A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN104124354A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN104124344A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN104124377A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN104218168A (en) * | 2013-05-30 | 2014-12-17 | 海洋王照明科技股份有限公司 | Organic light emission diode device and fabrication method thereof |
| CN103872261B (en) * | 2014-02-28 | 2017-03-15 | 京东方科技集团股份有限公司 | A kind of organic electroluminescence device and display device |
| CN109585685B (en) * | 2018-12-07 | 2021-06-01 | 纳晶科技股份有限公司 | Light extraction structure, manufacturing method thereof and light emitting device |
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