CN104037350A - Organic light emission diode and preparation method thereof - Google Patents
Organic light emission diode and preparation method thereof Download PDFInfo
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- CN104037350A CN104037350A CN201310073046.1A CN201310073046A CN104037350A CN 104037350 A CN104037350 A CN 104037350A CN 201310073046 A CN201310073046 A CN 201310073046A CN 104037350 A CN104037350 A CN 104037350A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
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- H10K50/844—Encapsulations
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- H—ELECTRICITY
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask
Abstract
The invention discloses an organic light emission diode (OLED) and a preparation method thereof. The organic light emission diode comprises a transparent substrate layer, an anode layer, an organic functional layer, a cathode layer, an organic barrier layer and an inorganic barrier layer, wherein the transparent substrate layer, the anode layer, the organic functional layer, and the cathode layer are successively laminated and combined and the organic barrier layer and the inorganic barrier layer are successively and alternately laminated at the outer surface of the cathode layer. Materials used by the inorganic barrier layer include fluorides, sulfides, and oxides, wherein the components are doped mutually; the fluorides account for 10% to 30%, by mole, of the inorganic barrier layer materials and the oxides account for 10% to 30%, by mole, of the inorganic barrier layer materials. According to the invention, corrosion of active materials like water and oxygen and the like on the organic light emission diode can be effectively reduced, thereby obviously improving the stable performance of the OLED and prolonging the service life of the OLED. Besides, the preparation method has advantages of simple process, easily-controlled condition, and easily-large area preparation.
Description
Technical field
The invention belongs to electric light source technology field, include specifically organic electroluminescence devices and preparation method thereof.
Background technology
Organic electroluminescence device (Organic Light Emission Diode, hereinafter to be referred as OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is that the luminous organic material of making one deck tens nanometer thickness on ito glass is made luminescent layer, and there is the metal electrode of one deck low work function luminescent layer top.
The principle of luminosity of OLED is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.
The advantages such as OLED has that luminous efficiency is high, material range of choice is wide, driving voltage is low, entirely solidifies active illuminating, light, thin, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, therefore, by insider, thought to be most likely at the device of new generation that occupies dominance on following illumination and display device market.As a brand-new illumination and Display Technique, the ten years development in the past of OLED technology is swift and violent, has obtained huge achievement.Because the whole world is increasing, throw light on and show that producer drops into research and development one after another, having promoted greatly the industrialization process of OLED, making the growth rate of OLED industry surprising, having arrived the eve of scale of mass production at present.
But find in actual applications, in OLED, organic function layer electroluminescent organic material used is invaded sensitivity especially to oxygen and steam, causes the poor stability of OLED, and useful life is short, thereby has affected applying of OLED.This is because oxygen is triplet state quencher, and luminous quantum efficiency is significantly declined; On the other hand, oxygen can generate carbonyls to the oxidation of luminescent layer, and the carbonyls of this generation is also equivalent to quencher, affecting luminous quantum efficiency significantly declines, meanwhile, after this oxidized luminescent layer is rotten, can form blackspot, and follow luminous efficiency decline energy gap to increase; In addition, oxygen also can be decline its transmission to the oxidation of hole transmission layer.The impact of steam is more obvious, and its main failure mode is the hydrolysis of conduction and organic layer compound, and stability is declined greatly.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of effectively organic electroluminescence device of waterproof, anti-oxygen is provided.
Another object of the present invention is to provide a kind of technique simple organic electroluminescence device preparation method.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of organic electroluminescence device, comprise the light-transmissive substrates layer, anode layer, organic function layer and the cathode layer that stack gradually combination, described organic function layer is included in luminescent layer luminous under the driving of additional power source, on described cathode layer outer surface stacked organic substance barrier layer and the inorganic matter barrier layer that is combined with alternately laminated setting successively also, described inorganic matter barrier material comprises fluoride, sulfide and the oxide of mutual doping; Wherein, described fluoride accounts for 10%～30% of inorganic matter barrier material mole percent, and described oxide accounts for 10%～30% of inorganic matter barrier material mole percent; And described fluoride is LiF, CeF
2, MgF
2, AlF
3, CaF
2or BaF
2, described sulfide is CdS, PbS, FeS
2, CuS, ZnS or NiS, described oxide is TiO
2, MgO, SiO
2, ZrO
2, ZnO or Al
2o
3.
And the preparation method of above-mentioned organic electroluminescence device, comprises the steps:
In vacuum coating system, described organic substance barrier material evaporation is made to organic substance functional layer at cathode layer outer surface;
In vacuum coating system, described inorganic matter barrier material doping is steamed at described organic function layer outer surface and made inorganic described barrier layer altogether;
In described inorganic matter barrier layer outer surface, repeat to prepare successively the step on described organic function layer and inorganic matter barrier layer;
Wherein, the described inorganic matter barrier material in the step of preparation described inorganic matter barrier layer comprises fluoride, sulfide and the oxide of mutual doping; Described fluoride accounts for 10%～30% of inorganic matter barrier layer mole percent, and described oxide accounts for 10%～30% of inorganic matter barrier layer mole percent; And described fluoride is LiF, CeF
2, MgF
2, AlF
3, CaF
2or BaF
2, described sulfide is CdS, PbS, FeS
2, CuS, ZnS or NiS, described oxide is TiO
2, MgO, SiO
2, ZrO
2, ZnO or Al
2o
3.
