CN102468446A - Cathode injection material, and manufacturing method and application thereof - Google Patents
Cathode injection material, and manufacturing method and application thereof Download PDFInfo
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- CN102468446A CN102468446A CN2010105491514A CN201010549151A CN102468446A CN 102468446 A CN102468446 A CN 102468446A CN 2010105491514 A CN2010105491514 A CN 2010105491514A CN 201010549151 A CN201010549151 A CN 201010549151A CN 102468446 A CN102468446 A CN 102468446A
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Abstract
The invention discloses a cathode injection material, and a manufacturing method and an application thereof. The cathode injection material comprises nano-titanium dioxide and a cesium salt doped mutually. The manufacturing method comprises the following steps of: preparing a nano-titanium dioxide solution and a cesium salt solution respectively; mixing a nano-titanium dioxide solution dispersion system with the cesium salt solution to obtain a mixed solution; and coating the mixed solution onto a conductive substrate in a spinning way, and heating and drying to obtain the cathode injection material. The cathode injection material disclosed by the invention has the advantages of low cost, capability of effectively enhancing the input and the transmission of charges, increase in the LUMO energy level of a cathode when applied to an organic electroluminescent device, matching with the energy level of an organic electroluminescent structure, reduction in a potential barrier between the cathode injection material and the organic electroluminescent structure, more suitability for electron injection, increase in the electron injection efficiency, preferable increase in the light extraction capability of the organic electroluminescent device, high luminance and long service life. The manufacturing method of the cathode injection material has a simple procedure and high production efficiency.
Description
Technical field
The invention belongs to the electric light source technology field, relate to a kind of negative electrode injection material and preparation method thereof and application specifically.
Background technology
The electric light source industry is the focus that countries in the world are competitively studied always, in World Economics in occupation of important status.Present widely used light source is a glow discharge spot lamp, and the principle of this light source is that the inside with lamp charges into mercurous mist after vacuumizing, and utilizes the ultraviolet excitation light-emitting phosphor that gas discharge is luminous or gas discharge produces.Yet the pulse color break-up of glow discharge spot lamp causes people's visual fatigue easily, and the mercury pollution environment, and along with the progress of society with science and technology, the green light source of researching and developing energy-conservation environmental protection again substitutes conventional light source, becomes the important topic that various countries are competitively studied.
Organic electroluminescence device is a kind of in the electric light source.1987, the C.W.Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in the organic electroluminescent research.Utilize the ultrathin film technology to prepare high brightness, and high efficiency double-deck micromolecule organic electroluminescence device (Organic Light-Emitting Device, OLED).In this double-deck device, brightness reaches 1000cd/m under the 10V
2, its luminous efficiency is that 1.51lm/W, life-span were 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 (Lower Unoccupied Molecular Orbital LUMO) from negative electrode, and the hole is injected into organic highest occupied molecular orbital (Highest Occupied Molecular Orbital HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton move under electric field action, gives luminescent material with NE BY ENERGY TRANSFER, and excitation electron is from the ground state transition to excitation state, excited energy is through the radiation inactivation, generation photon, release luminous energy.Because the transmission rate of hole and electronics is inconsistent; Often caused the recombination probability in electronics-hole on the low side, the brightness of device and efficient can not get improving, therefore in order effectively to improve the recombination probability in electronics and hole; Need to improve the injection efficiency and the transmission rate of charge carrier; Equilibrium carrier, the control recombination region, thus obtain desirable luminosity and luminous efficiency.Usually in device, add the injection efficiency that carrier injection layer is improved charge carrier; This device architecture has not only guaranteed the good adhesion between organic function layer and conductive substrates, but also makes and to be injected in the organic functional thin film from the charge carrier of anode and metallic cathode is easier.But this method makes the processing technology of device become complicated owing to having increased functional layer, and these injection materials are synthetic complicated, and productive rate is lower, is unfavorable for following suitability for industrialized production.Therefore, the exploitation injection efficiency is high, and the simple negative electrode of material source is to reduce device cost, is one of present urgent problem.The work content of present some negative electrodes (like Al, Ag or Au etc.) material of using always is all than higher, and electronics injects difficulty, and in addition, also there are some other shortcomings in these negative electrodes, and is high like cost, under water oxygen environment, compares deficiencies such as sensitivity.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of and can effectively improve the input of electric charge and 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 the foregoing invention purpose, technical scheme of the present invention is following:
A kind of negative electrode injection material comprises the nano titanium oxide and the cesium salt of mutual doping.
