CN104183718A - Organic light emission diode and preparation method thereof - Google Patents
Organic light emission diode and preparation method thereof Download PDFInfo
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- CN104183718A CN104183718A CN201310193518.7A CN201310193518A CN104183718A CN 104183718 A CN104183718 A CN 104183718A CN 201310193518 A CN201310193518 A CN 201310193518A CN 104183718 A CN104183718 A CN 104183718A
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/18—Carrier blocking layers
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- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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Abstract
The invention discloses an organic light emission diode and a preparation method thereof. The organic light emission diode comprises a substrate, an anode layer, an organic function layer and a cathode layer which are in stack combination in sequence. The organic function layer comprises a hole transfer layer, a light-emitting layer, an organometallic complex barrier layer, an n-dopant-doped organometallic complex barrier layer and an electron transfer layer which are in stack combination in sequence. A preparation method comprises the steps of providing the substrate, preparing the anode layer, preparing the organic function layer comprising the n-dopant-doped barrier layer, and preparing the cathode layer and the like. The organic light emission diode has excellent use stability, long service life, and excellent luminous efficiency; the process is simple and easy to control the condition; the qualified rate of the finished product is high; the production efficiency is improved effectively; the production cost is reduced; and the organic light emission diode and the preparation method are suitable for industrialized production.
Description
Technical field
The invention belongs to electric light source technology field, relate to specifically a kind of Organnic electroluminescent device 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.
Up to the present, although the scientific research personnel of various countries, the whole world is by selecting suitable organic material and rational OLED device structure design, the indices of OLED device performance is greatly improved.For example adopt the technique of PN doping transport layer, can reduce the starting resistor of OLED device to improve light efficiency, and be conducive to life-time dilatation, but also have problems: P dopant is as relatively poor in the thermal stability of F4-TCNQ, in the use procedure of OLED device, just there is unsteadiness in doped structure itself, particularly for the N doping of electron transfer layer, conventionally adopt alkali metal compound to adulterate, but because alkali metal ion volume is little, diffusivity is strong, diffusion length in organic layer is long, alkali metal ion is except being diffused in transport layer, also can diffuse in luminescent layer, directly cause the cancellation of exciton, affect light efficiency and the life-span of device.
In order to stop the diffusion of dopant, also have at present researcher to adopt organic material to make barrier layer as Bphen, PBD etc., but due to the organic material quality of forming film such as Bphen, PBD and thermal stability poor, its blocking effect is very limited.And in the transmitting procedure of electronics, electronics is from the transport layer of doping while being injected into barrier layer, because the conductivity of bi-material differs larger, therefore has the injection barrier of electronics, for charge carrier, compound in luminescent layer is disadvantageous for this, hinders the raising to OLED device light efficiency.In addition, along with the variation of driving voltage, this barrier properties also can change, thereby causes the unsteadiness of light efficiency.
Therefore, how to extend that on the OLED device basis in useful life, to give the light efficiency that OLED device is higher be a technical barrier that need to overcome simultaneously.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of Organnic electroluminescent device simultaneously with long service life, the high characteristic of luminous efficiency is provided.
Another object of the present invention is to provide a kind of technique simple Organnic electroluminescent device preparation method.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of Organnic electroluminescent device, comprise the substrate, anode layer, organic function layer and the cathode layer that stack gradually combination, wherein, described organic function layer comprises and stacks gradually hole transmission layer, luminescent layer, the organometallic complex barrier layer of combination, organometallic complex barrier layer and the electron transfer layer of n dopant doping.
And the preparation method of above-mentioned Organnic electroluminescent device, comprises the steps:
In vacuum coating system, organometallic complex evaporation is prepared to organometallic complex barrier layer at the luminescent layer outer surface of organic function layer;
In vacuum coating system, n dopant, organometallic complex evaporation are prepared to the organometallic complex barrier layer of n dopant doping in described organometallic complex barrier layer outer surface.
In above-mentioned Organnic electroluminescent device, resilient coating effect, owing to there is no Doped n dopant in organometallic complex, is played in organometallic complex barrier layer, can effectively stop that the quenching phenomenon that n dopant doping causes to diffusion in luminescent layer occurs.The organometallic complex barrier layer of n dopant doping is due to Doped n dopant in organometallic complex, due to organometallic complex self-characteristic, can effectively stop this diffusion of n dopant in organometallic complex, thereby and effectively improved conductivity, and and electron transfer layer between form good ohmic contact, the injection barrier of itself and electron transfer layer contact interface is reduced, improved electron transport ability.In addition, the organometallic complex barrier layer of organometallic complex barrier layer and the doping of this n dopant is all to take organometallic complex as basis material, therefore, does not deposit or Presence of an interface potential barrier hardly at the interface, organometallic complex barrier layer of organometallic complex barrier layer and n dopant doping, thereby be more conducive to the transmission of electronics.Thus, the organometallic complex barrier layer of above-mentioned Organnic electroluminescent device organometallic complex barrier layer and the doping of n dopant forms n doping blocking layer, this n doping blocking layer is thermally-stabilised good, can effectively improve the transmission performance of electronics, and effectively prevent that the quenching phenomenon that n dopant causes to the diffusion of luminescent layer from occurring, and therefore, gives the stability in use of this Organnic electroluminescent device excellence, in long useful life, there is excellent luminous efficiency simultaneously.