Above-mentioned organic electroluminescence device is by organic substance barrier layer and inorganic matter barrier layer in cathode layer outer surface setting successively alternately laminated combination; by the synergistic function on this two-layer barrier layer; water, the erosion of oxygen isoreactivity material to this organic electroluminescence device have effectively been reduced; device organic functional material and electrode are formed to effective protection; thereby significantly improved the stability of OLED device, extended the useful life of OLED device.Wherein, adulterated mutually and played synergistic function by fluoride, sulfide and oxide inorganic material in this inorganic matter barrier layer, effectively reduce the stress on inorganic matter barrier layer, make organic substance barrier layer and inorganic matter barrier layer in conjunction with firmly, given the anti-corrosion capability of inorganic matter barrier layer excellence.In addition, the barrier layer light transmittance consisting of organic substance barrier layer and inorganic matter barrier layer is high.
The preparation method of above-mentioned organic electroluminescence device prepares respectively organic substance barrier layer and the inorganic matter barrier layer of alternately laminated combination successively at cathode layer outer surface by evaporation coating method, its operation is simple, condition is easily controlled, easily large area preparation, product qualified rate is high, effectively improved production efficiency, reduced production cost, be applicable to industrialization and produce.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention organic electroluminescence device structural representation;
Fig. 2 is another preferred structure schematic diagram of embodiment of the present invention organic electroluminescence device;
Fig. 3 is embodiment of the present invention organic electroluminescence device preparation method's schematic flow sheet.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of effectively organic electroluminescence device of the anti-oxygen of waterproof, and its structure as shown in Figure 1 to Figure 2.This organic electroluminescence device comprises the light-transmissive substrates layer 1 that stacks gradually, anode layer 2, organic function layer 3, cathode layer 4 and alternately laminated organic substance barrier layer 5 and the inorganic matter barrier layer 6 that is combined in cathode layer 4 outer surfaces successively.
Particularly, the selected material of above-mentioned light-transmissive substrates layer 1 is transparent glass, transparent polymer film material or metal etc., as the flexible OLED device of preparing with the substrate of plastics or metal material.Certainly the selected material of light-transmissive substrates layer 1 also can adopt this area other materials to substitute.The thickness of substrate layer 1 also can adopt the conventional thickness in this area.
The selected material of above-mentioned anode layer 2 is preferably but is not only indium tin oxide (ITO), can also be other anode materials well known in the art.The thickness of thickness anode layer 2 also can adopt the conventional thickness in this area.
Above-mentioned organic function layer 3 comprises hole injection layer 31, hole transmission layer 32, luminescent layer 33, electron transfer layer 34, the electron injecting layer 35 that stacks gradually combination, and the stacked combination in the relative surface of face that combines with substrate layer 1 of hole injection layer 31 and anode layer 2, the stacked combination in the relative surface of face that combines with organic substance barrier layer 5 of electron injecting layer 35 and cathode layer 4, as shown in Figure 1.
In this organic function layer 3, the selected material of hole injection layer 31 can be MoO
3with N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the compound of 4'-diamines (NPB), wherein, MoO
3preferably but not only account for the 30wt% of this compound total weight.Certainly, the selected material of this hole injection layer 31 can be WO
3, VO
xor WO
xetc. other materials well known in the art.The thickness of hole injection layer 31 also can arrange according to the thickness of this area routine.The setting of this hole injection layer 31, can effectively strengthen the ohmic contact of 2 of itself and anode layers, has strengthened electric conductivity, improves the hole injectability of anode layer 4 ends.
The selected material of hole transmission layer 32 can be 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).Certainly, the selected material of this hole transmission layer 32 can be selected from 4,4', 4''-tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4, other known hole mobile materials of at least one in 4'-diamines (TPD) or this area, its thickness also can arrange according to the thickness of this area routine.
Luminescent layer 33 luminescent material used can be selected flexibly according to actual demand (as requirements such as glow colors).As selected TPBI:Ir (ppy)
3, wherein, TPBI(1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene) be material of main part, Ir (ppy)
3(three (2-phenylpyridines) close iridium) is guest materials, and main, object doping weight ratio is 5:100.Certainly, this luminescent layer 33 luminescent material used also can be selected the other materials of this area, as the doping NPB:Ir (MDQ) that is 5wt%
2(acac), wherein, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) is material of main part, two (2-methyl-diphenyl [f, h] quinoxaline (acetylacetone,2,4-pentanedione) (Ir (MDQ)
2(acac)) be guest materials.Can also be that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls close iridium (FIrpic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) and close iridium (Ir (MDQ)
2(acac)), at least one waits luminescent material.The thickness of this luminescent layer 33 can be the thickness range of this area routine.
The selected material of electron transfer layer 34 can be 4,7-diphenyl-1,10-phenanthroline (Bphen).Certainly, the selected material of electron transfer layer 34 can also be other materials well known in the art, as (oxine)-aluminium (Alq
3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2, at least one in 4-triazole derivative (TAZ).The thickness of electron transfer layer 34 also can arrange other thickness ranges of ability routine.In order further to improve the efficiency of transmission of electron transfer layer 34, this electron transfer layer 34 can also be to mix layer structure of mixing that has electric transmission dopant, and wherein, this dopant can be alkali-metal-doped agent, as lithium carbonate (Li
2cO
3), Lithium Azide (LiN
3), cesium azide (CsN
3), cesium carbonate (Cs
2cO
3), one or more in cesium fluoride (CsF) composite.