And above-mentioned negative electrode injection material preparation method comprises the steps:
Preparation nanometer titanium dioxide titanium solution, with nano titanium oxide with alcoholic solvent or/and redistilled water mixes, compound concentration is 0.1～2% nanometer titanium dioxide titanium solution;
The preparation cesiated salt solution is mixed cesium salt with alcohol or ether solvents, compound concentration is 0.1～2% cesiated salt solution;
Said nanometer titanium dioxide titanium solution is mixed with cesiated salt solution, obtain mixed liquor;
Mixed liquor is spun on the conductive substrates, and heat drying obtains the 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 has the following advantages at least:
1. negative electrode injection material of the present invention comprises the nano titanium oxide and the cesium salt of mutual doping; This nano titanium oxide HOMO energy level is low; In the time of in applying it to organic electroluminescence device, effectively hole confinement in the organic electroluminescence structure of organic electroluminescence device, and carry out compound with electronics; Play the effect of hole barrier, effectively avoided directly not arriving the formed leakage current of negative electrode through compound hole; This titanium dioxide is nanoscale simultaneously, helps the injection and the transmission of electric charge on the one hand, and light is repeatedly reflected at this nano titanium oxide intercrystalline, has reduced the loss of light.The lumo energy of cesium salt is higher, can effectively improve the injection of electronics after the doping, and stable in properties, is difficult for reacting with oxygen.
2. with mix mutually back and when being applied in the organic electroluminescence device of this nano titanium oxide and cesium salt, make the lumo energy of organic electroluminescence device negative electrode be improved, match each other with the energy level of organic electroluminescence structure; Reduced potential barrier between the two; Be more suitable for the injection of electronics, electron injection efficiency strengthened, simultaneously; Cesium salt has good stable property; Can not be condensed into piece, effectively suppress the shrinkage cracking of organic electroluminescence device cathode surface, the positive role that life-span of improving organic electroluminescence device has been played.
3. this nano titanium oxide and cesium salt cost are low, are prone to obtain, and 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 needs this nano titanium oxide and cesium salt are mixed, and is coated on the conductive substrates, gets final product through heat drying, and its preparation method operation is simple, has improved production efficiency, has reduced production cost, is suitable for suitability for industrialized production.
5. organic electroluminescence device of the present invention makes that organic electroluminescence device light extraction ability of the present invention is strong owing to contain above-mentioned negative electrode injection material, and luminosity is high, and the life-span is long.
Description of drawings
Fig. 1 is embodiment of the invention negative electrode injection material preparation method's a schematic flow sheet;
Fig. 2 is a kind of structural representation of the organic electroluminescence device of the embodiment of the invention;
Fig. 3 is the another kind of structural representation of the organic electroluminescence device of the embodiment of the invention;
Fig. 4 is the energy level sketch map of the organic electroluminescence device of the embodiment of the invention 1;
Fig. 5 is that (its structure is: ITO substrate/TiO for the organic electroluminescence device of the embodiment of the invention 1 preparation
2With Cs
2CO
3Negative electrode implanted layer/the PBD/AlQ that mixes
3/ TPD/MoO
3/ Au) with the existing TiO that is not provided with
2With Cs
2CO
3(its structure is the organic electroluminescence device of the negative electrode implanted layer that mixes: ITO substrate/Al/PBD/AlQ
3/ TPD/MoO
3/ Au) current density and voltage relationship figure.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention will be solved, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The embodiment of the invention provides a kind of negative electrode injection material, comprises the nano titanium oxide and the cesium salt of mutual doping.Negative electrode injection material of the present invention like this comprises the nano titanium oxide and the cesium salt of mutual doping; This nano titanium oxide HOMO energy level is low; Be about-7.6ev, effectively hole confinement in the organic electroluminescence structure of organic electroluminescence device, and carry out compound with electronics; Play the effect of hole barrier, effectively avoided directly not arriving the formed leakage current of negative electrode through compound hole; This nano titanium oxide has porosity height, design feature that specific area is big simultaneously, helps the injection and the transmission of electric charge on the one hand, and light is repeatedly reflected at this nano titanium oxide intercrystalline, has reduced the loss of light.The lumo energy of cesium salt is higher, can effectively improve the injection of electronics after the doping, and stable in properties, is difficult for reacting with oxygen.
Particularly, above-mentioned nanometer is that particle diameter is the anatase titanium dioxide of 20～200nm.This anatase titanium dioxide has voidage height, design feature that specific area is big; The nano titanium oxide of this structure and particle diameter more helps the injection and the transmission of electric charge; And help light and reflect at the nano titanium oxide intercrystalline, reduced the loss of light.
Above-mentioned cesium salt is preferably cesium carbonate (Cs
2CO
3), cesium azide (CsN
3), at least a in cesium chloride (CsCl), cesium bromide (CsBr) or the cesium iodide (CsI).The higher injection that can more effective improvement electronics of the lumo energy of this cesium salt, and stable in properties are difficult for reacting with oxygen.
The mass ratio of above-mentioned nano titanium oxide and cesium salt is preferably 1: 0.1～and 1, more preferably 1: 1.Suitably adjust the mass ratio of this nano titanium oxide and cesium salt, can effectively 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; Further reduced potential barrier between the two, made electron injection efficiency obtain further reinforcement.