The preparation method of above-mentioned Organnic electroluminescent device prepares each layer of structure of organic function layer by evaporation coating method successively at anode layer outer surface, its operation is simple, condition is easily controlled, and product qualified rate is high, has effectively improved production efficiency, reduced production cost, be applicable to industrialization and produce.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention Organnic electroluminescent device structural representation;
Fig. 2 is another preferred structure schematic diagram of embodiment of the present invention Organnic electroluminescent device;
Fig. 3 is embodiment of the present invention Organnic electroluminescent device preparation method's schematic flow sheet;
Fig. 4 is that embodiment 1 and the comparison example 1 of embodiment 1 preparation and comparison example 2 are at 1000cd/m
2under carry out relative brightness-life-span attenuation characteristic curve figure.
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 can effectively solve electronic injection difficulty, and the high Organnic electroluminescent device of luminous efficiency, and its structure as shown in Figure 1 to Figure 2.This Organnic electroluminescent device comprises substrate 1, anode layer 2, organic function layer 3 and the cathode layer 4 that stacks gradually combination.
Particularly, the material of aforesaid substrate 1 is transparent glass, transparent polymer film material etc., as the flexible OLED device of preparing with polymer thin-film material substrate.Certainly, the material of substrate 1 also can adopt this area other materials to substitute.The thickness of substrate 1 also can adopt the conventional thickness in this area or select flexibly according to the requirement of application.
The selected anode material of above-mentioned anode layer 2 is transparent conductive oxide.This transparent conductive oxide is preferably at least one in tin oxide film (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO), gallium zinc oxide (GZO).This preferred transparent conductive oxide has excellent light transmission rate, can effectively improve the light emission rate of this Organnic electroluminescent device, and in addition, this preferred transparent conductive oxide electric conductivity is excellent.These anode layer 2 thickness are preferably 70～200nm.
Above-mentioned organic function layer 3 comprises hole transmission layer 31, luminescent layer 32, n doping blocking layer 33, the electron transfer layer 34 that stacks gradually combination, and the stacked combination in the relative surface of face that combines with substrate layer 1 of hole transmission layer 31 and anode layer 2, electron transfer layer 34 and the stacked combination of cathode layer 6, as shown in Figure 1.
In specific embodiment, the selected material of hole transmission layer 31 in this organic function layer 3 can be 4,4', 4''-tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), N, N, N', N '-tetramethoxy phenyl) at least one in-benzidine (MeO-TPD).Its thickness is between 30nm～80nm.Certainly, hole transmission layer 31 can also be other hole mobile materials well known in the art, and its thickness also can adopt the conventional thickness in this area.
As preferred embodiment, in the hole transmission layer 31 in above-mentioned organic function layer 3, doped with P dopant, that is to say that this hole transmission layer 31 is for the hole transmission layer of P dopant doping.In hole transmission layer 31, doped with P dopant, can effectively improve the transmission performance in these 31 pairs of holes of hole transmission layer.In order to improve as far as possible the hole transport performance of this hole transmission layer 31, in the hole transmission layer of this P dopant doping, the mass ratio of P dopant and hole mobile material is (5～30): 100.
In a preferred embodiment, the P dopant in above-described embodiment is organic substance P dopant or inorganic matter P dopant.Wherein, organic substance P dopant is preferably 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan to naphthoquinones (F6-TNAP), 2, at least one in 2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) two malononitrile (F2-HCNQ); Inorganic matter P dopant is preferably rheium oxide (ReO
3), tungsten oxide (WO
3), molybdenum oxide (MoO
3) at least one.This preferred P dopant can not only improve the transmission performance in 31 pairs of holes of hole transmission layer, the more important thing is and there is good thermal stability, make doped structure in long-term use procedure, be not easy to occur the situation that dedoping or dopant decompose, be conducive to improve Organnic electroluminescent device useful life.Certainly, if do not consider the thermal stability of this P dopant, this P dopant can also be selected other P dopants well known in the art.