The selected material of electron injecting layer 35 can be CsN
3with the compound of Bphen, the doping of Bphen is for preferably but be not only 30wt%.Certainly, this electron injecting layer 35 can also be selected other materials well known in the art, as in lithium iodide, KI, sodium iodide, cesium iodide, rubidium iodide at least one etc. alkali-metal halide.The thickness of electron injecting layer 35 also can arrange according to the thickness of this area routine.The arranging of this electron injecting layer 35 can effectively strengthen the ohmic contact between itself and cathode layer 4, strengthened electric conductivity, further improve the electronic injection ability of cathode layer 4 ends, with further equilibrium carrier, control recombination region, in luminescent layer 33, increase exciton amount, obtained desirable luminosity and luminous efficiency.
Certainly, whether the hole injection layer 31 in above-mentioned organic function layer 3 can arrange according to actual needs.Equally, whether electron injecting layer 35 can arrange according to actual needs.
Further, as the preferred embodiment of the present invention, on the basis of organic function layer 3 as shown in Figure 1, electronic barrier layer 36 and hole blocking layer 37 can also be set, wherein, the stacked hole transmission layer 32 that is combined in of this electronic barrier layer 36 is between luminescent layer 33, hole blocking layer 37 is stacked to be combined between luminescent layer 33 and electron transfer layer 34, and its structure as shown in Figure 2.The setting of this electronic barrier layer 36 and hole blocking layer 37, can respectively electronics and hole be trapped in luminescent layer 33 as much as possible, to improve hole and electronics meeting rate in luminescent layer 33, to improve both exciton amounts compound and that form, and exciton energy is passed to luminescent material, thereby the electronics of excitation light-emitting material is from ground state transition to excitation state, excited energy passes through Radiation-induced deactivation, produce photon, discharge luminous energy, to reach the object of the luminous intensity that strengthens luminescent layer 33.As electronic barrier layer 36 can will be trapped in luminescent layer 33 as much as possible from cathode layer 4 injected electrons, hole blocking layer 37 can will be trapped in luminescent layer 33 as much as possible from anode layer 2 injected holes.
Particularly, the selected material of this electronic barrier layer 36 can but be not only N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] material such as cyclohexane (TAPC).The selected material of hole blocking layer 37 can but be not only that TPBi, Bphen are or/and BAlq etc.
Certainly, in the organic function layer shown in Fig. 23, electronic barrier layer 36 and hole blocking layer 37 can be selected a setting according to actual needs.
The structure of above-mentioned cathode layer 4 is ZnS layer, Ag layer and the ZnS layer (being ZnS/Ag/ZnS structure) that stacks gradually combination.Wherein, the thickness of ZnS layer can but be not only 30nm, the thickness of Ag can but be not only 10nm.Certainly, the selected material of this cathode layer 4 can also substitute with other materials known in this field.The thickness of this cathode layer 4 can be the thickness range of this area routine.
The above-mentioned alternately laminated alternately laminated number of times in organic substance barrier layer 5 and inorganic matter barrier layer 6 that is combined in cathode layer 4 outer surfaces successively can be adjusted flexibly according to the emission wavelength of this organic electroluminescence device, so that this organic electroluminescence device has the prerequisite of excellent waterproof, anti-oxygen performance, is issued to the best light effect that goes out.Inventor finds under study for action, when the alternately laminated number of times in organic substance barrier layer 5 and inorganic matter barrier layer 6 is 4～6 times, this two barrier layer can make the effective exclusion of water in this barrier layer, the erosion of oxygen isoreactivity material to this organic electroluminescence device on the one hand, and OLED device is played a protective role; Can also make on the other hand to there is excellent light transmittance by alternately laminated the formed barrier layer in this organic substance barrier layer 5 and inorganic matter barrier layer 6.Therefore the barrier layer structure, consisting of organic substance barrier layer 5 and the inorganic matter barrier layer 6 of this alternately laminated combination has following several preferred embodiment:
The first, organic substance barrier layer 5 and inorganic matter barrier layer 6 successively alternately laminated number of times are 4 times, therefore, the structure on this barrier layer is: 54/ inorganic matter barrier layer 64,63/ organic substance barrier layer, 53/ inorganic matter barrier layer, 62/ organic substance barrier layer, 52/ inorganic matter barrier layer, 61/ organic substance barrier layer, 51/ inorganic matter barrier layer, organic substance barrier layer, as shown in Figure 2;
The second, organic substance barrier layer 5 and inorganic matter barrier layer 6 successively alternately laminated number of times are 5 times, therefore, the structure on this barrier layer is on the basis on barrier layer as shown in Figure 2 how alternately laminated for 1 time, is specially: organic substance barrier layer/inorganic matter barrier layer/organic substance barrier layer/inorganic matter barrier layer/organic substance barrier layer/inorganic matter barrier layer/organic substance barrier layer/inorganic matter barrier layer/organic substance barrier layer/inorganic matter barrier layer;
The third, organic substance barrier layer 5 and inorganic matter barrier layer 6 successively alternately laminated number of times are 6 times, therefore, the structure on this barrier layer is on the basis on barrier layer as shown in Figure 2 how alternately laminated for 2 times, is specially: organic substance barrier layer/inorganic matter barrier layer/organic substance barrier layer/inorganic matter barrier layer/organic substance barrier layer/inorganic matter barrier layer/organic substance barrier layer/inorganic matter barrier layer/organic substance barrier layer/inorganic matter barrier layer/organic substance barrier layer/inorganic matter barrier layer.
Certainly, the alternately laminated number of times in above-mentioned organic substance barrier layer 5 and inorganic matter barrier layer 6 is to be only for 4～6 times preferred embodiment, therefore, organic substance barrier layer 5 and inorganic matter barrier layer 6 successively alternately laminated number of times can also be more than 1 time, and 3 times following or more than 7 times.
