CN104183713A - Top-emission organic light emission diode and preparation method thereof - Google Patents
Top-emission organic light emission diode and preparation method thereof Download PDFInfo
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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Abstract
The invention discloses a top-emission organic light emission diode and a preparation method thereof. The top-emission organic light emission diode includes a substrate, an anode layer, an organic function layer, a PN junction and a cathode layer, which are sequentially laminated and combined. The organic function layer includes a light-emitting layer, and a P-type semiconductor layer of the PN junction and the cathode layer are laminated and combined, and an N-type semiconductor layer of the PN junction and the organic function layer are laminated and combined, wherein the material of the P-type semiconductor layer is a phthalocyanine compound and the material of the N-type semiconductor layer is a fullerene material. The preparation method includes a step of sequential vapor deposition of the PN junction and the cathode layer on the outer surface of the organic function layer. The top-emission organic light emission diode is high in light-emitting efficiency, low in start voltage, simple in working procedure, easy in condition control, high in finished-product qualified rate, capable of effectively improving production efficiency and reducing production cost, and suitable for industrialized production.
Description
Technical field
The invention belongs to electric light source technology field, relate to specifically a kind of top radiation organic EL part 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, thought to be most likely at by insider 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.Throw light on because the whole world is increasing 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.
At present, the development of OLED is very rapid, and in order to expand its application and to simplify its manufacture craft, researchers have developed the OLED light-emitting device of various structures, for example top transmitting light-emitting device, inverted type light-emitting device.Be applied at present in the OLED device of display unit, conventionally adopt the structure of top transmitting, this is that bright dipping can only be from the cathode emission at top because display unit needs opaque silicon materials as substrate conventionally.And the material of top negative electrode normally adopts metal film layer, but the transmitance of this metal film layer only has between 60%～70%, thereby affected the light extraction efficiency of device.In order to improve the structure OLED light extraction efficiency of top transmitting, the transparent conductive oxide film alternative metals thin layer adopting at present.As ITO has up to more than 80% transmitance, its electric conductivity is also very excellent, but the work content of this conductive oxide film is high, if the work content of ito thin film is up to 4.7eV, during as negative electrode, its work content is too high and cause electronic injection difficulty, makes the luminous efficiency of device very low.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide one can effectively solve electronic injection difficulty, and the high top radiation organic EL device of luminous efficiency.
Another object of the present invention is to provide the simple top radiation organic EL device of a kind of technique preparation method.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of top radiation organic EL device, comprise the substrate, anode layer, organic function layer and the cathode layer that stack gradually combination, described organic function layer comprises luminescent layer, described top radiation organic EL device is the folded PN junction being combined between described cathode layer and organic function layer of covering also, the p type semiconductor layer of described PN junction and the stacked combination of described cathode layer, the n type semiconductor layer of described PN junction and the stacked combination of described organic function layer; Wherein, described P type semiconductor layer material is phthalocyanine compound, and described N type semiconductor layer material is fullerene-based material.
And the preparation method of above-mentioned top radiation organic EL device, comprises the steps:
In vacuum coating system, fullerene-based material evaporation is prepared to n type semiconductor layer at organic function layer outer surface;
In vacuum coating system, phthalocyanine compound evaporation is prepared to p type semiconductor layer at described n type semiconductor layer outer surface, described p type semiconductor layer and described n type semiconductor layer form PN junction;
In vacuum systems, transparent conductive oxide magnetron sputtering is prepared to cathode layer at described PN junction outer surface.
Above-mentioned top radiation organic EL device arranges PN junction layer between organic function layer and cathode layer, when under the effect in external electrical field, in the interface formation separation of charge of this PN junction layer, and hole is moved to cathode layer, electronics moves to organic function layer, make in electronic injection organic function layer and to arrive luminescent layer excitation light-emitting material luminous, cause the technical problem of electronic injection difficulty because work content is high thereby efficiently solve as the negative electrode of light-emitting area, and give the luminous efficiency that this top radiation organic EL device is high.In PN junction, the stability that employing fullerene-based material is prepared n type semiconductor layer is high, is combined firmly with p type semiconductor layer, is not easy to produce the phenomenon of phase-splitting, and gives hole-electronics separating effect of this PN junction excellence.
