CN102468446B - A kind of negative electrode injection material and preparation method thereof and application - Google Patents
A kind of negative electrode injection material and preparation method thereof and application Download PDFInfo
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- CN102468446B CN102468446B CN201010549151.4A CN201010549151A CN102468446B CN 102468446 B CN102468446 B CN 102468446B CN 201010549151 A CN201010549151 A CN 201010549151A CN 102468446 B CN102468446 B CN 102468446B
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Abstract
The invention discloses a kind of negative electrode injection material and preparation method thereof and application, this negative electrode injection material comprises nano titanium oxide and the cesium salt of doping mutually.Its preparation method comprises the steps: preparation of nano titania solution, cesiated salt solution respectively; Described nano titanium oxide Solution Dispersion system is mixed with cesiated salt solution, obtains mixed liquor; Mixed liquor is spin-coated in conductive substrates, heat drying, obtains described negative electrode injection material.Negative electrode injection material cost of the present invention is low, effectively can improve electric charge input and transmission, when applying it in organic electroluminescence device, the lumo energy of its negative electrode is improved, match each other with the energy level of organic electroluminescence structure, reduce potential barrier between the two, be more suitable for the injection of electronics, electron injection efficiency is strengthened, preferably improve organic electroluminescence device light extractability strong, luminosity is high, and the life-span is long.This negative electrode injection material preparation method operation is simple, and production efficiency is high.
Description
Technical field
The invention belongs to electric light source technology field, relate to a kind of negative electrode injection material and preparation method thereof and application 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 EastmanKodak 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 (OrganicLight-EmittingDevice, 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.
The principle of luminosity of OLED is under the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LowerUnoccupiedMolecularOrbitalLUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HighestOccupiedMolecularOrbitalHOMO) 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.Because the transmission rate of hole and electronics is inconsistent, the recombination probability that often result in electron-hole is on the low side, the brightness of device and efficiency can not get improving, therefore in order to effectively improve the recombination probability of electronics and hole, need injection efficiency and the transmission rate of improving charge carrier, equilibrium carrier, controls recombination region, thus obtains desirable luminosity and luminous efficiency.Usually carrier injection layer is added in the devices to improve the injection efficiency of charge carrier, this device architecture not only ensure that the good adhesion between organic function layer and conductive substrates, but also makes that the charge carrier from anode and metallic cathode is easier to be injected in organic functional thin film.But this method makes the processing technology of device become complicated owing to adding functional layer, and the synthesis of these injection materials is complicated, and productive rate is lower, is unfavorable for following suitability for industrialized production.Therefore, exploitation injection efficiency is high, and the simple negative electrode of material source reduces device cost, is one of current urgent problem.The work content of at present conventional some negative electrodes (as Al, Ag or Au etc.) material is all higher, electron injection difficulty, and in addition, these negative electrodes also exist some other shortcomings, as cost is high, and the deficiency such as more responsive under water oxygen environment.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, provide a kind of and effectively can improve the input of electric charge and the negative electrode injection material of transmission and preparation method thereof.
And, the application of above-mentioned negative electrode injection material in organic electroluminescence device is provided.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of negative electrode injection material, comprises nano titanium oxide and the cesium salt of doping mutually.
And above-mentioned negative electrode injection material preparation method, comprises the steps:
Prepare nanometer titanium dioxide titanium solution, by nano titanium oxide with alcoholic solvent or/and redistilled water mixes, compound concentration is the nanometer titanium dioxide titanium solution of 0.1 ~ 2%;
Preparation cesiated salt solution, mixed with alcohol or ether solvents by cesium salt, compound concentration is the cesiated salt solution of 0.1 ~ 2%;
Described nanometer titanium dioxide titanium solution is mixed with cesiated salt solution, obtains mixed liquor;
Mixed liquor is spun in conductive substrates, heat drying, obtains negative electrode injection material.
And, the application of above-mentioned negative electrode injection material in organic electroluminescence device.
The present invention compared with prior art, at least has the following advantages:
1. negative electrode injection material of the present invention comprises nano titanium oxide and the cesium salt of doping mutually, this nano titanium oxide HOMO energy level is low, when applying it in organic electroluminescence device, effectively hole is limited in the organic electroluminescence structure of organic electroluminescence device, and carry out compound with electronics, play the effect of hole barrier, effectively avoid the leakage current directly not arriving negative electrode through the hole of compound and formed; This titanium dioxide is nanoscale simultaneously, is conducive to injection and the transmission of electric charge on the one hand, light can be made to carry out multiple reflections at this nano titanium oxide intercrystalline on the other hand, decrease the loss of light.The lumo energy of cesium salt is higher, effectively can improve the injection of electronics after doping, and stable in properties, not easily react with oxygen.