Particularly, the organic substance barrier layer 5 of above-mentioned alternately laminated combination and selected material and the thickness in different organic substances barrier layer 5 in inorganic matter barrier layer 6 can be the same or different.Equally, different inorganic matter barrier layer 6 selected material and thickness can be the same or different.
In addition, which kind of structure no matter the barrier layer structure that the above-mentioned organic substance barrier layer 5 by this alternately laminated combination and inorganic matter barrier layer 6 form be, above-mentioned inorganic matter barrier layer 6 materials comprise fluoride, sulfide and the oxide of mutual doping.Wherein, this fluoride accounts for 10%～30% of inorganic matter barrier material mole percent, and this oxide accounts for 10%～30% of inorganic matter barrier material mole percent.
In specific embodiment, the fluoride in 6 materials of above-mentioned inorganic matter barrier layer is LiF, CeF
2, MgF
2, AlF
3, CaF
2or BaF
2, sulfide is CdS, PbS, FeS
2, CuS, ZnS or NiS, oxide is TiO
2, MgO, SiO
2, ZrO
2, ZnO or Al
2o
3.
In 6 materials of above-mentioned inorganic matter barrier layer, oxide stress is little, and fluoride waterproof oxygen ability is strong, has strong anti-corrosion capability; The stress of oxide is minimum, plays stress buffer effect, and sulfide can supplement the room in oxide.Therefore, by fluoride, sulfide and oxide inorganic material, adulterate mutually and play synergistic function, effectively reduce the stress on inorganic matter barrier layer 6, make organic substance barrier layer 5 and inorganic matter barrier layer 6 in conjunction with firm, give the anti-corrosion capability of OLED device excellence, thereby extended the useful life of OLED device.Certainly, it is composite that fluoride, sulfide and every kind of component of oxide also can select two or more corresponding materials to carry out separately, all in scope disclosed by the invention.
In a preferred embodiment, organic substance barrier layer 5 materials in the various embodiments described above comprise organic material and oxide, and wherein, the mole percent that oxide accounts for organic substance barrier layer 5 materials is 30%～50%.In further preferred embodiment, this oxide is MoO
3, V
2o
5, WO
3, Cs
2o, Ni
2o or MnO
2.Certainly this oxide can be also two or more compounds, so long as select wherein a kind of or more than both, all in scope disclosed by the invention.
In further preferred embodiment, organic material in 5 materials of the various embodiments described above organic substance barrier layer is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane (TAPC), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), oxine aluminium (Alq3), 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 4,7-diphenyl-1,10-Phen (BCP), 1,3, at least one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
In the preferred embodiment, this organic substance barrier layer 5 is by this quasi-metal oxides of adulterating in preferred organic material, effectively improved on the one hand the compactness on organic substance barrier layer 5, make on the other hand organic substance barrier layer 5 there is excellent film forming evenness, be beneficial to the film forming on inorganic matter barrier layer 6, effectively prevent the be full of cracks of inorganic matter barrier layer, strengthen the intensity of organic substance barrier layer 5 with the 6 stacked combinations of inorganic matter barrier layer, guaranteed the quality of forming film of organic substance barrier layer 5 with inorganic matter barrier layer 6.Certainly, the material on above-mentioned organic substance barrier layer 5 can be also organic material.
Therefore, above-described embodiment OLED device is the synergistic function with inorganic matter barrier layer 6 by organic substance barrier layer 5, effectively avoid water, the erosion of oxygen isoreactivity material to this organic electroluminescence device, significantly improved the stability of OLED device, extended the useful life of OLED device.Wherein, organic substance barrier layer 5 can supply smooth surface for inorganic matter barrier layer 6, and slows down the stress on inorganic matter barrier layer 6, guarantees the quality of forming film of inorganic matter and prevents its be full of cracks.Inorganic matter barrier layer 6 compactness are high, effectively block water oxygen effect.By making to selecting of organic material and inorganic material the barrier layer densification consisting of organic substance barrier layer 5 and inorganic matter barrier layer 6 respectively, stability is more excellent, waterproof, anti-oxygen better effects if, thereby the useful life of further OLED device simultaneously.Meanwhile, by adjusting organic substance barrier layer 5 and the alternately laminated number of times in inorganic matter barrier layer 6, can also effectively regulate the light transmittance on the barrier layer being formed by organic substance barrier layer 5 and inorganic matter barrier layer 6.
Therefore, as preferred embodiment, the thickness on organic substance barrier layer 5 is 200nm～300nm, and the thickness on inorganic matter barrier layer 6 is 100nm～200nm.
From the above; above-mentioned OLED device is by organic substance barrier layer 5 and inorganic matter barrier layer 6 in cathode layer outer surface setting successively alternately laminated combination; by the synergistic function on this two-layer barrier layer; water, the erosion of oxygen isoreactivity material to this organic electroluminescence device have effectively been reduced; device organic functional material and electrode are formed to effective protection; thereby significantly improved the stability of OLED device, extended the useful life of OLED device.The light transmittance on the barrier layer consisting of this alternately laminated organic substance barrier layer 5 and inorganic matter barrier layer 6 in addition, is high.If the useful life of OLED device in table 1 is below up to more than 3300 hours, light transmittance is up to more than 50%.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method of organic electroluminescence device mentioned above.So the method process chart shows as Fig. 3, simultaneously referring to Fig. 1～2, the method comprises the steps:
S01., light-transmissive substrates layer 1 is provided;
S02. prepare anode layer 2: at the light-transmissive substrates layer 1 one plated surface anode layer 2 of step S01;
S03. prepare organic function layer 3: that at step S02, prepares anode layer 2 plates hole injection layer 31, hole transmission layer 32, luminescent layer 33, electron transfer layer 34, electron injecting layer 35 successively with the light-transmissive substrates layer 1 relative surface of face that combines, and forms organic function layer 3;
S04. prepare cathode layer 4: at the organic function layer 3 outer surface plating cathode layers 4 of step S03;
S05. preparation and cathode layer 4 outer surfaces successively organic substance barrier layer 5 and the inorganic matter barrier layer 6 of alternately laminated combination:
In vacuum coating system, organic substance barrier material evaporation is made to organic substance functional layer 5 at cathode layer 4 outer surfaces;
In vacuum coating system, the doping of inorganic matter barrier material is steamed altogether at organic function layer 5 outer surfaces and made inorganic described barrier layer 6;
At inorganic matter barrier layer 6 outer surfaces, repeat successively to prepare the step on organic function layer 5 and inorganic matter barrier layer 6.