In specific embodiment, the selected material of luminescent layer 32 in this organic function layer 3 can be guest materials and material of main part dopant mixture or phosphor material.These luminescent layer 32 thickness are 1～20nm.Certainly, these luminescent layer 32 materials can also be other luminescent materials well known in the art, and its thickness also can adopt the conventional thickness in this area.
When luminescent layer 32 materials are guest materials and material of main part dopant mixture, the mass ratio of guest materials and material of main part is 1～20:100.Wherein, guest materials is luminescent material, it comprises 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3), three (2-phenylpyridines) close at least one in iridium (Ir (ppy) 3).Material of main part comprises 4,4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq
3), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, at least one in 4'-diamines (NPB).
When luminescent layer 32 materials are phosphor material, this phosphor material is 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi), 5,6, in 11,12-tetraphenyl naphthonaphthalene (Rubrene) at least one.
In specific embodiment, the n doping blocking layer 33 in this organic function layer 3 consists of with the organometallic complex barrier layer 332 of n dopant doping the organometallic complex barrier layer 331 of stacked combination.Wherein, the stacked combination in the relative surface of face that combines with hole transmission layer 31 of this organometallic complex barrier layer 331 and luminescent layer 32, the stacked combination in the relative surface of face that combines of the organometallic complex barrier layer 332 of n dopant doping and the cathode layer 4 of electron transfer layer 34.
The organometallic complex barrier layer 332 of n dopant in this n doping blocking layer 33 doping is due to Doped n dopant in organometallic complex basis material, thereby effectively improved conductivity.The organometallic complex barrier layer 332 of this n dopant doping simultaneously can and electron transfer layer 34 between form good ohmic contact, the injection barrier of itself and electron transfer layer 34 contact interfaces is reduced, improved electron transport ability, improve electronics in luminescent layer 33 and the probability of hole-recombination, thereby improved this Organnic electroluminescent device luminous efficiency.In addition, the relation of the metal-complexing of organometallic complex in the organometallic complex barrier layer 332 of this n dopant doping, it has higher glass transition temperature, and thermal stability is better.And in organometallic complex part, contain hydroxyl, oxygen key, easily form hydrogen-oxygen key in intermolecular and molecule, make its coplanarity better, and between molecule and molecule, form stronger being connected, thereby one-tenth thickness homogeneous, the compactness of film is good, stable, and the diffusion of n dopant is played to barrier effect.
Organometallic complex barrier layer 331 in this n doping blocking layer 33 is owing to there is no Doped n dopant in organometallic complex, and this organometallic complex has in the relation of metal-complexing as above and its part and contains hydroxyl, oxygen key, easily form hydrogen-oxygen key in intermolecular and molecule, make its coplanarity better, and between molecule and molecule, form stronger being connected, thereby become thickness homogeneous, the compactness of film is good, glass transition temperature is high, and thermal stability is better.Therefore, resilient coating effect is played on this organometallic complex barrier layer 331, can effectively stop that the quenching phenomenon that n dopant in the electron transfer layer 34 of the organometallic complex barrier layer 332 of n dopant doping or the organometallic complex barrier layer 332 of n dopant doping and n dopant doping hereinafter described causes to diffusion in luminescent layer 32 occurs.Therefore, this organometallic complex barrier layer 331 can make this Organnic electroluminescent device have excellent stability in use, significantly improves its useful life.In addition, the organometallic complex barrier layer 332 of this organometallic complex barrier layer 331 and the doping of n dopant is all to take organometallic complex as basis material, therefore, the organometallic complex barrier layer 332 of organometallic complex barrier layer 331 and n dopant doping does not exist or Presence of an interface potential barrier hardly, thereby be more conducive to the transmission of electronics, improve the light efficiency of this Organnic electroluminescent device.