2. after this nano titanium oxide and cesium salt being adulterated mutually and when being applied in organic electroluminescence device, the lumo energy of organic electroluminescence device negative electrode is improved, match each other with the energy level of organic electroluminescence structure, reduce potential barrier between the two, be more suitable for the injection of electronics, electron injection efficiency is strengthened, simultaneously, cesium salt has good stability, block can not be condensed into, effectively inhibit the shrinkage cracking of organic electroluminescence device cathode surface, the positive role that the life-span of improving organic electroluminescence device is served.
3. this nano titanium oxide and cesium salt cost low, easily obtain, therefore, negative electrode injection material Financial cost of the present invention is low.
4. the preparation of negative electrode injection material of the present invention only need by this nano titanium oxide and cesium salt mixing, and be coated in conductive substrates, through heat drying, its preparation method operation is simple, improves production efficiency, reduces production cost, be suitable for suitability for industrialized production.
5. organic electroluminescence device of the present invention is due to containing above-mentioned negative electrode injection material, and make organic electroluminescence device light extractability of the present invention strong, luminosity is high, and the life-span is long.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of embodiment of the present invention negative electrode injection material preparation method;
Fig. 2 is a kind of structural representation of organic electroluminescence device of the embodiment of the present invention;
Fig. 3 is the another kind of structural representation of organic electroluminescence device of the embodiment of the present invention;
Fig. 4 is the energy level schematic diagram of the organic electroluminescence device of the embodiment of the present invention 1;
Fig. 5 be the embodiment of the present invention 1 prepare organic electroluminescence device (its structure is: ITO substrate/TiO
2with Cs
2cO
3negative electrode implanted layer/the PBD/AlQ of doping
3/ TPD/MoO
3/ Au) be not provided with TiO with existing
2with Cs
2cO
3(its structure is the organic electroluminescence device of the negative electrode implanted layer of doping: ITO substrate/Al/PBD/AlQ
3/ TPD/MoO
3/ Au) current density 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.
The embodiment of the present invention provides a kind of negative electrode injection material, comprises nano titanium oxide and the cesium salt of doping mutually.Such negative electrode injection material of the present invention comprises nano titanium oxide and the cesium salt of doping mutually, this nano titanium oxide HOMO energy level is low, be about-7.6ev, effectively hole is limited in the organic electroluminescence structure of organic electroluminescence device, and carry out compound with electronics, play the effect of hole barrier, effectively avoid the leakage current directly not arriving negative electrode through the hole of compound and formed; This nano titanium oxide has the design feature that porosity is high, specific area is large simultaneously, is conducive to injection and the transmission of electric charge on the one hand, light can be made to carry out multiple reflections at this nano titanium oxide intercrystalline on the other hand, decrease the loss of light.The lumo energy of cesium salt is higher, effectively can improve the injection of electronics after doping, and stable in properties, not easily react with oxygen.
Particularly, the anatase titanium dioxide of above-mentioned nanometer to be particle diameter be 20 ~ 200nm.This anatase titanium dioxide has the design feature that voidage is high, specific area is large, the nano titanium oxide of this structure and particle diameter is more conducive to injection and the transmission of electric charge, and be conducive to light and reflect at nano titanium oxide intercrystalline, decrease the loss of light.
Above-mentioned cesium salt is preferably cesium carbonate (Cs
2cO
3), cesium azide (CsN
3), at least one in cesium chloride (CsCl), cesium bromide (CsBr) or cesium iodide (CsI).The lumo energy of this cesium salt is higher can the injection of more effective improvement electronics, and stable in properties, not easily react with oxygen.
The mass ratio of above-mentioned nano titanium oxide and cesium salt is preferably 1: 0.1 ~ 1, is more preferably 1: 1.The mass ratio of this nano titanium oxide of suitable adjustment and cesium salt, effectively can improve the performance of negative electrode injection material.This nano titanium oxide of the mutual doping of this preferred mass ratio and cesium salt make the lumo energy of this negative electrode injection material obtain further raising, match each other with the energy level of organic electroluminescence structure, reduce further potential barrier between the two, make electron injection efficiency obtain further reinforcement.
The embodiment of the present invention also provides described negative electrode injection material preparation method, and as shown in Figure 1, the method comprises the steps:
S1: prepare nanometer titanium dioxide titanium solution, by nano titanium oxide with alcoholic solvent or/and redistilled water mixes, preparation mass concentration be 0.1 ~ 2% nanometer titanium dioxide titanium solution;
S2: preparation cesiated salt solution, mixes cesium salt with alcohol or ether solvents, preparation mass concentration is the cesiated salt solution of 0.1 ~ 2%;
S3: described nanometer titanium dioxide titanium solution is mixed with cesiated salt solution, obtains mixed liquor;
S4: be spun to by mixed liquor in conductive substrates, heat drying, obtains negative electrode injection material.