Particularly, in above-mentioned S01 step, the structure of light-transmissive substrates layer 1, material and specification as described above, for length, do not repeat them here.In addition, in this S01 step, also comprise the treatment step in early stage to light-transmissive substrates layer 21, as cleaned the step of decontamination.
In above-mentioned steps S02, substrate is placed in to magnetic control sputtering system at substrate surface spatter film forming, forms anode layer 2.Its sputtering condition adopts the process conditions of this area routine.
Preferably, before carrying out following step S03, also comprise the anode layer 2 in step S02 is carried out to plasma treatment: the substrate that this is coated with to anode layer 2 is placed in plasma processing chamber, carries out plasma treatment.This plasma treatment condition adopts the process conditions of this area routine.After plasma treatment, anode layer 2 can effectively improve anode work function, reduces the injection barrier in hole.
Certainly, also can directly select and be coated with anode as being coated with the transparent substrates of ITO, the transparent substrates that this is coated with to anode is carried out the preliminary treatment in early stage, as carried out following step S03 after the PROCESS FOR TREATMENT such as cleaning, plasma treatment.
In above-mentioned steps S03, after anode layer 2 outer surfaces have plated hole transmission layer 31, at hole transmission layer 31 outer surfaces successively evaporation hole transmission layer 32, luminescent layer 33, electron transfer layer 34, electron injecting layer 35, plate this each layer selected material and even thickness as described above.Each layer of involved process conditions of evaporation are according to the condition of this area routine.
Further, when organic function layer 3 also contains electronic barrier layer 36 and hole blocking layer 37, as shown in Figure 2.Therefore, in this step S03, after hole transmission layer 32, plate and also comprise before luminescent layer 33 before plating the step of electronic barrier layer 36 and plate electron transfer layer 34 after the step of plating luminescent layer 33 and also comprise the step of plating hole blocking layer 37.Plating electronic barrier layer 36, the selected material of hole blocking layer 37 and thickness are respectively as described above.These two-layer involved process conditions of evaporation are according to the condition of this area routine.
In above-mentioned steps S04, the substrate that is coated with organic function layer 3 is placed in to coating system, the cathode material mentioned above of take carries out plated film as plating source at organic function layer 3 outer surfaces, forms cathode layer 4.Its evaporation condition adopts the process conditions of this area routine.
In above-mentioned steps S05, the step of plating organic substance functional layer 5 time, the cathode layer 4 outside evaporations that the selected material of organics function layer 5 is prepared in above-mentioned steps S04 as plating source form organic substance functional layers 5.
Wherein, as described above, its material comprises organic material and oxide to the selected material of organics function layer 5, and wherein, the mole percent that oxide accounts for organic substance barrier layer 5 materials is 30%～50%.Preferably, this oxide is MoO
3, V
2o
5, WO
3, Cs
2o, Ni
2o or MnO
2.This organic substance is at least one in TAPC, NPB as described above, Alq3, m-MTDATA, BCP, TPBi preferably.This organic material and this quasi-metal oxides are carried out common steaming and are formed organic substance functional layer 5.Certainly, the selected material of organics function layer 5 can only select organic material to carry out evaporation masking.
In a preferred embodiment, the process conditions of evaporation formation organic substance functional layer 5 are as follows:
Vacuum degree when the selected material of organics function layer 5 steams is altogether 1 * 10
-5pa～1 * 10
-3pa, the evaporation rate of material is
the process conditions of this preferred evaporation can make the organics function layer 5 of formation more smooth, fine and close.Under the process conditions of this evaporation, the time of evaporation can be adjusted flexibly and control according to the thickness of this organics function layer 5.
In above-mentioned steps S05, the step on plating inorganic matter barrier layer 6 time, the material that plating inorganic matter barrier layer 6 is selected as described above, its material comprises fluoride, sulfide and the oxide of mutual doping, wherein, this fluoride accounts for 10%～30% of inorganic matter barrier layer 6 material mole percents, oxide accounts for 10%～30% of inorganic matter barrier layer 6 material mole percents, and the kind of fluoride, sulfide and the oxide of doping respectively as described above mutually, in order to save length, do not repeat them here.
In a preferred embodiment, the process conditions on evaporation formation inorganic matter barrier layer 6 are as follows:
Vacuum degree when the selected material in inorganic matter barrier layer 6 carries out common steaming is 1 * 10
-5pa～1 * 10
-3pa, the evaporation rate of material is
inorganic matter barrier layer 6 densifications that the process conditions of this preferred evaporation can make to form, evenly.Under the process conditions of this evaporation, the time of evaporation can be adjusted flexibly and control according to the thickness on this inorganic matter barrier layer 6.