The preparation method of above-mentioned top radiation organic EL device prepares n type semiconductor layer and p type semiconductor layer formation PN junction by evaporation coating method successively at organic function layer outer surface, its operation is simple, condition is easily controlled, product qualified rate is high, effectively improve production efficiency, reduce production cost, be applicable to industrialization and produce.
Brief description of the drawings
Fig. 1 is embodiment of the present invention top radiation organic EL apparatus structure schematic diagram;
Fig. 2 is another preferred structure schematic diagram of embodiment of the present invention top radiation organic EL device;
Fig. 3 is embodiment of the present invention top radiation organic EL device preparation method's schematic flow sheet;
Fig. 4 is the voltage-to-current density characteristic curve figure of the device made of the top radiation organic EL device prepared of embodiment 1 and comparison example 1.
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 one can effectively solve electronic injection difficulty, and the high top radiation organic EL device of luminous efficiency, and its structure as shown in Figure 1 to Figure 2.This Organnic electroluminescent device comprises the substrate 1, anode layer 2, organic function layer 3, PN junction 4 and the cathode layer 6 that stack gradually combination.
Particularly, the material of aforesaid substrate 1 is transparent glass, transparent polymer film material etc., as the flexible top transmitting 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.
Above-mentioned anode layer 2 materials can be selected metal, as one or more the alloy in Ag, Au, Cu, Ni, Pt etc.The thickness of anode layer 2 can but be not only 70～200nm.Certainly, anode layer 2 can also be other anode materials well known in the art, and its thickness also can adopt the conventional thickness in this area.
Above-mentioned organic function layer 3 comprises the hole transmission layer 31, luminescent layer 32, the electron transfer layer 33 that stack 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 33 and the stacked combination in the relative surface of face that combines with cathode layer 6 of PN junction 4 be and the stacked combination of n type semiconductor layer 41 of PN junction 4, 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), 4, 4', at least one in 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).Its thickness is between 20～60nm.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.
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.
In the time that 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 1～10:100.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 (Alq3), 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).
In the time that luminescent layer 32 materials are phosphor material, this phosphor material is 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4, two [4-(di-p-tolyl amino) styryl] biphenyl (DPAVBi), 5,6 of 4'-, in 11,12-tetraphenyl naphthonaphthalene (Rubrene) at least one.
In specific embodiment, the selected material of electron transfer layer 33 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 33 thickness are 20～60nm.Certainly, electron transfer layer 33 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.
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 (Fig. 1,2 does not show).This hole injection layer is stacked to be combined between anode layer 2 and hole transmission layer 31.
Particularly, the selected material of hole injection layer can be hole-injecting material, as WO
3, V
2o
5, or MoO
3in at least one, or WO
3, V
2o
5or 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, V
2o
5or MoO
3preferably but not only account for the 30wt% of this compound total weight.Certainly, the selected material of this hole injection layer can be other materials well known in the art.The thickness of hole injection 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 between itself and anode layer 2, has strengthened electric conductivity, improves the hole injectability of anode layer 2 ends.
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 arrange electronic barrier layer and hole blocking layer (Fig. 1,2 does not show), wherein, this electronic barrier layer is stacked to be combined between hole transmission layer 31 and luminescent layer 32, and hole blocking layer is stacked to be combined between luminescent layer 32 and electron transfer layer 33.The setting of this electronic barrier layer and hole blocking layer, can respectively electronics and hole be trapped in luminescent layer 32 as much as possible, to improve hole and electronics meeting rate in luminescent layer 32, 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 32.As electronic barrier layer can will be trapped in luminescent layer 32 as much as possible from cathode layer 6 injected electrons, hole blocking layer can will be trapped in luminescent layer 32 as much as possible from anode layer 2 injected holes.
Particularly, the selected material of this electronic barrier layer 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 can but be not only that TPBi, Bphen are or/and BAlq etc.
Certainly, this electronic barrier layer and hole blocking layer also can be selected a setting according to actual needs.