As preferred embodiment, in the organometallic complex barrier layer 332 of above-mentioned organometallic complex barrier layer 331 and the doping of n dopant, the metal in this organometallic complex is at least one in beryllium, gallium, zinc, indium, aluminium; Organic ligand in organometallic complex is at least one in oxyquinoline, 8-hydroxyquinoline derivative, hydroxy benzo quinoline, hydroxy benzo quinoline.Therefore, this organometallic complex can preferably be selected two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium (BAlq), oxine gallium (Gaq
3), oxine indium (Inq
3), oxine zinc (Znq
2), oxine beryllium (Beq
2), two (10-hydroxy benzo [h] quinoline) beryllium (Bebq
2), three (5-methylol-oxine) aluminium) at least one in (AlOq).The glass transition temperature that this preferred organometallic complex tool is higher is high, and excellent thermal stability is better to the barrier effect of n dopant, thus the life-span that makes of further improving embodiment of the present invention Organnic electroluminescent device.In order further to reduce or to eliminate the interface potential barrier between organometallic complex barrier layer 331 and the organometallic complex barrier layer 332 of n dopant doping completely, the basis material on the organometallic complex barrier layer 332 of organometallic complex barrier layer 331 and the doping of n dopant is selected same organometallic complex.Particularly, BAlq, Gaq
3, Inq
3, Znq
2, Beq
2, Bebq
2, AlOq molecular structural formula as follows:
Because organometallic complex in the organometallic complex barrier layer 332 of said n dopant doping has above-mentioned characteristic, the n dopant that therefore, can adulterate relatively a small amount of in organometallic complex can be realized the electronic transmission performance of organometallic complex barrier layer 332 excellences of n dopant doping.As preferred embodiment, the n dopant in the organometallic complex barrier layer 332 of said n dopant doping and the mass ratio of organometallic complex are (0.5～5): 100.Wherein, n dopant is preferably alkali metal compound, as lithium carbonate (Li
2cO
3), Lithium Azide (LiN
3), cesium azide (CsN
3), cesium carbonate (Cs
2cO
3) etc. at least one in material.This preferred n dopant can not only improve the transmission performance of the 332 pairs of electronics in organometallic complex barrier layer of n dopant doping, and this n dopant Heat stability is good, this doped structure making is not easy to occur the situation that dedoping or dopant decompose in long-term use procedure, is conducive to improve embodiment of the present invention Organnic electroluminescent device useful life.
Further, because above-mentioned organometallic complex has as the glass transition temperature of above-mentioned excellence and thermal stability and the barrier effect good to n dopant, therefore, can the Thickness Design on the organometallic complex barrier layer 332 of organometallic complex barrier layer 331 and the doping of n dopant is thinner.As preferred embodiment, the thickness on above-mentioned organometallic complex barrier layer 331 is 5nm～10nm, and the thickness on the organometallic complex barrier layer 332 of n dopant doping is 5nm～10nm.
In specific embodiment, the selected material of electron transfer layer 34 in this organic function layer 3 can be 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), 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, in 4-triazole derivative (TAZ) at least one.These electron transfer layer 34 thickness are 30～100nm.Certainly, electron transfer layer 34 materials can also be other electron transport materials well known in the art, and its thickness also can adopt the conventional thickness in this area.
As preferred embodiment, in the electron transfer layer 34 in above-mentioned organic function layer 3, doped with n dopant, that is to say that this electron transfer layer 34 is for the electron transfer layer of n dopant doping.In electron transfer layer 34, doped with n dopant, can effectively improve the transmission performance of 34 pairs of electronics of this electron transfer layer.In order to improve as far as possible the electronic transmission performance of this electron transfer layer 34, in the electron transfer layer of this n dopant doping, the mass ratio of n dopant and electron transport material is (5～30): 100.
In a preferred embodiment, the n dopant in above-described embodiment is preferably alkali metal compound, as lithium carbonate (Li
2cO
3), Lithium Azide (LiN
3), cesium azide (CsN
3), cesium carbonate (Cs
2cO
3) etc. at least one in material.This preferred n dopant can not only improve the transmission performance of 34 pairs of electronics of electron transfer layer, and this n dopant Heat stability is good, make doped structure in long-term use procedure, be not easy to occur the situation of dedoping or dopant decomposition, be conducive to improve Organnic electroluminescent device useful life and luminous efficiency.In order to make the electronic transmission performance in the various embodiments described above Organnic electroluminescent device better, the n dopant doping in the organometallic complex barrier layer 332 of this n dopant and the doping of n dopant is above identical.Certainly, this n dopant can also select other n dopants well known in the art to improve 34 pairs of electronic transmission performances of electron transfer layer.
In further preferred embodiment, on the basis of organic function layer 3 as shown in Figure 1, above-mentioned organic function layer 3 can also arrange electronic barrier layer 30, as shown in Figure 2.Wherein, this electronic barrier layer 30 is stacked is combined between hole transmission layer 31 and luminescent layer 32.Arranging of this electronic barrier layer 30 can stop electronics as much as possible and be trapped in luminescent layer 32, with improve electronics in luminescent layer 32 with hole meeting rate, 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, and excited energy, by Radiation-induced deactivation, produces photon, discharge luminous energy, to reach the object of the luminous intensity that strengthens luminescent layer 32.
Particularly, the selected material of this electronic barrier layer 30 can be 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), certainly can also be N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4, the materials such as 4'-diamines (TPD).
In further preferred embodiment, on the basis of organic function layer 3 as shown in Figure 1, 2, above-mentioned organic function layer 3 can also comprise the functional layers such as hole injection layer and electron injecting layer (Fig. 1,2 does not show).This hole injection layer is stacked to be combined between anode layer 2 and hole transmission layer 31, and electron injecting layer is stacked to be combined between electron transfer layer 34 and negative electrode 4.