In above-mentioned steps S05, when inorganic matter barrier layer 6 outer surfaces repeat to prepare the step on organic function layer 5 and inorganic matter barrier layer 6 successively, the number of times that repeats to prepare organic function layer 5 and inorganic matter barrier layer 6 is preferably 4 to 6 times, certainly as described above, the number of times that repeats to prepare organic function layer 5 and inorganic matter barrier layer 6 can also be more than 1 time, below 3 times or more than 7 times, concrete stacked number of times can be adjusted flexibly according to the emission wavelength of this organic electroluminescence device, so that this organic electroluminescence device reaches the best light effect that goes out.
From the above, the preparation method of above-mentioned organic electroluminescence device prepares respectively organic substance barrier layer 5 and the inorganic matter barrier layer 6 of alternately laminated combination successively at cathode layer outer surface by evaporation coating method, make alternately laminated combined organic barrier layer 5 and inorganic matter barrier layer 6 performance synergistic functions, effectively exclusion of water, the erosion of oxygen equity active material to this organic electroluminescence device.In addition, by adjusting the process conditions of plated film, combined closely in organic substance barrier layer 5 and inorganic matter barrier layer 6, and smooth, fine and close, thus significant prolongation the useful life of OLED device.Its operation of the preparation method of above-mentioned organic electroluminescence device is simple, ripe, and condition is easily controlled, and product qualified rate is high, has effectively improved production efficiency, has reduced production cost, is applicable to industrialization and produces.
Now, in conjunction with instantiation, embodiment of the present invention organic electroluminescence device and preparation method thereof is further elaborated.
Embodiment 1
An organic electroluminescence device, its structure is: glass substrate/ITO/MoO
3: NPB/TCTA/TPBI:Ir (ppy)
3/ Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (MoO
3: TAPC/LiF:CdS:TiO
2)
6.
This organic electroluminescence device is preparation method comprise the following steps:
A) ito glass substrate pre-treatment: acetone cleaning → ethanol cleaning → washed with de-ionized water → ethanol cleans, all cleans with supersonic wave cleaning machine, and individual event washing is cleaned 5 minutes, then with nitrogen, dries up, and stove-drying is stand-by; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content of conductive surface layer, improve the work function of conductive layer surface; ITO thickness is 100nm;
B) preparation of organic function layer: the ITO layer outer surface in step a) plates hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer successively; Particularly,
The preparation of hole injection layer: by MoO
3be doped into N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, in 4'-diamines (NPB), doping is 30wt%, thickness 10nm, vacuum degree 1 * 10
-5pa, evaporation rate
The preparation of hole transmission layer: adopt 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) is as hole mobile material, vacuum degree 3 * 10
-5pa, evaporation rate
evaporation thickness 30nm;
The preparation of luminescent layer: material of main part adopts 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), guest materials adopts three (2-phenylpyridines) to close iridium (Ir (ppy)
3), doping is 5wt%, vacuum degree 3 * 10
-5pa, evaporation rate
evaporation thickness 20nm;
The preparation of electron transfer layer: evaporation one deck 4,7-diphenyl-1,10-phenanthroline (Bphen) is as electron transport material, vacuum degree 3 * 10
-5pa, evaporation rate
evaporation thickness 10nm;
The preparation of electron injecting layer: by CsN
3mix in Bphen, doping is 30wt%, vacuum degree 3 * 10
-5pa, evaporation rate
evaporation thickness 20nm;
C) preparation of cathode layer: negative electrode adopts ZnS/Ag/ZnS, ZnS thickness 30nm, Ag thickness 10nm, vacuum degree 3 * 10
-5pa, evaporation rate
D) making on organic substance barrier layer: organic substance barrier layer is organic material and the oxide-doped work that steams altogether, and organic material is TAPC, and oxide is MoO
3, wherein, MoO
3in organic substance barrier material, shared mole percent is 40%, adopts the mode of vacuum evaporation to prepare, vacuum degree 1 * 10
-5pa, evaporation rate
thickness 250nm;
E) making on inorganic matter barrier layer: inorganic matter barrier layer is fluoride, sulfide and the oxide-doped work that steams altogether, and fluoride is LiF, and sulfide is CdS, and oxide is TiO
2, wherein, in LiF 20% of inorganic matter barrier material mole percent, TiO
2account for 30% of inorganic matter barrier material mole percent, vacuum degree 1 * 10
-5pa, evaporation rate
thickness 150nm;
F) alternately repeat d) and e) 6 times.
Embodiment 2
An organic electroluminescence device, its structure is: glass substrate/ITO/MoO
3: NPB/TCTA/TPBI:Ir (ppy)
3/ Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (V
2o
5: NPB/CeF
2: PbS:MgO)
5.
This organic electroluminescence device is preparation method comprise the following steps:
A), b), c) with embodiment 1;
D) making on organic substance barrier layer: organic substance barrier layer is organic material and the oxide-doped work that steams altogether, and organic material is V
2o
5, oxide is NPB, wherein, and V
2o
5in organic substance barrier material, shared mole percent is 40%, adopts the mode of vacuum evaporation to prepare, vacuum degree 5 * 10
-5pa, evaporation rate
thickness 300nm;
E) making on inorganic matter barrier layer: inorganic matter barrier layer is fluoride, sulfide and the oxide-doped work that steams altogether, and fluoride is CeF
2, sulfide is PbS, oxide is MgO, wherein, CeF
2account for 15% of inorganic matter barrier material mole percent, MgO accounts for 15% of inorganic matter barrier material mole percent, vacuum degree 5 * 10
-5pa, evaporation rate
thickness 100nm;
F) alternately repeat d) and e) 5 times.