The setting of above-mentioned PN junction 4, when under the effect in external electrical field, in the interface formation separation of charge of PN junction layer 4, hole is moved to cathode layer 6, electronics moves to organic function layer 3, make in electronic injection organic function layer 3 and to arrive luminescent layer 32 excitation light-emitting materials luminous, thereby efficiently solve the technical problem that causes electronic injection difficulty as the negative electrode of light-emitting area because work content is high.Therefore, the embodiment of the present invention top radiation organic EL device that is arranged so that of PN junction 4 has high luminance, meanwhile, because PN junction 4 has reduced electronic injection difficulty, therefore, effectively reduces the starting resistor of top radiation organic EL device of the present invention.This PN junction 4 is made up of with p type semiconductor layer 42 n type semiconductor layer 41 of mutual stacked combination, and n type semiconductor layer 41 and the stacked combination of organic function layer 3, p type semiconductor layer 42 and the stacked combination of cathode layer 6.
In specific embodiment, n type semiconductor layer 41 materials in this PN junction 4 are fullerene-based material.This fullerene-based material is preferably carbon 60 and/or carbon 70.This preferred fullerene-based material can be prepared tunic with technique for vacuum coating, has excellent stability, makes n type semiconductor layer 41 firm with p type semiconductor layer 42 combinations, is not easy to produce the phenomenon of phase-splitting.In a preferred embodiment, the thickness of n type semiconductor layer 41 is 1nm～20nm.In this thickness range, the charge carrier of separation can effectively transmit, the charge carrier quenching phenomenon of avoiding long-distance migration to cause.
P type semiconductor layer 42 materials in this PN junction 4 are phthalocyanine compound.This phthalocyanine compound is preferably CuPc (CuPc), Phthalocyanine Zinc (ZnPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), at least one in phthalocyanine platinum (PtPc).In a preferred embodiment, the thickness of p type semiconductor layer 42 is 1nm～20nm.In this thickness range, the charge carrier of separation can effectively transmit, the charge carrier quenching phenomenon of avoiding long-distance migration to cause.
In further preferred embodiment, top radiation organic EL device in the various embodiments described above also comprises metal oxide layer 5, this metal oxide layer 5 is stacked to be combined between PN junction 4 and cathode layer 6, concrete is between the stacked p type semiconductor layer 42 and cathode layer 6 that is combined in PN junction 4, as shown in Figure 2.The setting of this metal oxide layer 5, can make, in the time of the cathode layer 6 of this top radiation organic EL device of preparation, can effectively protect the p type semiconductor layer 42 material phthalocyanine compounds in PN junction 4 not to be destroyed, and plays the cushioning effect of protectiveness.In order better to protect p type semiconductor layer 42 material phthalocyanine compounds not to be destroyed, particularly, this metal oxide layer material is MoO
3, ReO
3, WO
3, V
2o
5, Sb
2o
3in at least one.
As preferred embodiment, the thickness of this metal oxide layer 5 is 1nm～5nm.The metal oxide layer 5 of this preferred thickness can ensure that p type semiconductor layer 42 material phthalocyanine compounds are not destroyed, and can not affect again the transmitance of light.
The selected cathode material of above-mentioned cathode layer 6 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 top radiation organic EL device, in addition, and this preferred transparent conductive oxide electric conductivity excellence.These cathode layer 6 thickness are preferably 50～100nm.
From the above, above-mentioned top radiation organic EL device arranges PN junction layer 4 between organic function layer 3 and cathode layer 6, when under the effect in external electrical field, in the interface formation separation of charge of PN junction layer 4, hole is moved to cathode layer 6, electronics moves to organic function layer 3, make in electronic injection organic function layer 3 and to arrive luminescent layer 32 excitation light-emitting materials luminous, thereby efficiently solve the technical problem that causes electronic injection difficulty as the negative electrode of light-emitting area because work content is high, improved the high luminance of this top radiation organic EL device.Meanwhile, effectively reduce the starting resistor of embodiment of the present invention top radiation organic EL device.Metal oxide layer 5 is set between PN junction layer 4 and cathode layer 6 can effectively play a protective role to PN junction layer 4, has ensured PN junction layer 4 stable performances, has extended the useful life of this top radiation organic EL device.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method of top radiation organic EL 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: at the substrate 1 one plated surface anode layers 2 of step S01;
S03. prepare organic function layer 3: prepare anode layer 2 at step S02 with the light-transmissive substrates layer 1 relative surface each functional layer of organic function layer 3 successively of face that combines, form organic function layer 3;
S04. prepare PN junction 4:
In vacuum coating system, fullerene-based material evaporation is prepared to n type semiconductor layer 41 at organic function layer 3 outer surfaces;
In vacuum coating system, phthalocyanine compound evaporation is prepared to p type semiconductor layer 42 at n type semiconductor layer 41 outer surfaces, this p type semiconductor layer 42 forms PN junction 4 with n type semiconductor layer 41;
S05. prepare cathode layer 6: in vacuum systems, PN junction 4 outer surfaces that transparent conductive oxide magnetron sputtering is prepared at step S04 are prepared cathode layer 6.