Above-mentioned negative electrode injection material preparation method only need by this nano titanium oxide and cesium salt mixing, and be coated in substrate, through heat drying, its preparation method operation is simple, improves production efficiency, reduces production cost, be suitable for suitability for industrialized production.
Particularly, in the preparation method S1 step of above-mentioned negative electrode injection material, this nano titanium oxide solution preparation method is preferably and this grinding limit, nano titanium oxide limit is dripped alcoholic solvent or/and redistilled water.The nano titanium oxide dispersion of such preparation can be more even.This alcoholic solvent can make nano titanium oxide well disperse, and nano titanium oxide can be made to form homogeneous Solution Dispersion system.Wherein, the alcoholic solvent of nano titanium oxide Solution Dispersion system is preferably at least one in ethanol, n-butanol, isopropyl alcohol, terpinol.
In the preparation method S2 step of above-mentioned negative electrode injection material, the alcoholic solvent of cesiated salt solution is preferably at least one in ethanol, glyceryl alcohol, n-butanol, isopropyl alcohol, methyl alcohol, ethylene glycol ethyl ether, certainly, the alcoholic solvent of cesiated salt solution also can substitute with conventional ether solvents.
In the preparation method S3 step of above-mentioned negative electrode injection material, titanium dioxide in nano titanium oxide Solution Dispersion system and the cesium salt mass ratio in cesiated salt solution are 1: 0.1 ~ 1 to mix, and fully stirring makes both mix, the time of stirring is preferably 15 ~ 60min.In order to reach better doping effect, preferably mix with cesiated salt solution with the isopyknic nanometer titanium dioxide titanium solution of equal in quality mark during mixing.
In the preparation method S4 step of above-mentioned negative electrode injection material, the mode of spin coating is adopted the mixed liquor of nanometer titanium dioxide titanium solution and cesiated salt solution to be coated to conductive substrates surface, this is because spin coating can not be destroyed by the organic layer effectively ensured in organic electroluminescence devices.Certainly, as long as the coating method that the organic layer that can ensure organic electroluminescence devices kind is not destroyed, are all equivalent replacements of spin coating mode of the present invention.The mixed liquor being spun to surface needs drying, contains the impurity such as alcohol simultaneously, therefore need impurity to remove in this mixed liquor.Again due to this impurity mainly organic solvent such as alcohol, therefore preferably take the mode heated to remove impurity, allow impurity volatilize.The mode that the mode heated adopts this area conventional.The temperature of heat drying is preferably 100 ~ 200 DEG C, and heating time is preferably 15 ~ 60min.
The one that this conductive substrates is preferably indium tin oxide glass, mixes the tin oxide glass of fluorine, mixes the zinc oxide glass of aluminium or mix in the zinc oxide glass of indium.Before its this mixed liquor of surperficial spin coating, preferably conductive substrates is carried out oxygen plasma treatment, the time of this oxygen plasma treatment is preferably 5-15min, and power is preferably 10-50W.
Have above-mentioned advantage just because of negative electrode injection material, therefore, this negative electrode injection material can be applied in organic electroluminescence device.Embody rule mode at least can be as follows:
As shown in Figure 2.Organic electroluminescence device comprises negative electrode 1, and the organic electroluminescence structure 2, the anode 3 that are combined successively with described negative electrode 1.Wherein, negative electrode 1 comprises a conductive substrates 11, and is combined in conductive substrates 11 surface cathode implanted layer 12, this negative electrode implanted layer 12 by above-mentioned negative electrode injection material by the mode of spin coating be coated to conductive substrates 11 surface and be prepared from through super-dry.Like this, because the negative electrode 1 of this organic electroluminescence device is containing above-mentioned negative electrode injection material, the lumo energy of this negative electrode 1 is improved, match each other with the energy level of organic electroluminescence structure 2, reduce potential barrier between the two, be more suitable for the injection of electronics, electron injection efficiency is strengthened, simultaneously, cesium salt has good stability, block can not be condensed into, effectively inhibit the shrinkage cracking on negative electrode 1 surface, to the positive role that the life-span of improving organic electroluminescence device serves, in addition, this nano titanium oxide and cesium salt cost low, easy acquisition, therefore, reduce organic electroluminescence device biological economy cost.
The thickness of above-mentioned negative electrode implanted layer 12 is preferably 20 ~ 80nm.The negative electrode implanted layer 12 of this thickness can make electron injection efficiency be further strengthened, and meanwhile, more can carry out good reflection at this negative electrode implanted layer 12 by light, decrease the loss of light, improves the light extractability of organic electroluminescence device.