Embodiment 3
An organic electroluminescence device, its structure is: glass substrate/ITO/MoO
3: NPB/TCTA/TPBI:Ir (ppy)
3/ Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (WO
3: Alq3/MgF
2: FeS
2: SiO
2)
5.
This organic electroluminescence device is preparation method comprise the following steps:
A), b), c) with embodiment 1;
D) making on organic substance barrier layer: organic substance barrier layer is organic material and the oxide-doped work that steams altogether, and organic material is Alq3, and oxide is WO
3, wherein, WO
3in organic substance barrier material, shared mole percent is 30%, adopts the mode of vacuum evaporation to prepare, vacuum degree 5 * 10
-5pa, evaporation rate
thickness 200nm;
E) making on inorganic matter barrier layer: inorganic matter barrier layer is fluoride, sulfide and the oxide-doped work that steams altogether, and fluoride is MgF
2, sulfide is FeS
2, oxide is SiO
2, wherein, MgF
2account for 16% of inorganic matter barrier material mole percent, SiO
2account for 18% of inorganic matter barrier material mole percent, vacuum degree 5 * 10
-5pa, evaporation rate
thickness 200nm;
F) alternately repeat d) and e) 5 times.
Embodiment 4
An organic electroluminescence device, its structure is: glass substrate/ITO/MoO
3: NPB/TCTA/TPBI:Ir (ppy)
3/ Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (Cs
2o:m-MTDATA/AlF
3: CuS:ZrO
2)
5
This organic electroluminescence device is preparation method comprise the following steps:
A), b), c) with embodiment 1;
D) making on organic substance barrier layer: organic substance barrier layer is organic material and the oxide-doped work that steams altogether, and organic material is m-MTDATA, and oxide is Cs
2o, wherein, Cs
2o shared mole percent in organic substance barrier material is 50%, adopts the mode of vacuum evaporation to prepare, vacuum degree 5 * 10
-5pa, evaporation rate
thickness 240nm;
E) making on inorganic matter barrier layer: inorganic matter barrier layer is fluoride, sulfide and the oxide-doped work that steams altogether, and fluoride is AlF
3, sulfide is CuS, oxide is ZrO
2, wherein, AlF
3account for 15% of inorganic matter barrier material mole percent, ZrO
2in 20% of inorganic matter barrier material mole percent, vacuum degree 5 * 10
-5pa, evaporation rate
thickness 180nm;
F) alternately repeat d) and e) 5 times.
Embodiment 5
An organic electroluminescence device, its structure is: glass substrate/ITO/MoO
3: NPB/TCTA/TPBI:Ir (ppy)
3/ Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (Ni
2o:BCP/CaF
2: ZnS:ZnO)
5.
This organic electroluminescence device is preparation method comprise the following steps:
A), b), c) with embodiment 1;
D) making on organic substance barrier layer: organic substance barrier layer is organic material and the oxide-doped work that steams altogether, and organic material is BCP, and oxide is Ni
2o, wherein, Ni
2o shared mole percent in organic substance barrier material is 45%, adopts the mode of vacuum evaporation to prepare, vacuum degree 5 * 10
-5pa, evaporation rate
thickness 260nm;
E) making on inorganic matter barrier layer: inorganic matter barrier layer is fluoride, sulfide and the oxide-doped work that steams altogether, and fluoride is CaF
2, sulfide is ZnS, oxide is ZnO, wherein, CaF
2account for 30% of inorganic matter barrier material mole percent, ZnO accounts for 10% of inorganic matter barrier material mole percent, vacuum degree 5 * 10
-5pa, evaporation rate
thickness 140nm;
F) alternately repeat d) and e) 5 times.
Embodiment 6
An organic electroluminescence device, its structure is: glass substrate/ITO/MoO
3: NPB/TCTA/TPBI:Ir (ppy)
3/ Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (MnO
2: TPBi/BaF
2: NiS:Al
2o
3)
4.
This organic electroluminescence device is preparation method comprise the following steps:
A), b), c) with embodiment 1;
D) making on organic substance barrier layer: organic substance barrier layer is organic material and the oxide-doped work that steams altogether, and oxide is MnO
2, organic material TPBi, wherein, MnO
2in organic substance barrier material, shared mole percent is 40%, adopts the mode of vacuum evaporation to prepare, vacuum degree 1 * 10
-3pa, evaporation rate
thickness 220nm;
E) making on inorganic matter barrier layer: inorganic matter barrier layer is fluoride, sulfide and the oxide-doped work that steams altogether, and fluoride is BaF
2, sulfide is NiS, oxide is Al
2o
3, wherein, BaF
2account for 10% of inorganic matter barrier material mole percent, Al
2o
3account for 20% of inorganic matter barrier material mole percent, vacuum degree 1 * 10
-3pa, evaporation rate
thickness 150nm;
F) alternately repeat d) and e) 4 times.
Comparison example
An organic electroluminescence device, its structure is: glass substrate/ITO/MoO
3: NPB/TCTA/TPBI:Ir (ppy)
3/ Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (BaF
2)
4.
This organic electroluminescence device is preparation method comprise the following steps:
A), b), c) with embodiment 1;
D) making on inorganic matter barrier layer: inorganic matter barrier material is BaF
2, vacuum degree 1 * 10
-3pa, evaporation rate
thickness 150nm;
E) repetition d) 4 times.