Particularly, in above-mentioned S01 step, structure, material and the specification of substrate 1 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, substrate 1 is placed in to vacuum coating system at the surperficial evaporation anode layer 2 of substrate 1, its evaporation condition adopts the process conditions of this area routine.Wherein, the thickness of the anode material that evaporation anode layer 2 is used and the anode layer 2 preparing all as described above, does not repeat them here.While steaming anode layer 2, the evaporation rate of metal is preferably 0.2～2nm/s, and the operating pressure of vacuum moulding machine film forming is 1 × 10
-5～1 × 10
-3pa.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: this substrate 1 that is coated with anode layer 2 is placed in to 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.
In above-mentioned steps S03, when organic function layer 3 as described above, when it comprises hole transmission layer 31, luminescent layer 32, the electron transfer layer 33 that stacks gradually combination, the method for therefore preparing organic function layer 3 is at anode layer 2 outer surfaces successively evaporation hole transmission layer 31, luminescent layer 32, electron transfer layer 33;
When organic function layer 3 as described above, it comprises the hole injection layer that stacks gradually combination, hole transmission layer 31, luminescent layer 32, electron transfer layer 33, or comprise the hole injection layer that stacks gradually combination, hole transmission layer 31, electronic barrier layer, luminescent layer 32, hole blocking layer, when electron transfer layer 33, the method of preparing organic function layer 3 is at anode layer 2 outer surfaces successively evaporation hole injection layer, hole transmission layer 31, luminescent layer 32, electron transfer layer 33, or evaporation hole injection layer successively, hole transmission layer 31, electronic barrier layer, luminescent layer 32, hole blocking layer, electron transfer layer 33, form organic function layer 3.
Wherein, plate this each layer of selected material and even thickness 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.Certainly, preparing the each layer process condition of organic function layer 3 also can carry out according to existing processing parameter setting.
In above-mentioned steps S04, the preferred thickness of the preferred kind of fullerene-based material and phthalocyanine compound, n type semiconductor layer 41 and p type semiconductor layer 42 all as described above, does not repeat them here.
Preferably, to be preferably the operating pressure of vacuum moulding machine film forming be 1 × 10 for evaporation n type semiconductor layer 41 and the involved process conditions of p type semiconductor layer 42
-5～1 × 10
-3pa, the evaporation rate of fullerene-based material is 0.1～1nm/s, the evaporation rate of phthalocyanine compound is 0.01～1nm/s.
In above-mentioned steps S05, transparent conductive oxide and cathode layer 6 thickness all as described above, do not repeat them here.Preferably, to become the sputtering technology condition of cathode layer 6 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 cathode layer 6 also can be carried out according to existing processing parameter setting.
Further, when as shown in Figure 2 also stacked while being combined with metal oxide layer 5 of embodiment of the present invention top radiation organic EL device, between step S04 and S05, also comprise the step of preparing metal oxide layer 5:
In vacuum coating system, metal oxide evaporation is prepared to metal oxide layer 5 at PN junction 4 outer surfaces; Wherein, as described above, be preferably metal oxide layer material is MoO to this metal oxide
3, ReO
3, WO
3, V
2o
5, Sb
2o
3in at least one.
Particularly, the operating pressure of the vacuum moulding machine film forming of evaporation metal oxide skin(coating) 5 is 1 × 10
-5～1 × 10
-3pa, evaporation rate is 0.1～1nm/s, certainly, prepares the process conditions of metal oxide layer 5 and also can carry out according to existing processing parameter setting.