The one that above-mentioned conductive substrates 11 is preferably indium tin oxide glass (ito glass), mixes the tin oxide glass of fluorine (FTO glass), mixes the zinc oxide glass (AZO glass) of aluminium or mix in the zinc oxide glass (IZO glass) of indium.Particularly, above-mentioned conductive substrates 11 comprises light-transmissive substrates 111 and is incorporated into the conductive layer 112 on light-transmissive substrates 111 surface.Wherein, the thickness of this conductive layer 112 is preferably 100 ~ 200nm, and its material is preferably indium tin oxide (ITO), fluorine doped tin oxide (FTO), magnesium-indium oxide (IZO) or mixes the zinc oxide (AZO) of aluminium.The material of light-transmissive substrates 111 can be transparent glass.
Light-transmissive substrates 111, before being combined with conductive layer 112, is preferably preferably carried out pre-process by above-mentioned light-transmissive substrates 111, as clean and oxygen plasma treatment.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 light-transmissive substrates 111 surface, makes light-transmissive substrates 111 surface farthest clean; Light-transmissive substrates 111 is after clean, carry out oxygen plasma treatment again, the time of this oxygen plasma treatment is preferably 5-15min, power is preferably 10-50W, its Main Function is the roughness and the contact angle that reduce light-transmissive substrates 111 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 conductive substrates 11 of this structure effectively can strengthen the mechanical strength of this organic electroluminescence device, effectively isolated air, and has good electric conductivity.This conductive substrates 11 is at this also as transparent surface, and therefore, conductive substrates 1 should be transparent or semitransparent shape, preferably clear shape, and the light sent better to make organic electroluminescence device penetrates.
The material of anode 3 is preferably gold (Au), silver (Ag), platinum (Pt) or aluminium (Al), and its thickness is the thickness that the art is commonly used, but is preferably 100 ~ 150nm.
Above-mentioned organic electroluminescence structure 2 comprises luminescent layer 22; There is between this luminescent layer 22 and anode 3 at least one in hole transmission layer 23, hole injection layer 24, and/or between luminescent layer 22 and organic electroluminescence device negative electrode 1, there is electron transfer layer 21.Like this, organic electroluminescence structure 2 at least has following several structure, and certainly, except the following several structures enumerated, every is organic electroluminescence structure 2 within this organic electroluminescence structure 2 structural framing, all within technical solution of the present invention:
The first structure: as described in Figure 2, simultaneously see Fig. 1, this organic electroluminescence structure 2 comprises the electron transfer layer 21, luminescent layer 22, hole transmission layer 23 and the hole injection layer 24 that combine successively to its structure.Wherein, electron transfer layer 21 is combined on the surface relative with conductive substrates 11 of the negative electrode implanted layer 12 of organic electroluminescence device negative electrode 1, and hole injection layer 24 is combined with anode.
The second structure: this organic electroluminescence structure 2 comprises the luminescent layer 22, hole transmission layer 23 and the hole injection layer 24 that combine successively.Wherein, luminescent layer 22 is combined on the surface relative with conductive substrates 11 of the negative electrode implanted layer 12 of organic electroluminescence device negative electrode 1, and hole injection layer 24 is combined with anode.
The third structure: this organic electroluminescence structure 2 comprises the electron transfer layer 21, luminescent layer 22 and the hole injection layer 24 that combine successively.Wherein, electron transfer layer 21 is combined on the surface relative with conductive substrates 11 of the negative electrode implanted layer 12 of organic electroluminescence device negative electrode 1, and hole injection layer 24 is combined with anode.
4th kind of structure: as described in Figure 3, simultaneously see Fig. 1, this organic electroluminescence structure 2 is made up of luminescent layer 22 its structure, and this luminescent layer 22 is combined between organic electroluminescence device negative electrode 1 and anode 3.
Because above-mentioned 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, this luminescent layer 22, and/or hole injection layer 24, hole transmission layer 23, electron transfer layer 21 is arranged, the injection in effective adjustment electronics and hole and transmission rate, equilibrium carrier, control recombination region, to obtain desirable luminosity and luminous efficiency, simultaneously, embodiment of the present invention organic electroluminescence device is also made not only to ensure that organic function layer and the good adhesion between organic electroluminescence device negative electrode 1 and anode 3, but also make that the charge carrier from anode 3 and organic electroluminescence device negative electrode 1 is easier to be injected in organic functional thin film.Such as, hole injection layer 24 is preferably transition metal oxide, this material and organic cavity transmission layer 23 energy level comparison match, the hole of anode 3 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 described hole injection layer 24 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 23 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.The thickness of luminescent layer 22 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), dimethylquinacridone (DMQA), oxine aluminium (Alq
3) at least one.The thickness of electron transfer layer 21 is preferably 20 ~ 80nm, and its material is preferably 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-bis-(1-naphthyl)-1,3,4-diazole (BND), 1, at least one in 2,4-triazole derivative (as TAZ), N-aryl benzimidazole (TPBI), quinoxaline derivant (TPQ).