Particularly, hole injection layer material can be WO
3, VO
x, WO
xor MoO
3in at least one hole-injecting material, or WO
3, VO
x, WO
xor MoO
3in at least one and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the compound of 4'-diamines (NPB), wherein, WO
3, VO
x, WO
xor MoO
3preferably but not only account for the 30wt% of this compound total weight.This electronic injection layer material can lithium iodide, in KI, sodium iodide, cesium iodide, rubidium iodide at least one etc. alkali-metal halide.Certainly, this hole injection layer, electronic injection layer material can also be other materials well known in the art.The thickness of hole injection layer, electron injecting layer also can arrange according to the thickness of this area routine.The setting of this hole injection layer, can effectively strengthen the ohmic contact of 2 of itself and anode layers, has strengthened electric conductivity, improves the hole injectability of anode layer 2 ends.The arranging of electron injecting layer 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, increase exciton amount, obtained desirable luminosity and luminous efficiency.
Above-mentioned cathode layer 4 materials can be selected metal, as one or more the alloy in Ag, Au, Cu, Ni, Pt etc.The thickness of cathode layer 4 can but be not only 70～200nm.Certainly, cathode layer 4 can also be other cathode materials well known in the art, and its thickness also can adopt the conventional thickness in this area.
From the above, organometallic complex barrier layer 331 in above-mentioned Organnic electroluminescent device forms n doping blocking layer with the organometallic complex barrier layer 332 of n dopant doping, this n doping blocking layer is thermally-stabilised good, can effectively improve the transmission performance of electronics, and effectively prevent that the quenching phenomenon that n dopant causes to the diffusion of luminescent layer from occurring, and therefore, gives the stability in use of this Organnic electroluminescent device excellence, in long useful life, there is excellent luminous efficiency simultaneously.In addition, by what respectively hole transmission layer is carried out to P doping and electron transfer layer, carry out n doping, improved respectively the transmission performance of hole and electronics, effectively improved Organnic electroluminescent device light efficiency.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method of Organnic electroluminescent device above.So the method process chart shows as Fig. 3, simultaneously referring to Fig. 1～2, the method comprises the steps:
S01., substrate 1 is provided;
S02. prepare anode layer 2: in vacuum systems, transparent conductive oxide magnetron sputtering is prepared to anode layer 2 on substrate 1 one surfaces of step S01;
S03. prepare organic function layer 3: at step S02, prepare anode layer 2 with light-transmissive substrates layer 1 the combine relative surface of face evaporation hole transmission layer 31, luminescent layer 32, n doping blocking layer 33 and electron transfer layer 34 successively, form organic function layer 3;
S04. prepare cathode layer 4: in vacuum coating system, at organic function layer 3 outer surface evaporations, form cathode layer 4.
Particularly, in above-mentioned S01 step, the structure of substrate 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 substrate 1, as cleaned the step of decontamination, the step of specifically cleaning decontamination is as the step 1 of embodiment 1 below.
In above-mentioned steps S02, transparent conductive oxide and anode layer 2 thickness all as described above, do not repeat them here.Preferably, to become the sputtering technology condition of anode layer 2 be that base vacuum degree is 1 * 10 to sputter transparent conductive oxide
-5～1 * 10
-3pa, the evaporation rate of magnetron sputtering is 0.2～2nm/s.Certainly, the process conditions of preparing anode layer 2 also can be carried out according to existing processing parameter setting.
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, the material that evaporation hole transmission layer 31, luminescent layer 32, electron transfer layer 34 are selected and even thickness are as described above.The operating pressure that each layer of involved process conditions of evaporation are preferably vacuum moulding machine film forming is 1 * 10
-5～1 * 10
-3pa, the evaporation rate of organic material is 0.01～1nm/s.
In this step S03, during evaporating n doping blocking layer 33, concrete grammar is as follows:
In vacuum coating system, organometallic complex evaporation is prepared to organometallic complex barrier layer 331 at luminescent layer 32 outer surfaces of organic function layer 3, then n dopant, organometallic complex evaporation are prepared to the organometallic complex barrier layer 332 of n dopant doping at these organometallic complex barrier layer 331 outer surfaces.
Wherein, the preferred compound of n dopant in the organometallic complex barrier layer 332 of the organometallic complex in the organometallic complex barrier layer 332 of organometallic complex barrier layer 331 and the doping of n dopant and the doping of n dopant and this two-layer even thickness are as described above.The operating pressure that each layer of involved process conditions of evaporation are preferably vacuum moulding machine film forming is 1 * 10
-5～1 * 10
-3pa, evaporation rate is 0.01～1nm/s.Certainly, preparing organometallic complex barrier layer 331 also can carry out according to existing processing parameter setting with organometallic complex barrier layer 332 process conditions of n dopant doping.