The embodiment of the invention also provides said negative electrode injection material preparation method, and as shown in Figure 1, this method comprises the steps:
S1: preparation nanometer titanium dioxide titanium solution, with nano titanium oxide with alcoholic solvent or/and redistilled water mixes, prepare mass concentration and be 0.1～2% nanometer titanium dioxide titanium solution;
S2: the preparation cesiated salt solution, cesium salt to be mixed with alcohol or ether solvents, the preparation mass concentration is 0.1～2% cesiated salt solution;
S3: said nanometer titanium dioxide titanium solution is mixed with cesiated salt solution, obtain mixed liquor;
S4: mixed liquor is spun on the conductive substrates, and heat drying obtains the negative electrode injection material.
Above-mentioned negative electrode injection material preparation method only needs this nano titanium oxide and cesium salt are mixed, and is coated in the substrate, gets final product through heat drying, and its preparation method operation is simple, has improved production efficiency, has reduced production cost, is suitable for suitability for industrialized production.
Particularly, in the preparation method S1 step of above-mentioned negative electrode injection material, this nanometer titanium dioxide titanium solution compound method is preferably this nano titanium oxide is dripped alcoholic solvent or/and redistilled water while grinding.The nano titanium oxide dispersion of preparation can be more even like this.This alcoholic solvent can make nano titanium oxide well disperse, and can make nano titanium oxide form the solution dispersion of homogeneous.Wherein, the alcoholic solvent of nanometer titanium dioxide titanium solution dispersion is preferably in ethanol, n-butanol, isopropyl alcohol, the terpinol at least a.
In the preparation method S2 step of above-mentioned negative electrode injection material; The alcoholic solvent of cesiated salt solution is preferably in ethanol, glyceryl alcohol, n-butanol, isopropyl alcohol, methyl alcohol, the ethylene glycol ethyl ether at least a; Certainly, the alcoholic solvent of cesiated salt solution also can use ether solvents commonly used to substitute.
In the preparation method S3 step of above-mentioned negative electrode injection material; Titanium dioxide in the nanometer titanium dioxide titanium solution dispersion and cesium salt mass ratio in the cesiated salt solution are 1: 0.1～1 to mix; And fully stirring mixes both, and the time of stirring is preferably 15～60min.In order to reach better doping effect, preferably mix with cesiated salt solution during mixing with the isopyknic nanometer titanium dioxide titanium solution of equal in quality mark.
In the preparation method S4 step of above-mentioned negative electrode injection material; The mode of employing spin coating is coated to the conductive substrates surface with the mixed liquor of nanometer titanium dioxide titanium solution and cesiated salt solution, and this is because spin coating can guarantee effectively that the organic layer in the organic electroluminescence device is not destroyed.Certainly, so long as can guarantee the coating method that the organic layer of organic electroluminescence device kind is not destroyed, all are the replacements that are equal to of spin coating mode of the present invention.The mixed liquor that is spun to the surface needs drying, contains impurity such as alcohol simultaneously in this mixed liquor, therefore need impurity be removed.Because this impurity mainly is organic solvents such as alcohol, the mode of therefore preferably taking to heat is removed impurity again, lets impurity volatilize.The mode of heating adopts this area mode commonly used to get final product.The temperature of heat drying is preferably 100～200 ℃, is preferably 15～60min heating time.
This conductive substrates is preferably indium tin oxide glass, mix the tin oxide glass of fluorine, mix the zinc oxide glass of aluminium or mix a kind of 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 the negative electrode injection material, therefore, this negative electrode injection material can be used in organic electroluminescence device.Concrete application mode at least can be following:
As shown in Figure 2.Organic electroluminescence device comprises negative electrode 1 and the organic electroluminescence structure 2 that combines successively with said negative electrode 1, anode 3.Wherein, negative electrode 1 comprises a conductive substrates 11, and is combined in conductive substrates 11 surperficial negative electrode implanted layers 12, and this negative electrode implanted layer 12 is coated to conductive substrates 11 surfaces the mode of above-mentioned negative electrode injection material through spin coating and is prepared from through super-dry.Like this,, make the lumo energy of this negative electrode 1 be improved, match each other with the energy level of organic electroluminescence structure 2 because the negative electrode 1 of this organic electroluminescence device contains above-mentioned negative electrode injection material; Reduced potential barrier between the two, be more suitable for the injection of electronics, electron injection efficiency has been strengthened, simultaneously; Cesium salt has good stable property, can not be condensed into piece, has effectively suppressed the shrinkage cracking on negative electrode 1 surface; To the positive role that life-span of improving organic electroluminescence device has played, in addition, this nano titanium oxide and cesium salt cost are low; Be prone to obtain, therefore, reduced 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 simultaneously, more can carry out good reflection at this negative electrode implanted layer 12 by light, has reduced the loss of light, improves the light extraction ability of organic electroluminescence device.