Above-mentioned luminescent layer 22, and/or hole injection layer 24, hole transmission layer 23, combination between electron transfer layer 21 can adopt the modes such as evaporation, sputtering, spraying plating or chemical deposition.
Particularly, the preparation method that the preparation method of this organic electroluminescence device adopts this area conventional, the combination of organic electroluminescence device negative electrode 1, organic electroluminescence structure 2 and anode 3 can adopt the modes such as evaporation, sputtering, spin coating or spraying plating.
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 2, this organic electroluminescence device includes organic electroluminescence devices negative electrode 1, and the electron transfer layer 21, luminescent layer 22, hole transmission layer 23, hole injection layer 24 and the anode 3 that are combined successively with organic electroluminescence device negative electrode 1.Wherein, organic electroluminescence device negative electrode 1 comprises conductive substrates 11 and is combined in conductive substrates 11 surface cathode implanted layer 12.
Above-mentioned conductive substrates 11 be indium tin oxide glass (ito glass), the thickness of negative electrode implanted layer 12 is 50nm, and electron transfer layer 21 is PBD layer that 50nm is thick, luminescent layer 22 is the AlQ that 70nm is thick
3layer, hole transmission layer 23 are the TPD layer that 40nm is thick, the MoO that hole injection layer 2410nm is thick
3layer and anode 3 are the Au of 150nm.
Organic electroluminescence device preparation method is as follows:
(1) ito 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 100nm by commercially available particle diameter
2particle and absolute ethyl alcohol are configured to the TiO that mass fraction is 0.8%
2solution Dispersion system, during preparation, grinding limit in limit dropwise adds solvent, allows TiO
2evengranularly be dispersed in alcoholic solvent;
(22) by Cs
2cO
3inorganic matter and ethylene glycol ethyl ether are configured to the solution that mass fraction is 0.8%, stir 1h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) Cs
2cO
3solution be by volume 1: 1 ratio mix, fully stir 15min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 2000rpm, then be heated to 150 DEG C and carry out dry 40min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) evaporation is adopted to plate PBD layer 21, AlQ successively at negative electrode implanted layer 12 outer surface
3layer 22, TPD layer 23 and MoO
3layer 24;
(4) at MoO
3layer 24 outer surface evaporation layer of metal Au layer, as anode 3, thus obtain described organic electroluminescence device.
Organic electroluminescence device energy diagram prepared by the present embodiment as described in Figure 4, as shown in Figure 4, the lumo energy of organic electroluminescence device negative electrode 1 is improved, potential barrier between organic electroluminescence device negative electrode 1 and organic electroluminescence structure 2 is diminished, electronics more effectively can be transitted in organic electroluminescence structure 2 and carry out transferring charge, and, the HOMO energy level of this material is lower, can effective blocking hole, suppress hole arrive negative electrode form the leakage current being unfavorable for luminous efficiency.
(its structure is the organic electroluminescence device prepared of the present embodiment: ito glass/TiO
2-Cs
2cO
3negative electrode implanted layer/the PBD/AlQ of doping
3/ TPD/MoO
3/ Au) do not establish TiO with existing
2with Cs
2cO
3(its structure is: ito glass/Al/PBD/AlQ for the negative electrode implanted layer of doping organic electroluminescence device using Al as negative electrode
3/ TPD/MoO
3/ Au) current density and voltage relationship figure as shown in Figure 5.
As seen from Figure 5, 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 present embodiment prepares that the current density of organic electroluminescence device is relatively existing does not establish TiO
2with Cs
2cO
3the negative electrode implanted layer adulterated also obtains significant raising using Al as the current density of the organic electroluminescence device of negative electrode.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. 2.Its preparation method is as follows:
(1) ito 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 5min, and power is 50W, 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 20nm by commercially available particle diameter
2particle and absolute ethyl alcohol are configured to the solution that mass fraction is 0.2%, and during preparation, grinding limit in limit dropwise adds solvent, allow TiO
2evengranular dispersion in the solution;
(22) by Cs
2cO
3inorganic matter and ethylene glycol ethyl ether are configured to the solution that mass fraction is 0.2%, stir 2h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) Cs
2cO
3solution be by volume 1: 1 ratio mix, fully stir 30min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 2000rpm, then be heated to 100 DEG C and carry out dry 60min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) evaporation is adopted to plate the thick CuPc layer 23 of the thick BND layer 21 of 20nm, TBP layer 22 that 20nm is thick, 20nm and the thick MoO of 20nm successively at negative electrode implanted layer 12 outer surface
3layer 24;
(4) at MoO
3the Au layer that layer 24 outer surface evaporation layer of metal 100nm are thick, as anode 3, 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 3
The organic electroluminescence device structure of the present embodiment is as shown in embodiment 1 and Fig. 2.Its preparation method is as follows:
(1) ito 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 10min, and power is 30W, 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 150nm by commercially available particle diameter
2particle and n-butanol are configured to the solution that mass fraction is 0.5%, and during preparation, grinding limit in limit dropwise adds solvent, allow TiO
2evengranular dispersion in the solution;
(22) by Cs
2cO
3inorganic matter and ethylene glycol ethyl ether are configured to the solution that mass fraction is 0.5%, stir 2h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) Cs