From the above, the preparation method of above-mentioned top radiation organic EL device prepares respectively organic function layer 3, PN junction 4 and cathode layer 6 or metal oxide layer 5 and cathode layer 6 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 improve production efficiency, reduce production cost, be applicable to industrialization and produce.
Now, in conjunction with instantiation, embodiment of the present invention top radiation organic EL part and preparation method thereof is further elaborated.
Embodiment 1
A kind of top radiation organic EL device, its structure is: glass substrate/Ag (100nm)/NPB (30nm)/(Ir (ppy)
3: CBP (10%, 10nm)/Bphen (30nm)/C60 (1nm)/Zn Pc (5nm)/WO
3(1nm)/ITO (100nm).
This Organnic electroluminescent device is preparation method comprise the following steps:
1) glass substrate pre-treatment: washed with de-ionized water → isopropyl alcohol cleaning → acetone cleans, and all cleans with supersonic wave cleaning machine, and the time is 20 minutes, then dries up with nitrogen;
2) preparation of anode layer: in vacuum coating system, prepare metal A g layer as anode layer at substrate evaporation, its thickness is 100nm, and the vacuum degree of vacuum coating system is 5 × 10
-4pa;
3) preparation of organic function layer: in vacuum coating system, in step 2) the anode layer surface evaporation hole transmission layer successively prepared, luminescent layer, electron transfer layer; The vacuum degree of vacuum coating system is 5 × 10
-4pa;
4) preparation of PN junction: be 5 × 10 in vacuum degree
-4in the vacuum coating system of Pa, by thermal evaporation techniques, successively at organic function layer appearance evaporation n type semiconductor layer and p type semiconductor layer; Wherein, the material of evaporation n type semiconductor layer is C60, and evaporation rate is 0.2nm/s; The material of evaporation p type semiconductor layer is ZnPc, and evaporation rate is 0.2nm/s;
5) preparation of metal oxide layer: be 5 × 10 in vacuum degree
-4in the vacuum coating system of Pa, by thermal evaporation techniques, at PN junction appearance evaporation WO
3form metal oxide layer 5; WO
3evaporation rate be 0.5nm/s;
6) preparation of cathode layer: in vacuum systems, transparent conductive oxide ITO magnetron sputtering is formed to cathode layer 6 at metal oxide layer outer surface.
Embodiment 2
A kind of top radiation organic EL device, its structure is: glass substrate/Cu (70nm)/2-TNATA (60nm)/Ir (piq)
3: NPB (8%, 20nm)/TPBi (60nm)/C70 (5nm)/Cu Pc (2nm)/MoO
3(5nm)/AZO (70nm).
Its preparation method is with embodiment 1.
Embodiment 3
A kind of top radiation organic EL device, its structure is: glass substrate/Au (200nm)/m-MTDATA (20nm)/DCJTB:Alq
3(1%, 1nm)/PBD (20nm)/C60:C70 (40:60,15nm)/VOPc (10nm)/ReO
3(2nm)/GZO (200nm).
Its preparation method is with embodiment 1, and wherein N-type layer material is the mixture of C60 and C70, and both respectively account for mass percent 40:60, and thickness is 15nm.
Embodiment 4
A kind of top radiation organic EL device, its structure is: glass substrate/Pt (70nm)/TPD (40nm)/Rubrene (10nm)/BCP (30nm)/C60:C70 (20:80,20nm)/TiOP c (20nm)/V
2o
5(1nm)/IZO (100nm).
Its preparation method is with embodiment 1, and wherein N-type layer material is the mixture of C60 and C70, and both respectively account for mass percent 20:80, and thickness is 20nm.
Embodiment 5
A kind of top radiation organic EL device, its structure is: glass substrate/Ni (100nm)/TCTA (35nm)/DPVBi (10nm)/TAZ (30nm)/C60:C70 (50:50,10nm)/PtP c (15nm)/Sb
2o
3(1nm)/IZO (100nm).
Its preparation method is with embodiment 1, and wherein N-type layer material is the mixture of C60 and C70, and both respectively account for mass percent 50:50, and thickness is 10nm.