Above-mentioned conductive substrates 11 is preferably indium tin oxide glass (ito glass), mix the tin oxide glass of fluorine (FTO glass), mix the zinc oxide glass (AZO glass) of aluminium or mix a kind of in the zinc oxide glass (IZO glass) of indium.Particularly, above-mentioned conductive substrates 11 comprises light-transmissive substrates 111 and the conductive layer 112 that is incorporated into light-transmissive substrates 111 surfaces.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.
Above-mentioned light-transmissive substrates 111 is preferably preferably carried out pre-process with light-transmissive substrates 111, like clean and oxygen plasma treatment with before conductive layer 112 combines.Wherein, cleaning way is preferably and uses liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol successively, with the foreign matter on thorough removing light-transmissive substrates 111 surfaces, makes farthest cleaning of light-transmissive substrates 111 surfaces; Light-transmissive substrates 111 is after clean; Carry out oxygen plasma treatment again; The time of this oxygen plasma treatment is preferably 5-15min, and power is preferably 10-50W, and it mainly acts on is roughness and the contact angle that reduces light-transmissive substrates 111 surfaces; Be beneficial to improve the wettability and the adsorptivity of conductive glass surface, and through can further removing its surperficial organic pollution after the surface treatment.
The conductive substrates 11 of this structure can effectively strengthen the mechanical strength of this organic electroluminescence device, effective secluding air, and have excellent conducting performance.Also as transparent surface, therefore, conductive substrates 1 should be transparent or semitransparent shape to this conductive substrates 11 at this, and the preferably clear shape penetrates with the light that organic electroluminescence device is sent.
The material of anode 3 is preferably gold (Au), silver (Ag), platinum (Pt) or aluminium (Al), and its thickness gets final product for present technique field thickness commonly used, but is preferably 100～150nm.
Above-mentioned organic electroluminescence structure 2 comprises luminescent layer 22; Have at least a in hole transmission layer 23, the hole injection layer 24 between this luminescent layer 22 and the anode 3, and/or have electron transfer layer 21 between luminescent layer 22 and the organic electroluminescence device negative electrode 1.Like this, organic electroluminescence structure 2 has following several kinds of structures at least, and certainly, except the following several kinds of structures of enumerating, every is organic electroluminescence structure 2 within this organic electroluminescence structure 2 structural framings, all within technical scheme of the present invention:
First kind of structure: its structure such as Fig. 2 are said, and simultaneously referring to Fig. 1, this organic electroluminescence structure 2 comprises electron transfer layer 21, luminescent layer 22, hole transmission layer 23 and the hole injection layer 24 that combines successively.Wherein, electron transfer layer 21 be combined in organic electroluminescence device negative electrode 1 negative electrode implanted layer 12 with conductive substrates 11 facing surfaces on, hole injection layer 24 combines with anode.
Second kind of structure: this organic electroluminescence structure 2 comprises luminescent layer 22, hole transmission layer 23 and the hole injection layer 24 that combines successively.Wherein, luminescent layer 22 be combined in organic electroluminescence device negative electrode 1 negative electrode implanted layer 12 with conductive substrates 11 facing surfaces on, hole injection layer 24 combines with anode.
The third structure: this organic electroluminescence structure 2 comprises electron transfer layer 21, luminescent layer 22 and the hole injection layer 24 that combines successively.Wherein, electron transfer layer 21 be combined in organic electroluminescence device negative electrode 1 negative electrode implanted layer 12 with conductive substrates 11 facing surfaces on, hole injection layer 24 combines with anode.
The 4th kind of structure: its structure such as Fig. 3 are said, and simultaneously referring to Fig. 1, this organic electroluminescence structure 2 is made up of luminescent layer 22, and this luminescent layer 22 is combined between organic electroluminescence device negative electrode 1 and the anode 3.
Because above-mentioned organic electroluminescence device is in luminescence process, the transmission rate of hole and electronics is inconsistent, has often caused the recombination probability in electronics-hole on the low side, and the brightness of organic electroluminescence device and efficient can not get improving.Therefore; This luminescent layer 22, and/or hole injection layer 24, hole transmission layer 23, electron transfer layer 21 is provided with the injection and the transmission rate of effectively regulating electronics and hole; Equilibrium carrier; The control recombination region is to obtain desirable luminosity and luminous efficiency, simultaneously; Also make embodiment of the invention organic electroluminescence device not only guarantee the good adhesion of 3 on organic function layer and organic electroluminescence device negative electrode 1 and anode, but also make easier being injected in the organic functional thin film of charge carrier from anode 3 and organic electroluminescence device negative electrode 1.For example; Hole injection layer 24 is preferably transition metal oxide, and this material and organic cavity transmission layer 23 energy level comparison match make the hole injection of anode 3 obtain tangible reinforcement; Effectively regulate the injection and the transmission rate in electronics and hole; Equilibrium carrier, the control recombination region makes embodiment of the invention organic electroluminescence device obtain desirable luminosity and luminous efficiency.