When organic function layer 3 as described above, it comprises and stacks gradually hole injection layer, hole transmission layer 31, electronic barrier layer 30, luminescent layer 32, the organometallic complex barrier layer 331 of combination, when the organometallic complex barrier layer 332 of n dopant doping, electron transfer layer 34 and electron injecting layer, the method for preparing organic function layer 3 is in this each layer of structure of anode layer 2 outer surfaces successively evaporation.
In above-mentioned steps S04, the thickness of the cathode material that evaporation cathode layer 4 is used and the cathode layer 4 preparing all as described above, does not repeat them here.Its evaporation condition adopts the process conditions of this area routine, and as the evaporation rate of metal is preferably 0.2～2nm/s, the operating pressure of vacuum moulding machine film forming is 1 * 10
-5～1 * 10
-3pa.
Certainly, it is also understood that the preparation method about embodiment of the present invention Organnic electroluminescent device also should comprise the method for packing that this Organnic electroluminescent device is follow-up.
From the above, the preparation method of above-mentioned Organnic electroluminescent device prepares respectively organic function layer 3, cathode layer 4 by evaporation and sputtering method successively at anode layer 2 outer surfaces, its operation is simple, condition is easily controlled, product qualified rate is high, effectively improved production efficiency, reduced production cost, be applicable to industrialization and produce.
Now, in conjunction with instantiation, embodiment of the present invention Organnic electroluminescent device and preparation method thereof is further elaborated.
Embodiment 1
Penetrate an Organnic electroluminescent device, its structure is: and glass substrate/ITO (100nm)/F6-TNAP:MeO-TPD (1%, 60nm)/TAPC (10nm)/Ir (ppy)
3: TPBi (8%, 15nm)/BAlq (5n m)/BAlq:CsN
3(1%, 5nm)/CsN
3: Bphen (15%, 40nm)/Ag (100nm).
This Organnic electroluminescent device is preparation method comprise the following steps:
1) glass substrate pre-treatment: glass substrate is placed on to the deionized water for ultrasonic that contains washing agent and cleans, ultrasonic processing 20min in isopropyl alcohol, acetone successively after cleaning up, then dry up and obtain clean transparent substrates with nitrogen;
2) preparation of anode layer: in vacuum systems, transparent conductive oxide ITO magnetron sputtering is formed to anode layer in the glass substrate one side through step 1) pre-treatment, the thickness of anode layer is 100nm, then the glass substrate that is formed with anode layer is placed in to plasma processing chamber and carries out plasma treatment;
3) preparation of organic function layer: show hole transmission layer, electronic barrier layer, luminescent layer, the organometallic complex barrier layer of evaporation P dopant doping successively, organometallic complex barrier layer and the electron transfer layer of n dopant doping in anode layer outside; Particularly, each layer of preparation method is as follows:
The preparation of the hole transmission layer of P dopant doping: be 5 * 10 in vacuum degree
-4in the vacuum coating system of Pa, on anode layer outside table, evaporation forms the hole transmission layer that thickness is 60nm, and the material of hole transmission layer is the MeO-TPD of F6-TNAP of having adulterated, and the mass percent that F6-TNAP accounts for hole transmission layer is 1%;
Electronic barrier layer: be 5 * 10 in vacuum degree
-4in the vacuum coating system of Pa, on hole transmission layer, evaporation forms the electronic barrier layer that thickness is 10nm, and the material of electronic barrier layer is TAPC;
Luminescent layer: be 5 * 10 in vacuum degree
-4in the vacuum coating system of Pa, on electronic barrier layer, evaporation forms the luminescent layer that thickness is 15nm, and the material of luminescent layer is the Ir that adulterated (ppy)
3tPBi, Ir (ppy)
3the mass percent that accounts for luminescent layer is 8%;
Organometallic complex barrier layer: be 5 * 10 in vacuum degree
-4in the vacuum coating system of Pa, on luminescent layer, evaporation forms the organometallic complex barrier layer that thickness is 5nm, and material is BAlq;
The organometallic complex barrier layer of n dopant doping: be 5 * 10 in vacuum degree
-4in the vacuum coating system of Pa, by CsN
3, BAlq evaporation forms the organometallic complex barrier layer of n dopant doping in organometallic complex barrier layer outer surface, doping mass ratio is 1%, thickness is 5nm;
The electron transfer layer of n dopant doping: be 5 * 10 in vacuum degree
-4in the vacuum coating system of Pa, on the organometallic complex barrier layer of n dopant doping, evaporation forms the electron transfer layer that thickness is 40nm, and the material of electron transfer layer is the CsN that adulterated
3bphen, CsN
3the mass percent that accounts for electron transfer layer is 15%;
4) preparation of organic function layer: be 5 * 10 in vacuum degree
-4in the vacuum coating system of Pa, on electron transfer layer, evaporation forms negative electrode, and the material of negative electrode is Ag, and the thickness of negative electrode is 100nm, obtains Organnic electroluminescent device.