Comparison example 1
A kind of top radiation organic EL device, its structure is: glass substrate/Ag (100nm)/NPB (30nm)/(Ir (ppy)
3: CBP (10%, 10nm)/Bphen (30nm)/ITO (100nm).
Its preparation technology, with embodiment 1, does not still adopt pn knot layer between negative electrode and organic luminescence function layer, and all the other are with embodiment 1.
Organnic electroluminescent device carries out correlated performance test
Top radiation organic EL device prepared by above-described embodiment 1 to embodiment 5 and comparison example 1 carries out the performances such as starting resistor and luminous efficiency 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
As can be seen from Table 1, top radiation organic EL device prepared by the embodiment of the present invention, compared with common luminescent device, because the injection barrier of electronics reduces, therefore can improve the injection efficiency of electronics, thereby obtains lower starting resistor and light efficiency.In addition, because embodiment of the present invention top radiation organic EL device is also provided with a metal oxide layer as resilient coating between PN junction and transparent conductive oxide film cathode layer, avoid the destruction of sputtered film to organic layer in PN junction, further improved the light efficiency of top radiation organic EL device.
Above-described embodiment 1 and comparison example 1 are carried out to the test of voltage-to-current density feature, and test result as shown in Figure 4.As can be seen from Figure, under identical driving voltage, because the electronic injection of embodiment 1 is more prone to, and therefore the electronic injection difficulty of comparison example 1 is compared at identical driving voltage, and embodiment 1 has higher Injection Current.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments 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. a top radiation organic EL device, comprise the substrate, anode layer, organic function layer and the cathode layer that stack gradually combination, described organic function layer comprises luminescent layer, it is characterized in that: go back the folded PN junction being combined between described cathode layer and organic function layer of covering, the p type semiconductor layer of described PN junction and the stacked combination of described cathode layer, the n type semiconductor layer of described PN junction and the stacked combination of described organic function layer; Wherein, described P type semiconductor layer material is phthalocyanine compound, and described N type semiconductor layer material is fullerene-based material.
2. top radiation organic EL device as claimed in claim 1, is characterized in that: described phthalocyanine compound is at least one in CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc, phthalocyanine platinum.
3. top radiation organic EL device as claimed in claim 1, is characterized in that: described fullerene-based material is carbon 60 and/or carbon 70.
4. the top radiation organic EL device as described in as arbitrary in claim 1～3, is characterized in that: the thickness of described p type semiconductor layer is 1nm～20nm.
5. the top radiation organic EL device as described in as arbitrary in claim 1～3, is characterized in that: the thickness of described n type semiconductor layer is 1nm～20nm.
6. the top radiation organic EL device as described in as arbitrary in claim 1～3, is characterized in that: also comprise metal oxide layer, described metal oxide layer is stacked to be combined between PN junction and cathode layer; Wherein, described metal oxide layer material is MoO
3, ReO
3, WO
3, V
2o
5, Sb
2o
3in at least one.
7. a preparation method for top radiation organic EL device, comprises the steps:
In vacuum coating system, fullerene-based material evaporation is prepared to n type semiconductor layer at organic function layer outer surface;
In vacuum coating system, phthalocyanine compound evaporation is prepared to p type semiconductor layer at described n type semiconductor layer outer surface, described p type semiconductor layer and described n type semiconductor layer form PN junction;
In vacuum systems, transparent conductive oxide magnetron sputtering is prepared to cathode layer at described PN junction outer surface.
8. top radiation organic EL device as claimed in claim 7 or 8, is characterized in that: described phthalocyanine compound is at least one in CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc, phthalocyanine platinum.
9. top radiation organic EL device as claimed in claim 7 or 8, is characterized in that: described fullerene-based material is carbon 60 and/or carbon 70.
10. top radiation organic EL device as claimed in claim 7 or 8, it is characterized in that: preparing the step of PN junction and preparing between the step of cathode layer, also comprise the step of preparing metal oxide layer: in vacuum coating system, metal oxide evaporation is formed to metal oxide layer at PN junction outer surface; Wherein, described metal oxide is MoO
3, ReO
3, WO
3, V
2o
5, Sb
2o
3in at least one.
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Application publication date: 20141203 |