2cO
3solution be by volume 1: 1 ratio mix, fully stir 15min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 500rpm, then be heated to 150 DEG C and carry out dry 30min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) evaporation is adopted to plate the thick AlQ of 20nm successively at negative electrode implanted layer 12 outer surface
3the TDAPB layer 23 that layer 21, DCJTB layer 22 that 20nm is thick, 20nm are thick and the thick VO of 20nm
xlayer 24;
(4) at VO
xthe Au layer that layer 24 outer surface evaporation layer of metal 150nm are thick, as anode 3, 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. 3.Its preparation method is as follows:
(1) ito 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 10min, and power is 30W, 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 200nm by commercially available particle diameter
2particle and n-butanol are configured to the solution that mass fraction is 1%, and during preparation, grinding limit in limit dropwise adds solvent, allow TiO
2evengranular dispersion in the solution;
(22) by Cs
2cO
3inorganic matter and ethylene glycol ethyl ether are configured to the solution that mass fraction is 1%, stir 5h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) Cs
2cO
3solution be by volume 1: 1 ratio mix, fully stir 20min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 1000rpm, then be heated to 150 DEG C and carry out dry 30min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) evaporation is adopted to plate the thick AlQ of 80nm successively at negative electrode implanted layer 12 outer surface
3the TDAPB layer 23 that layer 21, BALQ layer 22 that 60nm is thick, 80nm are thick and the thick VO of 50nm
xlayer 24;
(4) at VO
xthe Al layer that layer 24 outer surface evaporation layer of metal 150nm are thick, as anode 3, 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. 3.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 carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 10min, and power is 30W, 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 200nm by commercially available particle diameter
2particle and redistilled water are configured to the solution that mass fraction is 0.8%, and during preparation, grinding limit in limit dropwise adds solvent, allow TiO
2evengranular dispersion in the solution;
(22) by Cs
2cO
3inorganic matter and ethylene glycol ethyl ether are configured to the solution that mass fraction is 0.8%, stir 5h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) Cs
2cO
3solution be by volume 1: 1 ratio mix, fully stir 60min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 4000rpm, then be heated to 200 DEG C and carry out dry 20min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) evaporation is adopted to plate the thick AlQ of 40nm successively at negative electrode implanted layer 12 outer surface
3the TDAPB layer 23 that layer 21, BALQ layer 22 that 60nm is thick, 40nm are thick and the thick VO of 80nm
xlayer 24;
(4) at VO
xthe Al layer that layer 24 outer surface evaporation layer of metal 200nm are thick, as anode 3, 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 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) 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 carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 10min, and power is 30W, 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 20nm by commercially available particle diameter
2particle and isopropyl alcohol are configured to the solution that mass fraction is 0.4%, and during preparation, grinding limit in limit dropwise adds solvent, allow TiO
2evengranular dispersion in the solution;
(22) CsCl inorganic matter and ethanol are configured to the solution that mass fraction is 0.4%, stir 10h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) CsCl solution press TiO
2the ratio being 1: 0.1 with the mass ratio of CsCl mixes, and fully stirs 60min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 3000rpm, then be heated to 200 DEG C and carry out dry 20min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) evaporation is adopted to plate the thick AlQ of 40nm successively at negative electrode implanted layer 12 outer surface
3the TDAPB layer 23 that layer 21, BALQ layer 22 that 60nm is thick, 40nm are thick and the thick VO of 80nm
xlayer 24;
(4) at VO
xthe Ag layer that layer 24 outer surface evaporation layer of metal 200nm are thick, as anode 3, 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 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) IZO 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 10min, and power is 30W, 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 180nm by commercially available particle diameter
2particle and isopropyl alcohol are configured to the solution that mass fraction is 0.1%, and during preparation, grinding limit in limit dropwise adds solvent, allow TiO
2evengranular dispersion in the solution;
(22) by CsN
3be configured to terpinol the solution that mass fraction is 0.1%, stir 10h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) CsN
3solution presses TiO
2with CsN
3mass ratio be 1: 0.8 ratio mix, fully stir 60min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 2500rpm, then be heated to 120 DEG C and carry out dry 50min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) adopting evaporation to plate the thick mass ratio of 40nm successively at negative electrode implanted layer 12 outer surface is the VO that TDAPB layer 23 that the TPQ layer 21 of 1: 1, BALQ layer 22 that 60nm is thick, 40nm are thick and 80nm are thick
xlayer 24;
(4) at VO
xthe Pt layer that layer 24 outer surface evaporation layer of metal 100nm are thick, as anode 3, 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 8
As Figure 1 and Figure 4, this organic electroluminescence device includes organic electroluminescence devices negative electrode 1 to the organic electroluminescence device structure of the present embodiment, and the luminescent layer 22 be combined successively with organic electroluminescence device negative electrode 1 and anode 3.Wherein, organic electroluminescence device negative electrode 1 comprises conductive substrates 11 and is combined in conductive substrates 11 surface cathode implanted layer 12.