5) encapsulation: after having made el light emitting device, need to encapsulate device, so that test, packaging technology adopts glass cover-plate encapsulation, adopts conventional technique in industry to make.
Embodiment 2
An Organnic electroluminescent device, its structure is: glass substrate/IZO (70nm)/MoO
3: 2-TNATA (10%, 30nm)/TAPC (5nm)/Ir (piq)
3: NPB (20%, 20nm)/Gaq
3(10nm)/Gaq
3: LiN
3(0.5%, 5nm)/LiN
3: TPBi (5%, 30nm)/Al (70nm).
Its preparation method is with embodiment 1.
Embodiment 3
An Organnic electroluminescent device, its structure is: glass substrate/AZO (100nm)/WO
3: NPB (15%, 40nm)/TAPC (10nm)/DCJTB:Alq
3(1%, 1nm)/Inq
3(10nm)/Inq
3: Li
2cO
3(5%, 10nm)/Li
2cO
3: BCP (5%, 100nm)/Al-Mg (200nm).
Its preparation method is with embodiment 1.
Embodiment 4
An Organnic electroluminescent device, its structure is: glass substrate/GZO (100nm)/F2-HCNQ:CuPc (10%, 30nm)/TAPC (20nm)/Rubrene (10nm)/Znq
2(8nm)/Znq
2: Cs
2cO
3(1%, 5nm)/Cs
2cO
3: TAZ (10%, 30nm)/Ag-Mg (70nm)
Its preparation method is with embodiment 1
Embodiment 5
An Organnic electroluminescent device, its structure is: glass substrate/ITO (100nm)/ReO
3: NPB (8%, and 60nm)/TAPC (10nm)/DPVBi (8%, 15nm)/Beq
2(10nm)/Beq
2: Cs
2cO
3(2%, 5nm)/Cs
2cO
3: PBD (15%, 40nm)/Ag (100nm)
Its preparation method is with embodiment 1
Embodiment 6
An Organnic electroluminescent device, its structure is: glass substrate/ITO (100nm)/F6-TCNQ:ZnPc (5%, and 60nm)/TAPC (10nm)/Ir (MDQ) 2 (acac): NPB (10%, 15nm)/Beb q
2(8nm)/Bebq
2: Cs
2cO
3(1%, 4nm)/Cs
2cO
3: Bphen (10%, 50nm)/Al (100nm)
Its preparation method is with embodiment 1
Embodiment 7
An Organnic electroluminescent device, its structure is: glass substrate/ITO (100nm)/F6-TCNQ:m-MTDATA (8%, and 80nm)/TAPC (10nm)/FIrpic:CBP (8%, 15nm)/AlOq (1 0nm)/AlOq:CsN
3(1%, 3nm)/CsN
3: Bphen (10%, 60nm)/Al (100nm)
Comparative example 1
An Organnic electroluminescent device, its structure is: glass substrate/ITO (100nm)/F6-TNAP:MeO-TPD (1%, 60nm)/TAPC (10nm)/Ir (ppy)
3: TPBi (8%, 15nm)/BAlq (1 0nm)/CsN
3: Bphen (15%, 40nm)/Ag (100nm).This device with embodiment 1 is compared, it is provided with BAlq organometallic complex barrier layer, there is no the organometallic complex barrier layer of n dopant doping.
Comparative example 2
An Organnic electroluminescent device, its structure is: glass substrate/ITO (100nm)/F6-TNAP:MeO-TPD (5%, 60nm)/TAPC (10nm)/Ir (ppy)
3: TPBi (6%, 15nm)/CsN
3: Bphen (15%, 40nm)/Ag (100nm).This device with embodiment 1 is compared, the organometallic complex barrier layer of BAlq organometallic complex barrier layer and n dopant doping is not set.