Organic electroluminescence device carries out correlated performance test
Organic electroluminescence device prepared by above-described embodiment 1 to embodiment 6 and comparison example carries out the performances such as WVTR, light transmittance and life-span to be tested, and properties method of testing is carried out according to existing known method, and test result is as following table 1:
Table 1
Data by the embodiment 1 to embodiment 6 in table 1 are known, the WVTR(water vapor permeable rate of organic electroluminescence device prepared by the embodiment of the present invention) reach 10
-4g/m
2day; Life-span reaches 3,300 hours above (T70@1000cd/m
2), and the light transmittance on the barrier layer consisting of organic substance barrier layer and inorganic matter barrier layer reaches more than 50%.Above-described embodiment 1 to embodiment 6 is compared with comparison example, the useful life of above-described embodiment 1-6 organic electroluminescence device is apparently higher than the useful life in comparison example, therefore, organic barrier layer in embodiment of the present invention organic electroluminescence device and the synergistic function on inorganic matter barrier layer, effectively avoid water, the erosion of oxygen isoreactivity material to this organic electroluminescence device, extended the useful life of OLED device.And in comparison example stress problem is frangible is prone to be full of cracks due to self on the barrier layer of OLED device, thereby further shortened the useful life of OLED device.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, comprise the light-transmissive substrates layer, anode layer, organic function layer and the cathode layer that stack gradually combination, described organic function layer is included in luminescent layer luminous under the driving of additional power source, it is characterized in that: on described cathode layer outer surface stacked organic substance barrier layer and the inorganic matter barrier layer that is combined with alternately laminated setting successively also, described inorganic matter barrier material comprises fluoride, sulfide and the oxide of mutual doping; Wherein, described fluoride accounts for 10%～30% of inorganic matter barrier material mole percent, and described oxide accounts for 10%～30% of inorganic matter barrier material mole percent; And described fluoride is LiF, CeF
2, MgF
2, AlF
3, CaF
2or BaF
2, described sulfide is CdS, PbS, FeS
2, CuS, ZnS or NiS, described oxide is TiO
2, MgO, SiO
2, ZrO
2, ZnO or Al
2o
3.
2. organic electroluminescence device as claimed in claim 1, is characterized in that: described organic substance barrier material comprises organic material and oxide, and the mole percent that described oxide accounts for described organic substance barrier material is 30%～50%.
3. organic electroluminescence device as claimed in claim 2, is characterized in that: described oxide is MoO
3, V
2o
5, WO
3, Cs
2o, Ni
2o or MnO
2.
4. organic electroluminescence device as claimed in claim 2 or claim 3, it is characterized in that: described organic material is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen, 1,3, at least one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.
5. the organic electroluminescence device as described in claim 1～3 any one, is characterized in that: the thickness on described organic substance barrier layer is 200nm～300nm, and the thickness on described inorganic matter barrier layer is 100nm～200nm.
6. the organic electroluminescence device as described in claim 1～3 any one, is characterized in that: the alternately laminated number of times on described organic substance barrier layer and inorganic matter barrier layer is 4～6 times.
7. a preparation method for organic electroluminescence device, comprises the steps:
In vacuum coating system, described organic substance barrier material evaporation is made to organic substance functional layer at cathode layer outer surface;
In vacuum coating system, described inorganic matter barrier material doping is steamed at described organic function layer outer surface and made inorganic described barrier layer altogether;
In described inorganic matter barrier layer outer surface, repeat to prepare successively the step on described organic function layer and inorganic matter barrier layer;
Wherein, described inorganic matter barrier material in the step of preparation described inorganic matter barrier layer comprises fluoride, sulfide and the oxide of mutual doping, described fluoride accounts for 10%～30% of inorganic matter barrier material mole percent, and described oxide accounts for 10%～30% of inorganic matter barrier material mole percent; And described fluoride is LiF, CeF
2, MgF
2, AlF
3, CaF
2or BaF
2, described sulfide is CdS, PbS, FeS
2, CuS, ZnS or NiS, described oxide is TiO
2, MgO, SiO
2, ZrO
2, ZnO or Al
2o
3.
8. the preparation method of organic electroluminescence device as claimed in claim 7, is characterized in that: in the step on the described organics function layer of preparation and/or inorganic matter barrier layer, vacuum degree during described evaporation is 1 * 10
-5pa～1 * 10
-3pa, described organic substance barrier material evaporation rate is
9. organic electroluminescence device as claimed in claim 7 or 8, is characterized in that: described organic substance barrier material comprises organic material and oxide, and the mole percent that described oxide accounts for described organic substance barrier material is 30%～50%.
10. organic electroluminescence device as claimed in claim 9, is characterized in that: described oxide is MoO
3, V
2o
5, WO
3, Cs
2o, Ni
2o or MnO
2.
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| CN1875664A (en) * | 2003-11-07 | 2006-12-06 | 出光兴产株式会社 | Barrier film for light-emitting display device and method for manufacturing same |
| US20070228382A1 (en) * | 2002-06-11 | 2007-10-04 | Shunpei Yamazaki | Light emitting device and manufacturing method thereof |
| US20090267487A1 (en) * | 2008-04-24 | 2009-10-29 | Kwack Jin-Ho | Organic light emitting display device |
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|---|---|---|---|---|
| CN1543514A (en) * | 2001-08-20 | 2004-11-03 | ��˹��ŵ�� | Coatings with low permeation of gases and vapors |
| US20070228382A1 (en) * | 2002-06-11 | 2007-10-04 | Shunpei Yamazaki | Light emitting device and manufacturing method thereof |
| CN1875664A (en) * | 2003-11-07 | 2006-12-06 | 出光兴产株式会社 | Barrier film for light-emitting display device and method for manufacturing same |
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Application publication date: 20140910 |