Preparation method is as follows for this organic electroluminescence device:
(1) FTO 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 10min, and power is 30W, 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 140nm by commercially available particle diameter
2particle and isopropyl alcohol are configured to the solution that mass fraction is 2%, and during preparation, grinding limit in limit dropwise adds solvent, allow TiO
2evengranular dispersion in the solution;
(22) CsI and ethanol are configured to the solution that mass fraction is 2%, stir 10h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) CsI solution press TiO
2the ratio being 1: 1 with the volume ratio of CsI mixes, and fully stirs 60min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 2500rpm, then be heated to 120 DEG C and carry out dry 50min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) evaporation is adopted to plate the thick AlQ of 60nm at negative electrode implanted layer 12 outer surface
3layer 22;
(4) at AlQ
3the Pt layer that layer 22 outer surface evaporation layer of metal 150nm are thick, as anode 3, thus obtains described organic electroluminescence device.
Embodiment 9
The organic electroluminescence device structure of the present embodiment is shown in Figure 3, this organic electroluminescence device includes organic electroluminescence devices negative electrode 1, and the luminescent layer 22, hole transmission layer 23, hole injection layer 24 and the anode 3 that are combined successively with organic electroluminescence device negative electrode 1.Wherein, organic electroluminescence device negative electrode 1 comprises conductive substrates 11 and is combined in conductive substrates 11 surface cathode implanted layer 12.
Organic electroluminescence device preparation method is as follows:
(1) FTO 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 10min, and power is 30W, 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 20nm by commercially available particle diameter
2particle and isopropyl alcohol are configured to the solution that mass fraction is 1%, fully stir, make TiO
2evengranular dispersion in the solution;
(22) CsBr and glyceryl alcohol are configured to the solution that mass fraction is 1%, stir 10h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) CsBr solution be by volume 1: 1 ratio mix, fully stir 60min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 500rpm, then be heated to 120 DEG C and carry out dry 50min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) evaporation is adopted to plate the thick TDAPB layer 23 of the thick BALQ layer 22 of 60nm, 40nm and the thick VO of 80nm successively at negative electrode implanted layer 12 outer surface
xlayer 24;
(4) at VO
xthe Pt layer that layer 24 outer surface evaporation layer of metal 150nm are thick, as anode 3, 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 10
The organic electroluminescence device structure of the present embodiment is shown in Figure 3, this organic electroluminescence device includes organic electroluminescence devices negative electrode 1, and the electron transfer layer 21, luminescent layer 22, hole injection layer 24 and the anode 3 that are combined successively with organic electroluminescence device negative electrode 1.Wherein, organic electroluminescence device negative electrode 1 comprises conductive substrates 11 and is combined in conductive substrates 11 surface cathode implanted layer 12.
Organic electroluminescence device preparation method is as follows:
(1) FTO 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 10min, and power is 30W, 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 conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) be the TiO of 20nm by commercially available particle diameter
2particle and isopropyl alcohol are configured to the solution that mass fraction is 1.5%, fully stir, make TiO
2evengranular dispersion in the solution;
(22) CsBr and glyceryl alcohol are configured to the solution that mass fraction is 1.5%, stir 10h stand-by;
(23) by TiO that step (21) is prepared
2solution and (22) CsBr solution be by volume 1: 1 ratio mix, fully stir 60min for subsequent use;
(24) mixed liquor step (23) prepared is spun to the surface of conductive substrates 11 with the rotating speed of 500rpm, then be heated to 120 DEG C and carry out dry 50min, thus forming negative electrode injection material on conductive substrates 11 surface, namely this negative electrode injection material also forms negative electrode implanted layer 12;
(3) evaporation is adopted to plate the thick BALQ layer 22 of the thick TPQ layer 21 of 70nm, 60nm and the thick VO of 80nm successively at negative electrode implanted layer 12 outer surface
xlayer 24;
(4) at VO
xthe Pt layer that layer 24 outer surface evaporation layer of metal 150nm are thick, as anode 3, 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.