Organnic electroluminescent device carries out correlated performance test
Above-described embodiment 1 to embodiment 7 and comparison example 1 to the Organnic electroluminescent device of comparison example 2 preparations is carried out to the performances such as useful life and luminous efficiency to be tested, properties method of testing is carried out according to existing known method, and test result is as following table 1:
Table 1
Table 1 is the luminescent properties data of Organnic electroluminescent device of embodiment 1-7 and comparative example 1,2 mades and the data in useful life.Under identical initial brightness, brightness decay is to 70% time, and embodiment 1-7 has all obtained the useful life that surpasses 2000 hours, and comparative example 2 only has 1000 hours.The barrier layer structure that the organometallic complex barrier layer that adopts organometallic complex barrier layer and n dopant to adulterate due to Organnic electroluminescent device of the present invention forms, the diffusion process of block electrons transport layer dopant, avoid luminous quenching phenomenon, thereby can obtain longer useful life.And in comparative example 2 in default of barrier layer structure, have serious luminous quenching phenomenon, so luminous efficiency is very low.Although comparative example 1 also can obtain longer useful life, but due in the transmitting procedure of charge carrier, due to Presence of an interface potential barrier between barrier layer and electron transfer layer, therefore its carrier transmission performance is not as embodiment 1, thereby its light efficiency will be lower than embodiment 1, obviously the Organnic electroluminescent device that prepared by embodiment 1-7 has have excellent luminous efficiency simultaneously long useful life, has higher Practical significance.
By above-described embodiment 1 and comparison example 1 and comparison example 2 at 1000cd/m
2under carry out the attenuation characteristic test of relative brightness-life-span, test result is as shown in Figure 4.As seen from Figure 4, under identical relative brightness, if brightness decay is to 70% time, the Organnic electroluminescent device life-span decay of embodiment 1 preparation slower, service time is longer.
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 Organnic electroluminescent device, comprise the substrate, anode layer, organic function layer and the cathode layer that stack gradually combination, it is characterized in that: described organic function layer comprises and stacks gradually hole transmission layer, luminescent layer, the organometallic complex barrier layer of combination, organometallic complex barrier layer and the electron transfer layer of n dopant doping.
2. Organnic electroluminescent device as claimed in claim 1, is characterized in that: in described organometallic complex barrier material organometallic complex, metal is at least one in beryllium, gallium, zinc, indium, aluminium; In described organometallic complex, organic ligand is at least one in oxyquinoline, 8-hydroxyquinoline derivative, hydroxy benzo quinoline, hydroxy benzo quinoline.
3. Organnic electroluminescent device as claimed in claim 1 or 2, it is characterized in that: described organometallic complex is two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) at least one in aluminium, oxine gallium, oxine indium, oxine zinc, oxine beryllium, two (10-hydroxy benzo [h] quinoline) beryllium, three (5-methylol-oxine) aluminium.
4. Organnic electroluminescent device as claimed in claim 1, is characterized in that: in the organometallic complex barrier layer of described n dopant doping, the mass ratio of described n dopant and organometallic complex is (0.5～5): 100.
5. the Organnic electroluminescent device as described in claim 1 or 4, is characterized in that: described n dopant is at least one in lithium carbonate, Lithium Azide, cesium azide, cesium carbonate.
6. the Organnic electroluminescent device as described in claim 1,2 or 4, is characterized in that: the thickness on described organometallic complex barrier layer is 5nm～10nm, and the thickness on the organometallic complex barrier layer of described n dopant doping is 5nm～10nm.
7. the Organnic electroluminescent device as described in claim 1,2 or 4, is characterized in that: described electron transfer layer is the electron transfer layer of n dopant doping, and wherein, the mass ratio of described n dopant and electron transport material is (5～30): 100.
8. the Organnic electroluminescent device as described in claim 1,2 or 4, is characterized in that: described hole transmission layer is the hole transmission layer of P dopant doping, and wherein, the mass ratio of described P dopant and hole mobile material is (1～10): 100.
9. Organnic electroluminescent device as claimed in claim 8, it is characterized in that: described P dopant is 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones, 2, and 2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) at least one in two malononitrile, rheium oxide, tungsten oxide, molybdenum oxide.
10. a preparation method for Organnic electroluminescent device, comprises the steps:
In vacuum coating system, organometallic complex evaporation is prepared to organometallic complex barrier layer at the luminescent layer outer surface of organic function layer;
In vacuum coating system, n dopant, organometallic complex evaporation are prepared to the organometallic complex barrier layer of n dopant doping in described organometallic complex barrier layer outer surface.
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| CN113972340A (en) * | 2021-10-12 | 2022-01-25 | 深圳市华星光电半导体显示技术有限公司 | OLED display panel and preparation method thereof |
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| CN111081887A (en) * | 2018-10-19 | 2020-04-28 | 上海和辉光电有限公司 | OLED device, preparation method thereof and OLED display device |
| CN111081887B (en) * | 2018-10-19 | 2022-04-26 | 上海和辉光电股份有限公司 | OLED device, preparation method thereof and OLED display device |
| CN113972340A (en) * | 2021-10-12 | 2022-01-25 | 深圳市华星光电半导体显示技术有限公司 | OLED display panel and preparation method thereof |
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