Further, the thickness of said hole injection layer 24 is preferably 20～80nm, and its material is preferably transition metal oxide, more preferably MoO
3, WO
3, VO
xOr WO
xHole transmission layer 23 thickness are preferably 20～80nm, and that its material is preferably the 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; 4 '-benzidine (TPD), 1,3, at least a among 5-triphenylbenzene (TDAPB), the 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 of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9; 10-two-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 of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq
3) at least a.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-two (1-naphthyl)-1,3,4-diazole (BND), 1,2, at least a in 4-triazole derivative (like TAZ), N-aryl benzimidazole (TPBI), the quinoxaline derivant (TPQ).
Above-mentioned luminescent layer 22, and/or the combination between the hole injection layer 24, hole transmission layer 23, electron transfer layer 21 can adopt modes such as vapor deposition, sputter, spraying plating or chemical deposition.
Particularly, the preparation method of this organic electroluminescence device adopts this area preparation method commonly used to get final product, and the combination of organic electroluminescence device negative electrode 1, organic electroluminescence structure 2 and anode 3 can adopt modes such as vapor deposition, sputter, spin coating or spraying plating.
Combine instantiation at present, the present invention is further elaborated.
Embodiment 1
The organic electroluminescence device structure of present embodiment is 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 combine 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 surperficial negative electrode implanted layers 12.
Above-mentioned conductive substrates 11 be indium tin oxide glass (ito glass), the thickness of negative electrode implanted layer 12 is 50nm, electron transfer layer 21 is that the thick PBD layer of 50nm, luminescent layer 22 is the thick AlQ of 70nm
3Layer, the MoO that hole transmission layer 23 is the thick TPD layer of 40nm, hole injection layer 2410nm is thick
3Layer and anode 3 are the Au of 150nm.
The organic electroluminescence device preparation method is following:
(1) ito glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 10W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 100nm
2It is 0.8% TiO that particle and absolute ethyl alcohol are configured to mass fraction
2The solution dispersion dropwise adds solvent while grinding during preparation, lets TiO
2Evengranular being dispersed in the alcoholic solvent;
(22) with Cs
2CO
3It is 0.8% solution that inorganic matter and ethylene glycol ethyl ether are configured to mass fraction, and it is for use to stir 1h;
(23) TiO that step (21) is prepared
2Solution and (22) Cs
2CO
3Solution is that 1: 1 ratio is mixed by volume, and it is subsequent use fully to stir 15min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 2000rpm; Be heated to 150 ℃ then and carry out dry 40min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopt vapor deposition to plate PBD layer 21, AlQ successively at negative electrode implanted layer 12 outer surfaces
3Layer 22, TPD layer 23 and MoO
3Layer 24;
(4) at MoO
3Layer 24 outer surface vapor deposition layer of metal Au layer as anode 3, thereby obtain described organic electroluminescence device.
Organic electroluminescence device energy diagram such as Fig. 4 of present embodiment preparation are said; Can know by Fig. 4; The lumo energy of organic electroluminescence device negative electrode 1 is improved, and makes the potential barrier of 2 of organic electroluminescence device negative electrode 1 and organic electroluminescence structures diminish, and electronics can more effectively be transitted to carry out charge transfer in the organic electroluminescence structure 2; And; The HOMO energy level of this material is lower, and effectively blocking hole suppresses hole arrival negative electrode and forms the leakage current that is unfavorable for luminous efficiency.
(its structure is the organic electroluminescence device of present embodiment preparation: ito glass/TiO
2-Cs
2CO
3Negative electrode implanted layer/the PBD/AlQ that mixes
3/ TPD/MoO
3/ Au) with the existing TiO that do not establish
2With Cs
2CO
3The negative electrode implanted layer that mixes and with Al (its structure is: ito glass/Al/PBD/AlQ as the organic electroluminescence device of negative electrode
3/ TPD/MoO
3/ Au) current density and voltage relationship figure sees shown in Figure 5.
Can see that from Fig. 5 cut-in voltage and current density that present embodiment prepares organic electroluminescence device all are significantly improved.After 7V, present embodiment prepares the existing relatively TiO that do not establish of current density of organic electroluminescence device at voltage
2With Cs
2CO
3The negative electrode implanted layer that mixes has also obtained significant raising with Al as the current density of the organic electroluminescence device of negative electrode.Also can draw thus, luminosity and efficient height that present embodiment prepares organic electroluminescence device are significantly improved.