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 (5)
1. a negative electrode injection material, comprises nano titanium oxide and the cesium salt of doping mutually; The mass ratio of described nano titanium oxide and cesium salt is 1:(0.8 ~ 1), and described negative electrode injection material is formed after heating 15 ~ 60min at 100 ~ 200 DEG C,
Described cesium salt is Cs
2cO
3, and described negative electrode injection material is the particle diameter being 0.8% by mass fraction is the TiO of 100nm
2ethanol solution and mass fraction are the Cs of 0.8%
2cO
3ethylene glycol ethyl ethers ethereal solution mixes for the ratio of 1:1 by volume, and after fully stirring 15min, rotating speed is spun to the surface of conductive substrates, and being then heated to 150 DEG C carries out dry 40min formation; Or
Described cesium salt is Cs
2cO
3, and described negative electrode injection material is the particle diameter being 0.2% by mass fraction is the TiO of 20nm
2ethanol solution and mass fraction are the Cs of 0.2%
2cO
3ethylene glycol ethyl ethers ethereal solution mixes for the ratio of 1:1 by volume, and after fully stirring 30min, rotating speed is spun to the surface of conductive substrates, and being then heated to 100 DEG C carries out dry 60min formation; Or
Described cesium salt is Cs
2cO
3, and described negative electrode injection material is the particle diameter being 0.8% by mass fraction is the TiO of 200nm
2the second distillation aqueous solution and mass fraction are the Cs of 0.8%
2cO
3ethylene glycol ethyl ethers ethereal solution mixes for the ratio of 1:1 by volume, and after fully stirring 60min, rotating speed is spun to the surface of conductive substrates, and being then heated to 200 DEG C carries out dry 20min formation; Or
Described cesium salt is CsCl, and described negative electrode injection material is the particle diameter being 0.4% by mass fraction is the TiO of 20nm
2aqueous isopropanol and mass fraction are that the CsCl ethanolic solution of 0.4% is according to TiO
2the ratio being 1:0.1 with the mass ratio of CsCl mixes, and after fully stirring 60min, rotating speed is spun to the surface of conductive substrates, is then heated to 200 DEG C and carries out dry 20min formation.
2. a preparation method for negative electrode injection material, comprises the steps:
Prepare nanometer titanium dioxide titanium solution, by nano titanium oxide with alcoholic solvent or/and redistilled water mixes, preparation mass concentration be 0.1 ~ 2% nanometer titanium dioxide titanium solution;
Preparation cesiated salt solution, mixes cesium salt with alcohol or ether solvents, and preparation mass concentration is the cesiated salt solution of 0.1 ~ 2%;
Described cesium salt is Cs
2cO
3, be that the particle diameter of 0.8% is the TiO of 100nm by mass fraction
2ethanol solution and mass fraction are the Cs of 0.8%
2cO
3ethylene glycol ethyl ethers ethereal solution mixes for the ratio of 1:1 by volume, and after fully stirring 15min, rotating speed is spun to the surface of conductive substrates, and being then heated to 150 DEG C carries out dry 40min; Or
Described cesium salt is Cs
2cO
3, be that the particle diameter of 0.2% is the TiO of 20nm by mass fraction
2ethanol solution and mass fraction are the Cs of 0.2%
2cO
3ethylene glycol ethyl ethers ethereal solution mixes for the ratio of 1:1 by volume, and after fully stirring 30min, rotating speed is spun to the surface of conductive substrates, and being then heated to 100 DEG C carries out dry 60min; Or
Described cesium salt is Cs
2cO
3, be that the particle diameter of 0.8% is the TiO of 200nm by mass fraction
2the second distillation aqueous solution and mass fraction are the Cs of 0.8%
2cO
3ethylene glycol ethyl ethers ethereal solution mixes for the ratio of 1:1 by volume, and after fully stirring 60min, rotating speed is spun to the surface of conductive substrates, and being then heated to 200 DEG C carries out dry 20min; Or
Described cesium salt is CsCl, is that the particle diameter of 0.4% is the TiO of 20nm by mass fraction
2aqueous isopropanol and mass fraction are that the CsCl ethanolic solution of 0.4% is according to TiO
2the ratio being 1:0.1 with the mass ratio of CsCl mixes, and after fully stirring 60min, rotating speed is spun to the surface of conductive substrates, is then heated to 200 DEG C and carries out dry 20min.
3. negative electrode injection material preparation method according to claim 2, is characterized in that, the one that described conductive substrates comprises indium tin oxide glass, mixes the tin oxide glass of fluorine, mixes the zinc oxide glass of aluminium or mix in the zinc oxide glass of indium.
4. negative electrode injection material preparation method according to claim 2, is characterized in that: described preparation method comprises further and carries out oxygen plasma treatment to conductive substrates, and the time of described oxygen plasma treatment is 5-15min, and power is 10-50W.
5. the application of negative electrode injection material according to claim 1 in organic electroluminescence device.
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| Doping of the metal oxide nanostructure and its influence in organic electronics;Mi-hyae Park, Juo-Hao Li, Ankit Kumar, et.al,;《Adv. Funct. Mater.》;20091231;第19卷;1241-1246 * |
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