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 2.Its preparation method is following:
(1) ito glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 5min, and power is 50W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 20nm
2It is 0.2% solution that particle and absolute ethyl alcohol are configured to mass fraction, dropwise adds solvent while grinding during preparation, lets TiO
2Evengranular being dispersed in the solution;
(22) with Cs
2CO
3It is 0.2% solution that inorganic matter and ethylene glycol ethyl ether are configured to mass fraction, and it is for use to stir 2h;
(23) TiO that step (21) is prepared
2Solution and (22) Cs
2CO
3Solution is that 1: 1 ratio is mixed by volume, and it is subsequent use fully to stir 30min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 2000rpm; Be heated to 100 ℃ then and carry out dry 60min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopt vapor deposition to plate 20nm thick BND layer 21,20nm thick TBP layer 22,20nm thick CuPc layer 23 and the thick MoO of 20nm successively at negative electrode implanted layer 12 outer surfaces
3Layer 24;
(4) at MoO
3The thick Au layer of layer 24 outer surface vapor deposition layer of metal 100nm as anode 3, thereby obtains described organic electroluminescence device.
The organic electroluminescence device performance classes of test present embodiment preparation is similar to the organic electroluminescence device performance of embodiment 1 preparation.
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 2.Its preparation method is following:
(1) ito glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 10min, and power is 30W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 150nm
2It is 0.5% solution that particle and n-butanol are configured to mass fraction, dropwise adds solvent while grinding during preparation, lets TiO
2Evengranular being dispersed in the solution;
(22) with Cs
2CO
3It is 0.5% solution that inorganic matter and ethylene glycol ethyl ether are configured to mass fraction, and it is for use to stir 2h;
(23) TiO that step (21) is prepared
2Solution and (22) Cs
2CO
3Solution is that 1: 1 ratio is mixed by volume, and it is subsequent use fully to stir 15min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 500rpm; Be heated to 150 ℃ then and carry out dry 30min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopt vapor deposition to plate the thick AlQ of 20nm successively at negative electrode implanted layer 12 outer surfaces
3Layer 21, thick TDAPB layer 23 and the thick VO of 20nm of DCJTB layer 22,20nm that 20nm is thick
xLayer 24;
(4) at VO
xThe thick Au layer of layer 24 outer surface vapor deposition layer of metal 150nm as anode 3, thereby obtains described organic electroluminescence device.
The organic electroluminescence device performance classes of test present embodiment preparation is similar to the organic electroluminescence device performance of embodiment 1 preparation.
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 3.Its preparation method is following:
(1) ito glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 10min, and power is 30W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 200nm
2It is 1% solution that particle and n-butanol are configured to mass fraction, dropwise adds solvent while grinding during preparation, lets TiO
2Evengranular being dispersed in the solution;
(22) with Cs
2CO
3It is 1% solution that inorganic matter and ethylene glycol ethyl ether are configured to mass fraction, and it is for use to stir 5h;
(23) TiO that step (21) is prepared
2Solution and (22) Cs
2CO
3Solution is that 1: 1 ratio is mixed by volume, and it is subsequent use fully to stir 20min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 1000rpm; Be heated to 150 ℃ then and carry out dry 30min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopt vapor deposition to plate the thick AlQ of 80nm successively at negative electrode implanted layer 12 outer surfaces
3Layer 21, thick TDAPB layer 23 and the thick VO of 50nm of BALQ layer 22,80nm that 60nm is thick
xLayer 24;
(4) at VO
xThe thick Al layer of layer 24 outer surface vapor deposition layer of metal 150nm as anode 3, thereby obtains described organic electroluminescence device.
The organic electroluminescence device performance classes of test present embodiment preparation is similar to the organic electroluminescence device performance of embodiment 1 preparation.
Embodiment 5
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 3.Its preparation method is following:
(1) AZO glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 10min, and power is 30W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 200nm
2It is 0.8% solution that particle and redistilled water are configured to mass fraction, dropwise adds solvent while grinding during preparation, lets TiO
2Evengranular being dispersed in the solution;
(22) with Cs
2CO
3It is 0.8% solution that inorganic matter and ethylene glycol ethyl ether are configured to mass fraction, and it is for use to stir 5h;
(23) TiO that step (21) is prepared
2Solution and (22) Cs
2CO
3Solution is that 1: 1 ratio is mixed by volume, and it is subsequent use fully to stir 60min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 4000rpm; Be heated to 200 ℃ then and carry out dry 20min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopt vapor deposition to plate the thick AlQ of 40nm successively at negative electrode implanted layer 12 outer surfaces
3Layer 21, thick TDAPB layer 23 and the thick VO of 80nm of BALQ layer 22,40nm that 60nm is thick
xLayer 24;
(4) at VO
xThe thick Al layer of layer 24 outer surface vapor deposition layer of metal 200nm as anode 3, thereby obtains described organic electroluminescence device.
The organic electroluminescence device performance classes of test present embodiment preparation is similar to the organic electroluminescence device performance of embodiment 1 preparation.
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 1.Its preparation method is following:
(1) AZO glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 10min, and power is 30W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 20nm
2It is 0.4% solution that particle and isopropyl alcohol are configured to mass fraction, dropwise adds solvent while grinding during preparation, lets TiO
2Evengranular being dispersed in the solution;
(22) CsCl inorganic matter and ethanol being configured to mass fraction is 0.4% solution, and it is for use to stir 10h;
(23) TiO that step (21) is prepared
2Solution is pressed TiO with (22) CsCl solution
2With the mass ratio of CsCl is that 1: 0.1 ratio is mixed, and it is subsequent use fully to stir 60min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 3000rpm; Be heated to 200 ℃ then and carry out dry 20min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopt vapor deposition to plate the thick AlQ of 40nm successively at negative electrode implanted layer 12 outer surfaces
3Layer 21, thick TDAPB layer 23 and the thick VO of 80nm of BALQ layer 22,40nm that 60nm is thick
xLayer 24;
(4) at VO
xThe thick Ag layer of layer 24 outer surface vapor deposition layer of metal 200nm as anode 3, thereby obtains described organic electroluminescence device.
The organic electroluminescence device performance classes of test present embodiment preparation is similar to the organic electroluminescence device performance of embodiment 1 preparation.
Embodiment 7
The organic electroluminescence device structure of present embodiment is as embodiment 1 and shown in Figure 1.Its preparation method is following:
(1) IZO glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 10min, and power is 30W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 180nm
2It is 0.1% solution that particle and isopropyl alcohol are configured to mass fraction, dropwise adds solvent while grinding during preparation, lets TiO
2Evengranular being dispersed in the solution;
(22) with CsN
3Being configured to mass fraction with terpinol is 0.1% solution, and it is for use to stir 10h;
(23) TiO that step (21) is prepared
2Solution and (22) CsN
3Solution is pressed TiO
2With CsN
3Mass ratio be that 1: 0.8 ratio is mixed, it is subsequent use fully to stir 60min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 2500rpm; Be heated to 120 ℃ then and carry out dry 50min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopting vapor deposition to plate the thick mass ratio of 40nm successively at negative electrode implanted layer 12 outer surfaces is 1: 1 thick thick TDAPB layer 23 and the thick VO of 80nm of BALQ layer 22,40nm of TPQ layer 21,60nm
xLayer 24;
(4) at VO
xThe thick Pt layer of layer 24 outer surface vapor deposition layer of metal 100nm as anode 3, thereby obtains described organic electroluminescence device.
The organic electroluminescence device performance classes of test present embodiment preparation is similar to the organic electroluminescence device performance of embodiment 1 preparation.
The organic electroluminescence device structure of present embodiment such as Fig. 1, shown in Figure 4, this organic electroluminescence device includes organic electroluminescence devices negative electrode 1, and the luminescent layer 22 and anode 3 that combine 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 surperficial negative electrode implanted layers 12.
The preparation method is following for this organic electroluminescence device:
(1) FTO glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 10min, and power is 30W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 140nm
2It is 2% solution that particle and isopropyl alcohol are configured to mass fraction, dropwise adds solvent while grinding during preparation, lets TiO
2Evengranular being dispersed in the solution;
(22) CsI and ethanol being configured to mass fraction is 2% solution, and it is for use to stir 10h;
(23) TiO that step (21) is prepared
2Solution is pressed TiO with (22) CsI solution
2With the volume ratio of CsI is that 1: 1 ratio is mixed, and it is subsequent use fully to stir 60min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 2500rpm; Be heated to 120 ℃ then and carry out dry 50min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopt vapor deposition to plate the thick AlQ of 60nm at negative electrode implanted layer 12 outer surfaces
3Layer 22;
(4) at AlQ
3The thick Pt layer of layer 22 outer surface vapor deposition layer of metal 150nm as anode 3, thereby obtains described organic electroluminescence device.
Embodiment 9
The organic electroluminescence device structure of present embodiment is referring to 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 combine 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 surperficial negative electrode implanted layers 12.
The organic electroluminescence device preparation method is following:
(1) FTO glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 10min, and power is 30W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 20nm
2It is 1% solution that particle and isopropyl alcohol are configured to mass fraction, fully stirs, and makes TiO
2Evengranular being dispersed in the solution;
(22) CsBr and glyceryl alcohol being configured to mass fraction is 1% solution, and it is for use to stir 10h;
(23) TiO that step (21) is prepared
2Solution and (22) CsBr solution are that 1: 1 ratio is mixed by volume, and it is subsequent use fully to stir 60min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 500rpm; Be heated to 120 ℃ then and carry out dry 50min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopt vapor deposition to plate thick TDAPB layer 23 of 60nm thick BALQ layer 22,40nm and the thick VO of 80nm successively at negative electrode implanted layer 12 outer surfaces
xLayer 24;
(4) at VO
xThe thick Pt layer of layer 24 outer surface vapor deposition layer of metal 150nm as anode 3, thereby obtains described organic electroluminescence device.
The organic electroluminescence device performance classes of test present embodiment preparation is similar to the organic electroluminescence device performance of embodiment 1 preparation.
The organic electroluminescence device structure of present embodiment is referring to 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 combine 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 surperficial negative electrode implanted layers 12.
The organic electroluminescence device preparation method is following:
(1) FTO glass is carried out photoetching treatment, be cut into needed light-emitting area, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol then successively; Clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 10min, and power is 30W; With roughness and the contact angle that reduces conductive glass surface; Improve its surperficial wettability and adsorptivity, remove the organic pollution of conductive glass surface, make conductive substrates 11;
(2) preparation of negative electrode injection material:
(21) with commercially available particle diameter be the TiO of 20nm
2It is 1.5% solution that particle and isopropyl alcohol are configured to mass fraction, fully stirs, and makes TiO
2Evengranular being dispersed in the solution;
(22) CsBr and glyceryl alcohol being configured to mass fraction is 1.5% solution, and it is for use to stir 10h;
(23) TiO that step (21) is prepared
2Solution and (22) CsBr solution are that 1: 1 ratio is mixed by volume, and it is subsequent use fully to stir 60min;
(24) step (23) liquid mixture prepared is spun to the surface of conductive substrates 11 with the rotating speed of 500rpm; Be heated to 120 ℃ then and carry out dry 50min; Thereby form the negative electrode injection material on conductive substrates 11 surfaces, this negative electrode injection material also promptly constitutes negative electrode implanted layer 12;
(3) adopt vapor deposition to plate thick BALQ layer 22 of 70nm thick TPQ layer 21,60nm and the thick VO of 80nm successively at negative electrode implanted layer 12 outer surfaces
xLayer 24;
(4) at VO
xThe thick Pt layer of layer 24 outer surface vapor deposition layer of metal 150nm as anode 3, thereby obtains described organic electroluminescence device.
The organic electroluminescence device performance classes of test present embodiment preparation is similar to the organic electroluminescence device performance of embodiment 1 preparation.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. negative electrode injection material comprises the nano titanium oxide and the cesium salt of mutual doping.
2. negative electrode injection material according to claim 1 is characterized in that: said nano titanium oxide is that particle diameter is the nano-anatase mine-titanium oxide of 20～200nm.
3. negative electrode injection material according to claim 1 is characterized in that: said cesium salt is at least a in cesium carbonate, cesium azide, cesium chloride, cesium bromide, the cesium iodide.
4. according to the arbitrary described negative electrode injection material of claim 1, it is characterized in that: the mass ratio of said nano titanium oxide and cesium salt is 1: 0.1～1.
5. the preparation method of a negative electrode injection material comprises the steps:
Preparation nanometer titanium dioxide titanium solution, with nano titanium oxide with alcoholic solvent or/and redistilled water mixes, prepare mass concentration and be 0.1～2% nanometer titanium dioxide titanium solution;
The preparation cesiated salt solution is mixed cesium salt with alcohol or ether solvents, the preparation mass concentration is 0.1～2% cesiated salt solution;
Said nanometer titanium dioxide titanium solution is mixed with cesiated salt solution, obtain mixed liquor;
Mixed liquor is spun on the conductive substrates, and heat drying obtains the negative electrode injection material.
6. negative electrode injection material preparation method according to claim 5 is characterized in that: the titanium dioxide in the said nanometer titanium dioxide titanium solution dispersion and the cesium salt mass ratio in the cesiated salt solution are 1: 0.1～1 to mix.
7. negative electrode injection material preparation method according to claim 5 is characterized in that, said conductive substrates comprises indium tin oxide glass, mix the tin oxide glass of fluorine, mix the zinc oxide glass of aluminium or mix a kind of in the zinc oxide glass of indium.
8. negative electrode injection material preparation method according to claim 5 is characterized in that: said preparation method further comprises conductive substrates carried out oxygen plasma treatment, and the time of said oxygen plasma treatment is 5-15min, and power is 10-50W.
9. negative electrode injection material preparation method according to claim 5 is characterized in that: the temperature of said heat drying is 100～200 ℃, and be 15～60min heating time.
10. according to each described negative electrode injection material application in organic electroluminescence device of claim 1～4.
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| CN104218177A (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 preparation method thereof |
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| CN104662690A (en) * | 2012-09-28 | 2015-05-27 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| JP2015534230A (en) * | 2012-09-28 | 2015-11-26 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | Organic electroluminescence device and manufacturing method thereof |
| CN104662690B (en) * | 2012-09-28 | 2016-10-26 | 海洋王照明科技股份有限公司 | A kind of organic electroluminescence device and preparation method thereof |
| US9570700B2 (en) | 2012-09-28 | 2017-02-14 | Ocean's King Lighting Science & Technology Co., Ltd. | Organic electroluminescent device and preparation method thereof including forming a cathode by combining zinc oxide, acetic acid and a phthalocyanine substance |
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